CN115957592B - Dealkalized refining agent and its preparation method and application in dealkalizing impurities in dry gas - Google Patents
Dealkalized refining agent and its preparation method and application in dealkalizing impurities in dry gas Download PDFInfo
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- CN115957592B CN115957592B CN202111191736.8A CN202111191736A CN115957592B CN 115957592 B CN115957592 B CN 115957592B CN 202111191736 A CN202111191736 A CN 202111191736A CN 115957592 B CN115957592 B CN 115957592B
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- Prior art keywords
- treatment
- dry gas
- filler
- dealkalization
- activator
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Abstract
本发明公开了一种脱碱精制剂及其制备方法和在干气脱碱性杂质中的应用。所述脱碱精制剂由内至外包括填料、硅烷层、改性层和第一活化层，所述改性层所含有的改性基团选自联苯基、二苯醚基或二硫醚基中的至少一种，第一活化层中含有磺酸基和仲胺基。所述脱碱精制剂的制备方法，包括：填料依次经硅烷化处理，用改性剂处理，再用第一活化剂处理，得到脱碱精制剂。本发明脱碱精制剂用于分离干气中显著影响乙苯烷基化催化剂活性的碱性杂质，有效消除碱性杂质对催化剂的累积影响，显著延长烷基化催化剂运行周期，实现低成本、连续化生产乙苯。
The present invention discloses a dealkalizing refining agent, a preparation method thereof, and an application thereof in dealkalizing impurities in dry gas. The dealkalizing refining agent comprises a filler, a silane layer, a modified layer, and a first activation layer from the inside to the outside, the modified group contained in the modified layer is selected from at least one of biphenyl, diphenyl ether, or disulfide, and the first activation layer contains a sulfonic acid group and a secondary amine group. The preparation method of the dealkalizing refining agent comprises: the filler is sequentially subjected to silanization treatment, treated with a modifier, and then treated with a first activating agent to obtain the dealkalizing refining agent. The dealkalizing refining agent of the present invention is used to separate alkaline impurities in dry gas that significantly affect the activity of ethylbenzene alkylation catalyst, effectively eliminate the cumulative effect of alkaline impurities on the catalyst, significantly extend the operation cycle of the alkylation catalyst, and realize low-cost and continuous production of ethylbenzene.
Description
Technical Field
The invention relates to the technical field of ethylbenzene production from dry gas, in particular to a dealkalization refining agent and a preparation method thereof, and application thereof in deep removal of impurities (especially alkaline impurities) in dry gas.
Background
Dry gas refers to tail gas which cannot be liquefied any more in a refinery and mainly comes from a secondary processing process of crude oil. The dry gas of oil refining enterprises mainly comes from catalytic cracking gas and is generally used as fuel. In order to fully utilize the part of dilute ethylene resources in the dry gas, improve the utilization rate of petroleum resources, solve the current shortage situation of ethylbenzene/styrene market at the same time, and further develop the process for preparing ethylbenzene by the dry gas. The process of preparing ethylbenzene with dry gas is generally to make ethylene, a small amount of propylene, butylene and the like in dry gas and benzene react in alkylation under the action of catalyst at the reaction temperature of 200-500 ℃ to generate ethylbenzene, propylbenzene, butylbenzene, polyalkylbenzene and the like.
The ethylbenzene alkylation catalyst generally adopts an acidic molecular sieve, and the running period of the ethylbenzene alkylation catalyst is obviously shortened due to the fact that impurities in dry gas are complex, and particularly certain alkaline impurities exist.
Patent CN109574780a discloses a method for absorbing ammonia in dry gas by using modified activated carbon, because the ammonia content in dry gas is unstable and generally fluctuates greatly at 1-500 ppm, the adsorbent is very easy to saturate when the ammonia content is higher, resulting in frequent loading and unloading of the adsorbent.
Patent CN111450662a discloses a combined deamination process of a water scrubber-cyclone-coalescer-adsorption tower, wherein the water scrubber is selected from industrial water or acidic aqueous solution, and the adsorbent is formed activated carbon, silica, alumina, formed molecular sieve, strong acid cation exchange resin and the like loaded by inorganic acid or organic acid. In the process, because the operation elasticity of the water washing rectifying tower is limited, when the ammonia content in the raw materials greatly fluctuates, the ammonia in the dry gas is difficult to effectively remove, and even if the adsorption tower is arranged at the back, the adsorbent in the adsorption tower is saturated rapidly due to the too high ammonia content in the dry gas.
The research of absorbing ammonia in phosphate fertilizer tail gas by using a rotary packed bed (chemical intermediate, 7 th 2009) discloses a process for absorbing ammonia in phosphate fertilizer tail gas by using phosphoric acid wastewater. Compared with the traditional tower equipment, the process has the advantages that the absorption efficiency is improved to a certain extent, but the deep deamination effect is general.
In conclusion, the field of removing alkaline impurities in the prior art mainly has the defects of small operation elasticity and low removal depth, so that the alkylation catalyst is continuously and slowly deactivated or rapidly deactivated. Therefore, the continuous deep and stable removal of alkaline impurities in dry gas is one of the important problems to be solved in the ethylbenzene device under the crude oil degradation background.
Disclosure of Invention
The invention aims to solve the technical problems of high content of alkaline impurities and high difficulty in continuous deep removal of alkaline impurities in dry gas in the prior art, and provides a dealkalization refined preparation, a preparation method thereof and application thereof in dealkalization of alkaline impurities in dry gas. The dealkalization refining agent is used for separating alkaline impurities in dry gas, which obviously influence the activity of an ethylbenzene alkylation catalyst, effectively eliminates the accumulated influence of the alkaline impurities on the catalyst, obviously prolongs the operation period of the alkylation catalyst, and realizes low-cost and continuous production of ethylbenzene.
The invention provides a dealkalization refining agent, which comprises a filler, a silane layer, a modified layer and a first activation layer from inside to outside, wherein the modified group contained in the modified layer is at least one selected from biphenyl, diphenyl ether or disulfide, and the first activation layer contains sulfonic acid groups and secondary amine groups.
In the technical scheme, in the silane layer, the molar ratio of the silicon ether group to the silicon carbon group is 0.8-1.2, and the thickness of the silane layer is 50-300 microns.
In the technical scheme, the content of the modifying groups in the modifying layer is 0.13-0.27 mol/m 2, and the thickness of the modifying layer is 40-80 microns.
In the above technical scheme, in the first activation layer, the content of sulfonic acid groups is 0.4-0.8 mol/m 2, and the content of secondary amine groups is 0.16-0.56 mol/m 2.
In the above technical scheme, preferably, the dealkalization refining agent further comprises a second activation layer on the outer surface of the first activation layer, and further preferably, in the second activation layer, the content of sulfonic acid groups is 10-50 mmol/m 2, the content of secondary amino groups is 16-90 mmol/m 2, and the content of methoxy groups is 40-270 mmol/m 2.
In the above technical scheme, the filler may be at least one of grid structured filler and corrugated structured filler, and the corrugated structured filler may be at least one of plate corrugated structured filler and net corrugated structured filler. The specific surface area of the filler is preferably 1000-2600 mm 2/m3. The porosity of the filler is preferably 74% -85%. The material of the filler can be metal, plastic or ceramic, wherein the metal material is preferably 304, 304L, 316 or 316L. The packing is preferably a corrugated wire mesh structured packing.
In the above technical solution, the silylation agent used for the silane layer is at least one selected from the group consisting of phenylmethyltriethoxysilane, phenylmethyltrimethoxysilane, and the like.
In the above technical solution, the modifying agent used for the modifying layer includes a first modifying component, a catalyst and a solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The first modifying component is selected from at least one of 2,2', 5-trichlorobiphenyl, 2, 4' -trichloro-2-hydroxydiphenyl ether and 3,3', 5' -tetrachlorodiphenyl disulfide, and preferably the first modifying component is 2, 4' -trichloro-2-hydroxydiphenyl ether.
In the above technical solution, the first activator used for the first activation layer includes aromatic hydrocarbon containing sulfonic acid group, catalyst and solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The aromatic hydrocarbon containing sulfonic acid group is preferably one or more of 3-sulfoaniline, 4-amino-1, 3-benzene disulfonic acid and 4-aniline sulfonic acid, and more preferably 4-amino-1, 3-benzene disulfonic acid. Preferably, the first activator comprises 4-amino-1, 3-benzenedisulfonic acid, zinc chloride and toluene.
In the above technical scheme, the second activator used for the second activation layer comprises sulfonic acid group-containing aliphatic hydrocarbon, 3, 5-dichloro-2-methoxyaniline, a catalyst and a solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The sulfonic acid group-containing aliphatic hydrocarbon is preferably N- (carbamoylmethyl) -2-aminoethanesulfonic acid. Preferably, the second activator comprises N- (carbamoylmethyl) -2-aminoethanesulfonic acid, 3, 5-dichloro-2-methoxyaniline, zinc chloride and toluene.
In the technical scheme, the contents of the modified groups in the modified layer, the sulfonic acid groups and the secondary amine groups in the first activated layer and the sulfonic acid groups, the secondary amine groups and the methoxy groups in the second activated layer are all based on the external surface area of the filler per square meter.
The second aspect of the present invention provides a method for preparing the dealkalization refinement agent, comprising:
(1) The filler is subjected to silanization treatment to obtain silanized filler;
(2) Treating the silanized filler obtained in step (1) with a modifier;
(3) Treating the filler obtained in the step (2) with a first activator to obtain a dealkalized refined preparation.
In the above technical solution, the packing in the step (1) may be at least one of a grid structured packing and a corrugated structured packing, and the corrugated structured packing may be at least one of a plate corrugated structured packing, a net corrugated structured packing, etc., such as at least one of a corrugated plate structured packing, a calendared orifice plate corrugated structured packing, a mesh grid structured packing, or a corrugated wire mesh structured packing. The specific surface area of the filler is preferably 1000-2600 mm 2/m3. The porosity of the filler is preferably 74% -85%. The material of the filler can be metal, plastic or ceramic, wherein the metal material is preferably 304, 304L, 316 or 316L. The packing is preferably a corrugated wire mesh structured packing.
In the above technical scheme, the silylation reagent used in the silylation in the step (1) is at least one selected from aniline methyltriethoxysilane, aniline methyltrimethoxysilane and the like.
In the above technical scheme, the silanized filler in the step (1) is a filler coated with a silane layer having a thickness of 50-300 micrometers.
In the above technical solution, the silylation treatment in step (1) may be performed by conventional electrodeposition methods in the art. For example, the filler may be first ultrasonically polished by using a suspension polishing liquid (e.g., silicon carbide), the polishing ultrasonic frequency is preferably 20-40 khz, then sequentially ultrasonically cleaned by using desalted water (the cleaning ultrasonic frequency is 30-70 khz, the temperature is 60-80 ℃ and the cleaning time is 30-40 minutes), ultrasonically cleaned by using acetone (the cleaning ultrasonic frequency is 40-80 khz, the temperature is 20-40 ℃ and the cleaning time is 20-30 minutes), ultrasonically cleaned by using alkali liquor (wherein the alkali liquor comprises, by mass, sodium hydroxide is 5% -7%, sodium phosphate is 0.5% -1%, the ultrasonic frequency is 50-90 khz, the alkali cleaning temperature is 60-90 ℃ and the alkali cleaning time is 20-30 minutes), and then rinsed by desalted water (e.g., 4-6 times) and blown dry by nitrogen (the temperature can be 20-40 ℃) in a silylation reagent solution), and then, and finally, the silane layer with the thickness of 50-300 micrometers is obtained by drying and solidifying. The silylation reagent solution comprises, by volume, desalted water, absolute ethyl alcohol= (4-6), 14-16, 78-92 and pH value of 8.5-9.5, wherein the preparation method of the silylation reagent solution comprises the steps of mixing the silylation reagent, the desalted water and the absolute ethyl alcohol according to a proportion for prehydrolysis, and the prehydrolysis time is 10-12 hours. In general, the silylation treatment is preferably carried out under the conditions of an electrodeposition voltage of 5V to 10V, an electrodeposition time of 30 to 50 minutes, a drying and curing temperature of 100 to 120 ℃, and a drying atmosphere of nitrogen.
In the above technical solution, the modifying agent in step (2) includes a first modifying component, a catalyst and a solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The first modifying component is selected from at least one of 2,2', 5-trichlorobiphenyl, 2, 4' -trichloro-2-hydroxydiphenyl ether and 3,3', 5' -tetrachlorodiphenyl disulfide, and preferably the first modifying component is 2, 4' -trichloro-2-hydroxydiphenyl ether. The catalyst comprises, by mass, a first modified component, a solvent= (10-20): (20-30): (200-300).
In the technical scheme, the modifier treatment in the step (2) can be soaking, and the modification treatment is carried out under the treatment conditions that the volume ratio (liquid-solid volume ratio) of the modifier to the silanized filler obtained in the step (1) is 1-4, the treatment temperature is 30-50 ℃, and the treatment time is 2-4 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate.
In the above technical scheme, in the step (2), it is preferable that the pre-activated modified silylated filler intermediate is obtained by performing a modification post-treatment after treating the silylated filler obtained in the step (1) with a modifier. The preactivator used for the modified post-treatment can be one or more of absolute methanol, absolute ethanol and absolute acetone, and the preferred preactivator is absolute ethanol. The modification post-treatment can be soaking, and the modification post-treatment conditions are that the volume ratio (liquid-solid volume ratio) of the preactivator to the modified silanized filler intermediate is 1-4, the temperature is 60-80 ℃, the treatment time is 0.5-1.0 hour each time, the treatment times are 2-3 times, and the modified silanized filler intermediate is dried for 0.5-1.0 hour in an inert atmosphere (such as nitrogen) at 110-130 ℃.
In the above technical scheme, in the step (3), the filler obtained in the step (2) (i.e. the silylated filler intermediate or the preactivated modified silylated filler intermediate) is treated with the first activator to obtain the dealkalized refined preparation. Wherein the content of sulfonic acid groups in the dealkalization refined agent which is treated by the first activator is 0.4-0.8 mol/m 2, and the content of secondary amino groups is 0.16-0.56 mol/m 2.
In the above technical solution, in step (3), the first activator used includes aromatic hydrocarbon containing sulfonic acid group, catalyst and solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The aromatic hydrocarbon containing sulfonic acid group is preferably one or more of 3-sulfoaniline, 4-amino-1, 3-benzene disulfonic acid and 4-aniline sulfonic acid, and more preferably 4-amino-1, 3-benzene disulfonic acid. Preferably, the first activator comprises 4-amino-1, 3-benzenedisulfonic acid, zinc chloride and toluene. According to the mass portion, the aromatic hydrocarbon containing the sulfonic group is catalyst, solvent= (20-30): (10-20): (200-300).
In the technical scheme, in the step (3), the treatment with the first activator can be soaking, and the treatment condition of the treatment with the first activator is that the volume ratio (liquid-solid volume ratio) of the first activator to the filler (the modified silanized filler intermediate or the preactivated modified silanized filler intermediate) obtained in the step (2) is 1-4, the treatment temperature of the activator is 40-60 ℃, and the treatment time is 3-6 hours.
In the above technical scheme, in step (3), preferably, the filler treated with the first activator is treated with the second activator to obtain the dealkalized refined agent. Specifically, after the treatment by the first activator, solid-liquid separation is carried out, and the obtained solid is contacted with the second activator to carry out the second activation treatment. Wherein the content of sulfonic acid groups in the dealkalized refined preparation after being treated by the second activator is 10-50 mmol/m 2, the content of secondary amino groups is 16-90 mmol/m 2, and the content of methoxy groups is 40-270 mmol/m 2.
In the above technical scheme, in step (3), preferably, the second activator used includes sulfonic acid group-containing aliphatic hydrocarbon, 3, 5-dichloro-2-methoxyaniline, catalyst and solvent. The catalyst is selected from one of Lewis acid or Lewis base, preferably at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride. The solvent is selected from at least one of toluene, paraxylene, metaxylene and orthoxylene. The sulfonic acid group-containing aliphatic hydrocarbon is preferably N- (carbamoylmethyl) -2-aminoethanesulfonic acid. Preferably, the second activator comprises N- (carbamoylmethyl) -2-aminoethanesulfonic acid, 3, 5-dichloro-2-methoxyaniline, zinc chloride and toluene. According to the mass portion, the catalyst comprises (by weight) 3, 5-dichloro-2-methoxyaniline serving as an aliphatic hydrocarbon containing sulfonic groups, (by weight) solvent= (10-20): (30-50): (15-30): (200-300).
In the technical scheme, in the step (3), the treatment with the second activator can be soaking, and the treatment condition of the second activator is that the volume ratio (liquid-solid volume ratio) of the second activator to the filler after the treatment with the first activator is 1-1.8, the treatment temperature is 30-45 ℃, and the treatment time is 20-50 minutes.
In the above technical solution, in step (3), preferably, the dealkalized refined preparation is obtained by using the filler obtained by the first activation treatment and/or the filler obtained by the second activation treatment and then performing the activation post-treatment. The agent used for the activation post-treatment is at least one of absolute ethyl alcohol and benzene, and preferably absolute ethyl alcohol. The activation post-treatment can be soaking, wherein the activation post-treatment conditions are that the volume ratio of an activation post-treatment agent to an activation modified silanized filler intermediate (namely, the liquid-solid volume ratio) is 1-4, the temperature is 65-100 ℃, the pressure (gauge pressure) is 200-400 kPa, the treatment time is 1.0-2.0 hours each time, the treatment times are 2-3 times, and the activated post-treatment is carried out in an inert atmosphere (such as nitrogen) for 0.5-1.0 hour at 100-120 ℃.
The third aspect of the invention provides an application of the dealkalization refined preparation provided in the first aspect or the dealkalization refined preparation prepared by the method in the second aspect in dealkalization impurities of dry gas.
In the technical scheme, the method comprises the steps of contacting raw material dry gas with a dealkalization refining agent to obtain purified dry gas with dealkalization impurities.
In the above technical scheme, preferably, in the application, a dealkalization refiner is adopted, wherein a dealkalization refiner bed layer is arranged, a static regenerant central shaft distributor is arranged at the axial central position of the dealkalization refiner, a gas collecting pipe is arranged at the outer side of the regenerant central shaft distributor, a raw material dry gas feeding hole is arranged on the side wall of the dealkalization refiner, a regenerant feeding hole is arranged at the upper part and communicated with the regenerant central shaft distributor, a regenerant discharging hole is arranged at the lower part, a purified dry gas discharging hole is arranged at the top part, and the dry gas discharging hole is communicated with the gas collecting pipe.
In the above technical solution, preferably, in the application, when the dealkalization refiner is started, the dry gas of the raw material flows from the wall side to the axis through the dealkalization refiner, and simultaneously the regenerant flows to the dealkalization refiner under the action of power through the regenerant central axis distributor, and adsorption and regeneration are realized, so as to obtain the purified dry gas and the regenerant solution after working, and the specific process is as follows: the method comprises the steps that raw dry gas enters a dealkalization refiner through a raw dry gas feed port, the axle center of the dealkalization refiner flows from the near wall side direction of the periphery of the dealkalization refiner bed, alkaline impurities in the dry gas are selectively adsorbed by the dealkalization refiner, meanwhile, a regenerant enters the dealkalization refiner from a regenerant feed port and flows to the dealkalization refiner through a regenerant central axis distributor under the action of power on one hand, part of regenerant regenerates the dealkalization refiner adsorbing alkaline impurities, on the other hand, part of regenerant directly reacts with alkaline impurities in the dry gas, the reacted regenerant is discharged from a regenerant discharge port, and the obtained purified dry gas is collected by a gas collecting tube and is discharged from the top of the dealkalization refiner.
In the above technical scheme, in the application, the dealkalization refining agent is filled in the dealkalization refiner to form a dealkalization refining agent bed layer, the liquid is accelerated to turbulent motion under the action of power, and the dealkalization refining agent is an adsorption refining bed layer integrating adsorption and regeneration, and the on-line in-situ real-time continuous adsorption and regeneration, namely in-situ regeneration while adsorption in the dealkalization refiner, is adopted, and the regeneration of the adsorption center is realized by contacting mass transfer with the adsorption center by the high-speed turbulent motion regenerant.
In the above technical solution, in the application, the power is a gas driving force and a liquid throwing inertial force, preferably a liquid throwing inertial force. The liquid throwing inertia force is derived from liquid high-pressure injection, and/or the motor drives the dealkalization refining agent bed layer to axially or radially circularly move.
In the technical scheme, the dealkalization refining conditions are preferably that the temperature is 20-50 ℃, the pressure is 500-1200 kPa, the dry gas feeding volume airspeed is 300-1500 h -1, and the feeding quantity ratio of the dry gas to the regenerant solution is 400-600 by volume.
In the above technical scheme, in the application, the regenerant is at least one selected from citric acid, tartaric acid, acetic acid-based succinic acid, methanesulfonic acid, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and acetic acid, preferably, the regenerant solution comprises, by mass, 10% -30% of tartaric acid, 2% -4% of acetic acid-based succinic acid, 1% -3% of methanesulfonic acid and the balance desalted water.
In the above technical scheme, in the application, the dealkalized and refined material is preferably subjected to demisting treatment for removing trace mist carried in the dealkalized and refined dry gas. The demisting treatment can be performed by adopting a conventional wire mesh demister in the field, the separation precision is 3-5 micrometers, and the thickness is 80-200 millimeters.
In the technical scheme, the raw material dry gas is derived from catalytic cracking, thermal cracking, delayed coking and hydrocracking of a refinery. The dry gas of the raw material comprises, but is not limited to, ethylene, methane, ethane, propane, propylene, isobutane, n-butane, fumaric acid, n-butene, isobutene, cis-butene, oxygen, nitrogen, hydrogen, carbon monoxide, carbon dioxide, acetylene, 1, 3-butadiene, alkane or alkene with more than five carbon atoms and alkaline impurities, wherein the alkaline impurities comprise at least one of chain or cyclic nitrogen-containing impurities, and are derived from the nitrogen-containing impurities and degradation components thereof, an amino desulfurizing agent and degradation components thereof in the crude oil. In the raw material dry gas, the volume content of ethylene is 5% -40%, preferably 10% -20%. The raw material dry gas has a volume content of not less than 5ppm, preferably not less than 50ppm, more preferably not less than 500ppm, based on total nitrogen elements, not more than 2000ppm, preferably not more than 1000ppm, based on total nitrogen elements.
In the above technical scheme, the alkaline impurities include, but are not limited to, at least one of ammonia, aminomethane, N-methyl methylamine, cyclopropanemethylamine, N-dimethyl methylamine, monoethanolamine, diethanolamine, aminocyclobutane, diisopropanolamine, N-methyldiethanolamine and the like.
In the above technical scheme, the raw material dry gas also includes sulfide (such as hydrogen sulfide, etc.). According to the requirements on the content of sulfide in the product dry gas, the raw material dry gas can be contacted with a desulfurizing agent to remove sulfide before the raw material dry gas is contacted with a dealkalized refining agent, so that the desulfurization purified dry gas is obtained. The desulfurizing agent is a conventional desulfurizing agent in the field, preferably an alcohol amine, such as at least one of diethanolamine and N-methyldiethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 15-45 ℃, the pressure is 500-1200 kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 5-10. The dosage ratio of the raw material dry gas to the desulfurizing agent is 50-100% by volume, and the mass concentration of the desulfurizing agent solution is 20-40%.
According to the technical scheme, according to the requirement on the propylene content in the product dry gas, the purified dry gas with the alkaline impurities removed can be contacted with a propylene removing agent to obtain the purified dry gas with propylene removed. Wherein the propylene removing agent is a conventional propylene removing agent in the field, and is preferably at least one of benzene and diethylbenzene. The condition of the contact of the dry gas and the propylene removing agent is that the temperature is 10-25 ℃, the pressure is 700-1500 kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 8-15. The dosage ratio of the dry gas to the propylene removing agent is 60-90 by volume.
In the above-described technical scheme, the total nitrogen volume content in the obtained purified dry gas is preferably not higher than 5ppm, more preferably not higher than 3ppm, and still more preferably not higher than 1ppm.
In the above technical scheme, preferably, the obtained purified dry gas can meet the requirement of long-period operation of the ethylbenzene alkylation catalyst.
In a fourth aspect, the present invention provides a separation system for removing impurities from dry gas, comprising:
1) The desulfurization contact tower is used for removing hydrogen sulfide in the dry gas raw material;
2) The dealkalization refining system is used for removing alkaline impurities in the desulfurized and purified dry gas;
3) The demister is used for removing trace mist carried in the dealkalized and refined dry gas;
4) The propylene removal contact tower is used for removing propylene in the dry gas after dealkalization and purification.
In the technical scheme, the dealkalization refining feeding buffer tank is arranged and is used for separating free liquid carried in the dry gas after desulfurization and purification.
In the technical scheme, the dealkalization refining system comprises a dealkalization refiner, wherein a dealkalization refining agent bed layer is arranged for removing alkaline impurities in dry gas.
In the above technical scheme, preferably, the dealkalization refiner is provided with a dealkalization refiner bed layer, a regenerant central shaft distributor is arranged in the axial center, a raw material dry gas feeding port is arranged on the side wall of the dealkalization refiner, a regenerant feeding port is arranged on the upper part and communicated with the regenerant central shaft distributor, a regenerant discharging port is arranged on the lower part, and a purified dry gas discharging port is arranged on the top.
In the above technical scheme, preferably, a demister or cyclone separator is arranged at the downstream of the dealkalization refiner in the dealkalization refining system for removing trace mist carried in the dry gas after dealkalization refining.
In the above technical solution, preferably, a regenerant storage tank is provided for buffering the regenerant, and the regenerant is led into and out of the dealkalized refiner through a liquid conveying device.
In the above technical solution, preferably, the regenerant storage tank is provided with a fresh regenerant or a regenerant lean solution inlet and a regenerant rich solution outlet for replacing the regenerant when the regenerant utilization rate reaches a process value (for example, not less than 95%).
In the technical scheme, the high-pressure pump is arranged for pressurized conveying of the regenerant.
Compared with the prior art, the invention has the following advantages:
1. The inventor of the present invention has found that alkaline impurities which have a significant influence on ethylbenzene alkylation catalysts exist in dry gas raw materials, and the impurities can be accumulated in the catalysts continuously, so that the activity of the ethylbenzene catalysts is reduced, and the operation period is shortened. Due to the fluctuation of the crude oil raw material and the fluctuation of the desulfurization process, the alkaline impurities in the dry gas raw material continuously and greatly fluctuate. If fixed bed adsorption is performed only by conventional adsorbents such as ion exchange resins, activated carbon, etc., the adsorbents are easily saturated, conventional regeneration operations are frequent, and the amount of wastewater discharge is large. The inventor finds through further research that through the modified filler, the alkaline impurities in the raw material dry gas are deeply adsorbed by utilizing the high active groups on the filler, and meanwhile, the preferable low-corrosivity regenerant with a desorption function is adopted to continuously replace and adsorb the micro-interface by utilizing the power such as the throwing inertia force of liquid, so that the problem that the dealkalization refined agent is difficult to regenerate in situ is solved, and the good effect of simultaneously carrying out continuous adsorption and regeneration is realized. Meanwhile, because the active center of the dealkalization refining agent is regenerated by adopting the high-frequency pulse of the regenerant, even if the content of alkaline impurities in the dry gas raw material greatly fluctuates, a sufficient number of fresh active centers are used for continuous adsorption, and the problem of low elasticity of the conventional rectification deamination operation is solved.
2. In the modification process of the filler, the silane layer is formed on the surface of the filler, and then the filler is modified by the modifier, so that the strong supporting and dispersing functions of the filler can be fully exerted, the filler is protected from corrosion, the service life is prolonged, and then the activator is used for modification, wherein the first activator can be used for modifying the surface of the silane layer to form a modified layer with an adsorption active center with proper adsorption strength, and the modified layer has good adsorption and regeneration effects in continuous adsorption and regeneration operation. Preferably, the second active agent is adopted to modify the filler, so that the air film resistance when the dry gas is contacted with the modified layer formed by the first active agent treatment can be reduced, the mass transfer rate is improved, the modified layer formed by the second active agent treatment has a certain absorption effect on each component in the dry gas, a dry gas concentration zone with a certain thickness is formed, the concentration zone and the dry gas main body zone are in dynamic balance, and the alkaline impurity components are continuously exchanged to the modified layer formed by the first active agent treatment, so that the deep removal of alkaline impurities in the dry gas is realized. Meanwhile, the regenerant disclosed by the invention is preferably good in permeability, and particularly alkaline impurities adsorbed in a modified layer formed by treating an active agent can be effectively desorbed so as to recover the active center of the dealkalized refined agent, so that good balance between continuous adsorption and regeneration is realized.
3. The method solves the problems of high content of trace alkaline impurities affecting the ethylbenzene alkylation catalyst and short operation period of the alkylation catalyst in the existing dry gas raw material, greatly improves the operation period of the alkylation catalyst by deeply and continuously adsorbing the alkaline impurities in the dry gas raw material, and reduces the ethylbenzene production cost.
Drawings
FIG. 1 is a schematic diagram of a separation system for removing impurities from dry gas according to the present invention;
wherein reference numerals are as follows:
0101 is a desulfurization contact tower, 0102 is a propylene removal contact tower, 1101 is a dealkalization refining feed buffer tank, 1102 is a dealkalization refiner, 1103 is a demister, 1104 is a motor, 1105 is a regenerant storage tank, 1106 is a regenerant high-pressure pump, 0201 is a desulfurizing agent lean solution inlet, 0202 is a raw material dry gas inlet, 0203 is a desulfurizing agent rich solution outlet, 0204 is a propylene removal agent inlet, 0205 is a propylene removal purification dry gas outlet, 0206 is a propylene removal agent rich solution outlet, 1201 is a dealkalization refining feed buffer tank condensate outlet, 1202 is a fresh regenerant or regenerant lean solution inlet, 1203 is a regenerant rich solution outlet;
FIG. 2 is a schematic diagram of the dealkalization refiner of the present invention;
wherein reference numerals are as follows:
1131 is a dealkalized refined agent bed, 1132 is a regenerant central axis distributor, 1133 is a gas collecting pipe, 1134 is a raw material dry gas feeding port, 1135 is a purified dry gas discharging port, 1136 is a regenerant feeding port, and 1137 is a regenerant discharging port;
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present invention, the specific surface area of the filler means the surface area per unit volume of the filler.
In the present invention, the analysis of the lower hydrocarbon component was carried out by using a gas chromatography Agilent 7890A GC (Agilent, usa) equipped with an HP-PLOT Al 2O3 KCl (50 m×0.53mm×15 μm) capillary chromatography column, the column temperature was maintained at 100 ℃ for 10 minutes, and then raised to 120 ℃ for 3 minutes at 30 ℃ minutes. Carrier gas He flow rate 3 mL/min, sample injection amount 0.1mL (quantitative loop), split ratio 5:1, sample inlet temperature 250 ℃, detector (FID) temperature 250 ℃. According to the invention, the nitrogen element content in the dry gas material is tested by adopting a Mitsubishi sulfur nitrogen analyzer NSX-2100V analyzer, wherein the analysis method is that the argon flow is 200 mL/min, the oxygen flow is 400 mL/min, and the combustion temperature is 1000-1050 ℃.
The invention discloses a separation system for removing impurities in dry gas (shown in figure 1), which comprises 0101, 0102, 1101, 1102, 1103, 1104, 1105 and 1106, wherein the 0101 is a desulfurization contact tower, the 0102 is a propylene removal contact tower, the 1101 is a dealkalization refining feeding buffer tank, the 1102 is a dealkalization refiner, 1103 is a demister, 1104 is a motor, 1105 is a regenerant storage tank, and 1106 is a regenerant high-pressure pump. The separation process is that dry gas raw materials (such as raw materials from catalytic cracking, thermal cracking, delayed coking and hydrocracking of a refinery) enter the desulfurization contact tower 0101 from a middle-lower raw material dry gas inlet 0202 of the desulfurization contact tower 0101, are in countercurrent contact with an amine desulfurizing agent entering from a desulfurizing agent lean solution inlet 0201 to remove hydrogen sulfide in the dry gas, the desulfurizing agent rich solution is led out to a desulfurizing agent regeneration unit from a desulfurizing agent rich solution outlet 0203 at the bottom of the desulfurization contact tower 0101, the dry gas coming out from the top of the desulfurization contact tower 0101 then enters a dealkalization feeding buffer 1101 to remove free liquid entrained in the dry gas, the condensate in the dealkalization feeding buffer 1101 is discharged to the desulfurizing agent regeneration unit from a condensate outlet 1201 of the dealkalization feeding buffer 1101, the top gas phase of the dealkalization feeding buffer 1101 then enters a Zhou Xiangke side of a dealkalization refiner 1102 provided with a bed layer, alkaline impurities in the dry gas are selectively adsorbed by an active base on the dealkalization refiner through the dealkalization refiner layer 1103 flowing towards the axis, and simultaneously, the regenerating agent in the dry gas is conveyed to a regenerator 1105 through a high-pressure regenerator 1106 in the high-pressure booster, or the dynamic pressure of the dynamic pressure is directly discharged from the dry gas storage tank, the dry gas is discharged into a dealkalization refiner liquid through a dynamic pressure booster, the dynamic pressure regulator is discharged from the dry gas storage device, the dry gas is discharged into a dynamic pressure regulator is discharged from the dry gas storage device, and the dry gas is discharged into a contact device is contacted with the dry gas is discharged through a high pressure absorbent, and the dynamic pressure absorber is discharged through a contact device, and is subjected to the dry gas is discharged into a high pressure absorbent, and is discharged through a contact device, and is easy to be a contact with a high pressure separator, and is easy to be discharged. The regenerant in the regenerant storage tank 1105 is continuously circulated through the regenerant high-pressure pump 1106, when the utilization rate of the regenerant reaches a process value (more than or equal to 95%), the liquid level in the regenerant storage tank 1105 is discharged to 1% -5% through the regenerant rich liquid outlet 1203, and then fresh regenerant or the regenerant lean liquid regenerated through the regenerant regeneration unit is added through the fresh regenerant or the regenerant lean liquid inlet 1202.
The structural schematic diagram of the dealkalization refiner of the invention is shown in figure 2. The dealkalization refiner 1102 is internally provided with a dealkalization refined agent bed 1131, the axial center position of the dealkalization refiner 1102 is provided with a static regenerant central shaft distributor 1132, the outer side of the regenerant central shaft distributor 1132 is provided with a gas collecting pipe 1133, the side wall of the dealkalization refiner 1102 is provided with a raw material dry gas feeding hole 1134, the upper part is provided with a regenerant feeding hole 1136 and is communicated with the regenerant central shaft distributor 1132, the lower part is provided with a regenerant discharging hole 1137, the top is provided with a purified dry gas discharging hole 1135, and the purified dry gas discharging hole 1135 is communicated with the gas collecting pipe 1133. The lower end of the gas collecting tube 1133 is connected with the motor 1104 through a shaft, and a sealing ring is arranged at the joint of the upper section of the gas collecting tube 1033 and the flange. When the dealkalization refiner is started, raw dry gas enters the dealkalization refiner 1102 through a raw dry gas feed port 1134, flows from the near wall sides around the dealkalization refiner bed 1131 to the axle center of the dealkalization refiner bed 1131, alkaline impurities in the dry gas are selectively adsorbed by the dealkalization refiner, meanwhile, a regenerant enters the dealkalization refiner 1102 from a regenerant feed port 1136 and flows to the dealkalization refiner 1102 through a regenerant central shaft distributor 1132 under the action of power on one hand, part of the regenerant regenerates the dealkalization refiner absorbing alkaline impurities, on the other hand, part of the regenerant directly reacts with the alkaline impurities in the dry gas, the reacted regenerant is discharged from a regenerant discharge port 1137, and the obtained purified dry gas is collected by a gas collecting tube and then discharged from a purified dry gas discharge port 1135 at the top of the dealkalization refiner.
[ Example 1]
The dry gas raw material in the embodiment is derived from a catalytic cracking device of a refinery, and the dry gas composition comprises the following components in percentage by volume:
Methane 17.8783%, ethane 8.1123%, ethylene 15.9995%, propane 0.1859%, propylene 0.8416%, isobutane 0.0811%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutylene 0.0381%, maleic acid 0.0002%, oxygen 0.1370%, nitrogen 13.5433%, hydrogen 29.4547%, carbon monoxide 1.4972%, carbon dioxide 3.3271%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6738%, ammonia 0.0260%, aminomethane 0.0028%, N-methyl methylamine 0.0020%, N, N-dimethyl methylamine 0.0016%, N-methyl diethanolamine 0.0016%, cyclopropanemethylamine 0.0028%, aminocyclobutane 0.0032%, alkanes or olefins 1.1938%, and other components 0.9500%. Wherein the alkaline impurity is present in an amount of 280ppm by volume based on total nitrogen element.
The separation flow of the embodiment is shown in fig. 1, and the schematic diagram of the dealkalization refiner is shown in fig. 2.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 30 ℃, the pressure is 850kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 7. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 75 percent by volume, and the mass concentration of the desulfurizing agent solution is 27 percent.
The preparation method of the dealkalization refined agent comprises the steps of performing silanization treatment on filler to obtain silanized filler, then using a modifier to treat the silanized filler, performing modification post-treatment, sequentially using a first activator and a second activator, and performing activation post-treatment to obtain the dealkalization refined agent.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1700m 2/m3 (model 1700Y, porosity 80%). The metal is 304L material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 1.0 and thickness of 175 microns through drying and solidification. The silanization treatment conditions are that the ultrasonic frequency of silicon carbide polishing is 30kHz, the ultrasonic cleaning condition of desalted water is that the ultrasonic frequency is 50kHz, the cleaning temperature is 75 ℃, the cleaning time is 35 minutes, the ultrasonic cleaning condition of acetone is that the ultrasonic frequency is 60kHz, the cleaning temperature is 30 ℃, the cleaning time is 25 minutes, the alkali liquor composition is that sodium hydroxide is 6%, sodium phosphate is 0.7%, the ultrasonic frequency of alkali cleaning is 70kHz, the alkali cleaning temperature is 75 ℃, the alkali cleaning time is 25 minutes, the alkali-washed filler is washed 5 times with desalted water and dried by nitrogen at 30 ℃, the silanization reagent solution composition is that the silylated water is that absolute ethyl alcohol=5:15:85, the pH value is 9, the pre-hydrolysis time is 11 hours, the electrodeposition voltage is 7V, the electrodeposition time is 40 minutes, the drying and curing temperature is 110 ℃, and the drying atmosphere is nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=15:25:250. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 2.5, the treatment temperature is 40 ℃ and the treatment time is 3 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate. And (3) carrying out modification post-treatment on the modified silanized filler intermediate to obtain the preactivated modified silanized filler intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The post-modification treatment conditions were as follows, the volume ratio of the pre-activator to the intermediate of the modified silanized filler was 2.5, the temperature was 70 ℃, the time per treatment was 0.7 hours, the number of treatments was 2, and the ethanol was dried under nitrogen at 120 ℃ for 0.8 hours.
The preactivated modified silanized filler intermediate is subjected to activation treatment by a first activator and a second activator in sequence. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=25:15:250. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight parts of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline and the zinc chloride are respectively 15:40:22.5:250. The zinc chloride is anhydrous zinc chloride. The first activator was treated under conditions such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate was 2.5, the treatment temperature was 50 ℃ and the treatment time was 4 hours. And after the treatment of the first activator is finished, taking out, draining until free liquid is not present, and putting the second activator into the second activator for the treatment of the second activator. The treatment conditions of the second activator treatment were such that the volume ratio of the second activator to the filler after the first activator treatment was 1.4, the activator treatment temperature was 37 ℃ and the treatment time was 35 minutes. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The conditions for the post-activation treatment were such that the volume ratio of the agent for the post-activation treatment to the intermediate for the activated modified silanized filler was 2.5, the temperature was 80℃and the pressure (gauge pressure) was 300kPa, the treatment time was 1.5 hours each, the number of treatments was 2 times, and the ethanol was dried in nitrogen at 110℃for 0.7 hours.
The prepared dealkalization refining agent has the content of modified groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.19mol/m 2, the thickness of a modified layer of 60 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.6mol/m 2, the content of secondary amino groups of 0.35mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 30mmol/m 2, the content of secondary amino groups of 53mmol/m 2 and the content of methoxy groups of 153mmol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1000h -1, the dealkalization refining agent, the adsorption temperature is 35 ℃, and the adsorption pressure (gauge pressure) is 800kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The dealkalized refining bed regenerant solution comprises 20 mass percent of tartaric acid, 3 mass percent of acetic acid-based succinic acid, 2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas to the regenerant solution is 500 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 4 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The conditions for contacting the dry raw material gas with the propylene removing agent are that the temperature is 17 ℃, the pressure is 1100kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 11. The ratio of the dry gas of the raw material to the propylene removing agent is 75 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 3.5ppm.
[ Example 2]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the raw material dry gas and the desulfurizing agent is that the temperature is 44 ℃, the pressure is 1100kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 9. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 58 percent by volume, and the mass concentration of the desulfurizing agent is 33 percent.
The preparation method of the dealkalization refined agent comprises the steps of performing silanization treatment on filler to obtain silanized filler, then using a modifier to treat the silanized filler, performing modification post-treatment, sequentially using a first activator and a second activator, and performing activation post-treatment to obtain the dealkalization refined agent.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 2500m 2/m3 (model 2500Y, porosity of 75%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 1.1 and thickness of 290 microns through drying and solidification. The silanization treatment conditions are that the ultrasonic frequency of silicon carbide polishing is 25kHz, the ultrasonic cleaning condition of desalted water is that the ultrasonic frequency of cleaning is 35kHz, the cleaning temperature is 78 ℃, the cleaning time is 39 minutes, the ultrasonic cleaning condition of acetone is that the ultrasonic frequency of cleaning is 45kHz, the cleaning temperature is 38 ℃ and the cleaning time is 29 minutes, the alkali liquor composition comprises 6.5% of sodium hydroxide, 0.9% of sodium phosphate by mass, the ultrasonic frequency of alkali cleaning is 55kHz, the alkaline cleaning temperature is 86 ℃, the alkaline cleaning time is 28 minutes, the filler after alkaline cleaning is washed 6 times by desalted water, and the filler is dried by blowing nitrogen at 38 ℃. The silylation reagent solution comprises, by volume, desalted water, absolute ethyl alcohol=5.8:15.9:91, a pH value of 9.3, a prehydrolysis time of 11.5 hours, an electrodeposition voltage of 9V, an electrodeposition time of 45 minutes, a drying and curing temperature of 117 ℃ and a drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=19:28:290. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 3, the treatment temperature is 46 ℃, and the treatment time is 3.8 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate. And (3) carrying out modification post-treatment on the modified silanized filler intermediate to obtain the preactivated modified silanized filler intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The post-modification treatment conditions were 3 volume ratio of pre-activator to modified silanized filler intermediate at 78 ℃, 0.9 hours per treatment time, 3 times of treatment, and 0.9 hours of drying in nitrogen at 125 ℃ after ethanol treatment.
The pre-activated modified silanized filler intermediate is subjected to a first activator treatment and a second activator treatment in sequence. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=28:17:285. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight parts of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride is toluene=17:48:26:220. The zinc chloride is anhydrous zinc chloride. The first activator is treated under the conditions that the volume ratio of the first activator to the preactivated modified silanized filler intermediate is 3, the treatment temperature is 55 ℃, and the treatment time is 5.8 hours. And after the treatment of the first activator is finished, taking out, draining until free liquid is not present, and putting the second activator into the second activator for the treatment of the second activator. The treatment conditions of the second activator treatment were such that the volume ratio of the second activator to the filler after the first activator treatment was 1.7, the activator treatment temperature was 32 ℃ and the treatment time was 25 minutes. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The conditions for the post-activation treatment were as follows, the volume ratio of the agent for the post-activation treatment to the intermediate for the activated modified silanized filler was 3, the temperature was 95 ℃, the pressure (gauge pressure) was 350kPa, the time per treatment was 1.9 hours, the number of treatments was 3, and the ethanol was dried under nitrogen at 117 ℃ for 0.9 hours.
The prepared dealkalization refining agent has the content of modified groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.26mol/m 2, the thickness of a modified layer of 75 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.7mol/m 2, the content of secondary amino groups of 0.52mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 40mmol/m 2, the content of secondary amino groups of 72mmol/m 2 and the content of methoxy groups of 260mmol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 430h -1, the dealkalization refining agent, the adsorption temperature is 47 ℃, and the adsorption pressure (gauge pressure) is 1100kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 28 mass percent of tartaric acid, 3.6 mass percent of acetic acid base succinic acid, 2.9 mass percent of methanesulfonic acid and the balance of desalted water. Wherein the feeding amount ratio of the desulfurization purified dry gas to the regenerant solution is 450 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 3 micrometers, and the thickness is 150 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The conditions for contacting the dry raw material gas with the propylene removing agent are that the temperature is 11 ℃, the pressure is 1400kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 14. The ratio of the dry gas of the raw material to the propylene removing agent is 65 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 1ppm.
[ Example 3]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 16 ℃, the pressure is 550kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 90 percent by volume, and the mass concentration of the desulfurizing agent is 25 percent.
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization preparation.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1100m 2/m3 (model 1100Y, porosity of 84%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and thickness of 74 microns through drying and solidification. The silanization treatment conditions comprise ultrasonic cleaning of silicon carbide with ultrasonic frequency of 35kHz, ultrasonic cleaning of desalted water with ultrasonic frequency of 65kHz, cleaning temperature of 65 ℃ and cleaning time of 35 minutes, ultrasonic cleaning of acetone with ultrasonic frequency of 75kHz, cleaning temperature of 23 ℃ and cleaning time of 21 minutes, alkali liquor composition, sodium hydroxide of 5.5% and sodium phosphate of 0.6% by mass, alkali cleaning temperature of 65 ℃ and alkali cleaning time of 20 minutes, flushing the alkali-washed filler with desalted water for 4 times and drying with nitrogen at 20 ℃, and silanization reagent solution composition, wherein the silylation reagent comprises, in parts by volume, desalted water, absolute ethyl alcohol=4.1:14.3:79, pH value of 8.7, prehydrolysis time of 10.5 hours, electrodeposition voltage of 6V, electrodeposition time of 35 minutes, drying and curing temperature of 105 ℃ and drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=11:22:210. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.5, the treatment temperature is 33 ℃ and the treatment time is 2.5 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate. And (3) carrying out modification post-treatment on the modified silanized filler intermediate to obtain the preactivated modified silanized filler intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The conditions for the post-modification treatment were such that the volume ratio of the pre-activator to the intermediate of the modified silanized filler was 1.5 at a temperature of 65℃for 0.6 hours per treatment, 2 times per treatment, and the ethanol was dried in nitrogen at 115℃for 0.6 hours after treatment.
The pre-activated modified silanized filler intermediate is subjected to a first activator and a second activator in sequence. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=23:12:220. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride is toluene=12:33:17:280. The zinc chloride is anhydrous zinc chloride. The first activator is treated under conditions such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate is 1.5, the treatment temperature is 45 ℃ and the treatment time is 3.5 hours. And after the treatment of the first activator is finished, taking out, draining until free liquid is not present, and putting the second activator into the second activator for the treatment of the second activator. The treatment conditions of the second activator treatment were such that the volume ratio of the second activator to the filler after the first activator treatment was 1.1, the activator treatment temperature was 43 ℃ and the treatment time was 45 minutes. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The conditions for the post-activation treatment were such that the volume ratio of the agent for the post-activation treatment to the intermediate for the activated modified silanized filler was 1.5, the temperature was 70℃for the liquid ethanol submerged in the solid filler, the pressure (gauge pressure) was 250kPa, the time per treatment was 1.1 hours, the number of treatments was 2, and the ethanol was dried under nitrogen at 105℃for 0.6 hours.
The prepared dealkalization refining agent has the content of modified groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.15mol/m 2, the thickness of a modified layer of 50 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.5mol/m 2, the content of secondary amino groups of 0.19mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 20mmol/m 2, the content of secondary amino groups of 28mmol/m 2 and the content of methoxy groups of 52mmol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1300h -1, the dealkalization refining agent, the adsorption temperature is 25 ℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 11 mass percent of tartaric acid, 2.1 mass percent of acetic acid base succinic acid, 1.2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas and the regenerant solution is 550 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 5 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 24 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9. The dosage ratio of the raw material dry gas to the propylene removing agent is 85 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.3ppm.
[ Example 4]
The dealkalization essential agent used in this example was the same as that used in example 2.
The separation process for dry gas feed of this example is the same as that of example 2. This example is only different from example 2 in the dry gas feed used. The dry gas comprises, by volume, methane 17.8711%, ethane 8.1090%, ethylene 15.9930%, propane 0.1859%, propylene 0.8412%, isobutane 0.0811%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutene 0.0381%, maleic acid 0.0002%, oxygen 0.1369%, nitrogen 13.5378%, hydrogen 29.4428%, carbon monoxide 1.4966%, carbon dioxide 3.3258%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6711%, ammonia 0.0520%, aminomethane 0.0056%, N-methyl methylamine 0.0040%, N, N-dimethyl methylamine 0.0032%, N-methyl diethanolamine 0.0032%, cyclopropane methylamine 0.0056%, aminocyclobutane 0.0064%, alkanes or olefins 1.1934%, and other components 0.9500%. Wherein the alkaline impurity is present in a volume content of 580ppm based on total nitrogen element.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 1.7ppm.
[ Example 5]
The dealkalization essential agent used in this example was the same as that used in example 2.
The separation process for dry gas feed of this example is the same as that of example 2. This example is only different from example 2 in the dry gas feed used. The dry gas comprises, by volume, methane 17.8853%, ethane 8.1155%, ethylene 16.0058%, propane 0.1860%, propylene 0.8419%, isobutane 0.0812%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutene 0.0381%, maleic acid 0.0002%, oxygen 0.1371%, nitrogen 13.5486%, hydrogen 29.4663%, carbon monoxide 1.4978%, carbon dioxide 3.3284%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6764%, ammonia 0.0007%, aminomethane 0.0001%, N-methyl methylamine 0.0001%, cyclopropane methylamine 0.0001%, aminocyclobutane 0.0001%, alkanes or olefins 1.1943% above carbon five and other components 0.9500%. Wherein the alkaline impurity is 7.5ppm by volume based on total nitrogen element.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 0.1ppm.
[ Example 6]
The dealkalization essential agent used in this example was the same as that used in example 2.
The separation process for dry gas feed of this example is the same as that of example 2. The present example is different from example 2 only in that the dealkalized purification bed regenerant is different in that the regenerant solution comprises, by mass, 25% citric acid and the balance desalted water.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.8ppm.
[ Example 7]
The dealkalization refining agent adopted in this example is different from that adopted in example 2 only in that 3,3', 5' -tetrachlorodiphenyl disulfide is adopted to replace the 2, 4' -trichloro-2-hydroxydiphenyl ether with equal quality.
The separation process for dry gas feed of this example is the same as that of example 2.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.6ppm.
[ Example 8]
The dealkalization refined agent adopted in the embodiment is different from the embodiment 2 only in that the modifier is different, and 2,4 '-trichloro-2-hydroxydiphenyl ether with the same quality is replaced by 2,2', 5-trichlorobiphenyl.
The separation process for dry gas feed of this example is the same as that of example 2.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.5ppm.
[ Example 9]
The dealkalization refinement used in this example was different from example 2 only in that the first activator was 3-sulfoaniline instead of the equivalent mass of 4-amino-1, 3-benzenedisulfonic acid.
The separation process for dry gas feed of this example is the same as that of example 2.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.9ppm.
[ Example 10]
The dealkalization refinement used in this example was different from example 2 only in that the first activator was 4-aniline sulfonic acid instead of equal mass of 4-amino-1, 3-benzene disulfonic acid.
The separation process for dry gas feed of this example is the same as that of example 2.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 4.8ppm.
[ Example 11]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 16 ℃, the pressure is 550kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 90 percent by volume, and the mass concentration of the desulfurizing agent is 25 percent.
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, then carrying out modification post-treatment, treating with a first activator, and then carrying out activation post-treatment to obtain the dealkalization preparation.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1100m 2/m3 (model 1100Y, porosity of 84%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and thickness of 74 microns through drying and solidification. The silanization treatment conditions comprise ultrasonic cleaning of silicon carbide with ultrasonic frequency of 35kHz, ultrasonic cleaning of desalted water with ultrasonic frequency of 65kHz, cleaning temperature of 65 ℃ and cleaning time of 35 minutes, ultrasonic cleaning of acetone with ultrasonic frequency of 75kHz, cleaning temperature of 23 ℃ and cleaning time of 21 minutes, alkali liquor composition, sodium hydroxide of 5.5% and sodium phosphate of 0.6% by mass, alkali cleaning temperature of 65 ℃ and alkali cleaning time of 20 minutes, flushing the alkali-washed filler with desalted water for 4 times and drying with nitrogen at 20 ℃, and silanization reagent solution composition, wherein the silylation reagent comprises, in parts by volume, desalted water, absolute ethyl alcohol=4.1:14.3:79, pH value of 8.7, prehydrolysis time of 10.5 hours, electrodeposition voltage of 6V, electrodeposition time of 35 minutes, drying and curing temperature of 105 ℃ and drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=11:22:210. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.5, the treatment temperature is 33 ℃ and the treatment time is 2.5 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate. And (3) carrying out modification post-treatment on the modified silanized filler intermediate to obtain the preactivated modified silanized filler intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The conditions for the post-modification treatment were such that the volume ratio of the pre-activator to the intermediate of the modified silanized filler was 1.5 at a temperature of 65℃for 0.6 hours per treatment, 2 times per treatment, and the ethanol was dried in nitrogen at 115℃for 0.6 hours after treatment.
The preactivated modified silylated filler intermediate is subjected to a first activator treatment. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=23:12:220. The zinc chloride is anhydrous zinc chloride. The activator treatment conditions were such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate was 1.5, the treatment temperature was 45 ℃ and the treatment time was 3.5 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The conditions for the post-activation treatment were such that the volume ratio of the agent for the post-activation treatment to the intermediate for the activated modified silanized filler was 1.5, the temperature was 70℃for the liquid ethanol submerged in the solid filler, the pressure (gauge pressure) was 250kPa, the time per treatment was 1.0 hour, the number of treatments was 2, and the ethanol was dried under nitrogen at 110℃for 0.6 hours.
The prepared dealkalization refining agent has the content of modifying groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.15mol/m 2, the thickness of a modified layer of 50 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.5mol/m 2 and the content of secondary amino groups of 0.19mol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1300h -1, the dealkalization refining agent, the adsorption temperature is 25 ℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 11 mass percent of tartaric acid, 2.1 mass percent of acetic acid base succinic acid, 1.2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas and the regenerant solution is 550 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 5 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 24 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9. The dosage ratio of the raw material dry gas to the propylene removing agent is 85 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 15.7ppm.
[ Example 12]
The separation flow of this example is the same as that of example 1. The dry gas raw material in the embodiment comprises, by volume, methane 17.8853%, ethane 8.1155%, ethylene 16.0058%, propane 0.1860%, propylene 0.8419%, isobutane 0.0812%, N-butane 0.0157%, fumaric acid 0.0067%, N-butene 0.0185%, isobutene 0.0381%, maleic acid 0.0002%, oxygen 0.1371%, nitrogen 13.5486%, hydrogen 29.4663%, carbon monoxide 1.4978%, carbon dioxide 3.3284%, acetylene 0.0053%,1, 3-butadiene 0.0001%, hydrogen sulfide 6.6764%, ammonia 0.0007%, methyl amine 0.0001%, N-methyl amine 0.0001%, cyclopropanemethyl amine 0.0001%, aminocyclobutane 0.0001%, alkane or alkene 1.1943% and other components 0.9500%. Wherein the alkaline impurity is 7.5ppm by volume based on total nitrogen element.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 16 ℃, the pressure is 550kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 90 percent by volume, and the mass concentration of the desulfurizing agent is 25 percent.
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, then carrying out modification post-treatment, treating with a first activator, and then carrying out activation post-treatment to obtain the dealkalization preparation.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1100m 2/m3 (model 1100Y, porosity of 84%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and thickness of 74 microns through drying and solidification. The silanization treatment conditions comprise ultrasonic cleaning of silicon carbide with ultrasonic frequency of 35kHz, ultrasonic cleaning of desalted water with ultrasonic frequency of 65kHz, cleaning temperature of 65 ℃ and cleaning time of 35 minutes, ultrasonic cleaning of acetone with ultrasonic frequency of 75kHz, cleaning temperature of 23 ℃ and cleaning time of 21 minutes, alkali liquor composition, sodium hydroxide of 5.5% and sodium phosphate of 0.6% by mass, alkali cleaning temperature of 65 ℃ and alkali cleaning time of 20 minutes, flushing the alkali-washed filler with desalted water for 4 times and drying with nitrogen at 20 ℃, and silanization reagent solution composition, wherein the silylation reagent comprises, in parts by volume, desalted water, absolute ethyl alcohol=4.1:14.3:79, pH value of 8.7, prehydrolysis time of 10.5 hours, electrodeposition voltage of 6V, electrodeposition time of 35 minutes, drying and curing temperature of 105 ℃ and drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=11:22:210. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.5, the treatment temperature is 33 ℃ and the treatment time is 2.5 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate. And (3) carrying out modification post-treatment on the modified silanized filler intermediate to obtain the preactivated modified silanized filler intermediate. The preactivator used for the modification post-treatment is absolute ethyl alcohol. The conditions for the post-modification treatment were such that the volume ratio of the pre-activator to the intermediate of the modified silanized filler was 1.5 at a temperature of 65℃for 0.6 hours per treatment, 2 times per treatment, and the ethanol was dried in nitrogen at 115℃for 0.6 hours after treatment.
The preactivated modified silylated filler intermediate is subjected to a first activator treatment. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=23:12:220. The zinc chloride is anhydrous zinc chloride. The activator treatment conditions were such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate was 1.5, the treatment temperature was 45 ℃ and the treatment time was 3.5 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation. The agent used for the activation post-treatment is absolute ethyl alcohol. The conditions for the post-activation treatment were such that the volume ratio of the agent for the post-activation treatment to the intermediate for the activated modified silanized filler was 1.5, the temperature was 70℃for the liquid ethanol submerged in the solid filler, the pressure (gauge pressure) was 250kPa, the time per treatment was 1.0 hour, the number of treatments was 2, and the ethanol was dried under nitrogen at 110℃for 0.6 hours.
The prepared dealkalization refining agent has the content of modifying groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.15mol/m 2, the thickness of a modified layer of 50 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.5mol/m 2 and the content of secondary amino groups of 0.19mol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1300h -1, the dealkalization refining agent, the adsorption temperature is 25 ℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 11 mass percent of tartaric acid, 2.1 mass percent of acetic acid base succinic acid, 1.2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas and the regenerant solution is 550 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 5 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 24 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9. The dosage ratio of the raw material dry gas to the propylene removing agent is 85 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 2.2ppm.
[ Example 13]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 16 ℃, the pressure is 550kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 90 percent by volume, and the mass concentration of the desulfurizing agent is 25 percent.
The preparation method of the dealkalizing agent comprises the steps of firstly carrying out silanization treatment on a filler to obtain a silanized filler, then sequentially treating the silanized filler with a modifier and treating the silanized filler with a first activator to obtain the dealkalizing agent.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1100m 2/m3 (model 1100Y, porosity of 84%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and thickness of 74 microns through drying and solidification. The silanization treatment conditions comprise ultrasonic cleaning of silicon carbide with ultrasonic frequency of 35kHz, ultrasonic cleaning of desalted water with ultrasonic frequency of 65kHz, cleaning temperature of 65 ℃ and cleaning time of 35 minutes, ultrasonic cleaning of acetone with ultrasonic frequency of 75kHz, cleaning temperature of 23 ℃ and cleaning time of 21 minutes, alkali liquor composition, sodium hydroxide of 5.5% and sodium phosphate of 0.6% by mass, alkali cleaning temperature of 65 ℃ and alkali cleaning time of 20 minutes, flushing the alkali-washed filler with desalted water for 4 times and drying with nitrogen at 20 ℃, and silanization reagent solution composition, wherein the silylation reagent comprises, in parts by volume, desalted water, absolute ethyl alcohol=4.1:14.3:79, pH value of 8.7, prehydrolysis time of 10.5 hours, electrodeposition voltage of 6V, electrodeposition time of 35 minutes, drying and curing temperature of 105 ℃ and drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=11:22:210. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.5, the treatment temperature is 33 ℃ and the treatment time is 2.5 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate.
The modified silylated filler intermediate is subjected to a first activator treatment. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=23:12:220. The zinc chloride is anhydrous zinc chloride. The activator treatment conditions were such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate was 1.5, the treatment temperature was 45 ℃ and the treatment time was 3.5 hours. And (3) performing activation post-treatment on the activated modified silanized filler intermediate to obtain the dealkalized refined preparation.
The prepared dealkalization refining agent has the content of modifying groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.15mol/m 2, the thickness of a modified layer of 50 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.49mol/m 2 and the content of secondary amino groups of 0.17mol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1300h -1, the dealkalization refining agent, the adsorption temperature is 25 ℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 11 mass percent of tartaric acid, 2.1 mass percent of acetic acid base succinic acid, 1.2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas and the regenerant solution is 550 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 5 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 24 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9. The dosage ratio of the raw material dry gas to the propylene removing agent is 85 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 18.6ppm.
[ Example 14]
The dry gas feed described in this example is the same as in example 1. The separation flow of this example is the same as that of example 1.
The desulfurizing agent in the desulfurizing contact tower is N-methyl diethanolamine. The condition of the contact of the dry raw gas and the desulfurizing agent is that the temperature is 16 ℃, the pressure is 550kPa according to the gauge pressure, and the theoretical plate number of the desulfurizing contact tower is 6. The dosage ratio of the dry gas of the raw material to the desulfurizing agent is 90 percent by volume, and the mass concentration of the desulfurizing agent is 25 percent.
The preparation method of the dealkalizing agent comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, and sequentially treating the silanized filler with a first activator and a second activator to obtain the dealkalizing agent.
The filler is a metal corrugated wire mesh structured filler with a specific surface area of 1100m 2/m3 (model 1100Y, porosity of 84%). The metal is 304 material. The silanization treatment adopts an electrodeposition method, firstly adopts silicon carbide suspension grinding liquid to carry out ultrasonic polishing on filler, then adopts desalted water to carry out ultrasonic cleaning, acetone to carry out ultrasonic cleaning, alkali liquor to carry out ultrasonic cleaning, desalted water to wash, nitrogen to blow and dry, then carries out cathodic electrodeposition in silanization reagent (phenylmethyltriethoxysilane) solution, and finally obtains the silane film with the molar ratio of silicon ether group to silicon carbon group of 0.9 and thickness of 74 microns through drying and solidification. The silanization treatment conditions comprise ultrasonic cleaning of silicon carbide with ultrasonic frequency of 35kHz, ultrasonic cleaning of desalted water with ultrasonic frequency of 65kHz, cleaning temperature of 65 ℃ and cleaning time of 35 minutes, ultrasonic cleaning of acetone with ultrasonic frequency of 75kHz, cleaning temperature of 23 ℃ and cleaning time of 21 minutes, alkali liquor composition, sodium hydroxide of 5.5% and sodium phosphate of 0.6% by mass, alkali cleaning temperature of 65 ℃ and alkali cleaning time of 20 minutes, flushing the alkali-washed filler with desalted water for 4 times and drying with nitrogen at 20 ℃, and silanization reagent solution composition, wherein the silylation reagent comprises, in parts by volume, desalted water, absolute ethyl alcohol=4.1:14.3:79, pH value of 8.7, prehydrolysis time of 10.5 hours, electrodeposition voltage of 6V, electrodeposition time of 35 minutes, drying and curing temperature of 105 ℃ and drying atmosphere of nitrogen.
The modifier is 2,4 '-trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene, and the weight portions of the modifier are 2, 4' -trichloro-2-hydroxydiphenyl ether, zinc chloride and toluene=11:22:210. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.5, the treatment temperature is 33 ℃ and the treatment time is 2.5 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate.
The modified silanized filler intermediate is sequentially treated with a first activator and a second activator. The first activator is 4-amino-1, 3-benzene disulfonic acid, zinc chloride and toluene, wherein the weight part of the first activator is 4-amino-1, 3-benzene disulfonic acid comprises zinc chloride and toluene=23:12:220. The second activator is N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid, 3, 5-dichloro-2-methoxyl aniline, zinc chloride and toluene, wherein the weight portion of the N- (carbamoylmethyl) -2-methoxyl ethane sulfonic acid is 3, 5-dichloro-2-methoxyl aniline, the zinc chloride is toluene=12:33:17:280. The zinc chloride is anhydrous zinc chloride. The first activator is treated under conditions such that the volume ratio of the first activator to the preactivated modified silylated filler intermediate is 1.5, the treatment temperature is 45 ℃ and the treatment time is 3.5 hours. And after the treatment of the first activator is finished, taking out, draining until free liquid is not present, and putting the second activator into the second activator for the treatment of the second activator. The treatment conditions of the second activator treatment were such that the volume ratio of the second activator to the filler after the first activator treatment was 1.1, the activator treatment temperature was 43 ℃ and the treatment time was 45 minutes. And (3) activating the modified silanized filler intermediate to obtain the dealkalized refined preparation.
The prepared dealkalization refining agent has the content of modified groups (diphenyl ether groups) introduced into the dealkalization refining agent through a modifying agent of 0.15mol/m 2, the thickness of a modified layer of 50 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.49mol/m 2, the content of secondary amino groups of 0.17mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 18mmol/m 2, the content of secondary amino groups of 26mmol/m 2 and the content of methoxy groups of 50mmol/m 2.
The desulfurization purified dry gas feeding volume space velocity of the dealkalization refining bed is 1300h -1, the dealkalization refining agent, the adsorption temperature is 25 ℃, and the adsorption pressure (gauge pressure) is 700kPa. The liquid power in the dealkalization refining bed is liquid throwing inertia force, and is derived from the high-pressure injection of liquid and the circular motion of the filler driven by a motor. The solution of the regeneration agent of the dealkalization refining bed comprises 11 mass percent of tartaric acid, 2.1 mass percent of acetic acid base succinic acid, 1.2 mass percent of methanesulfonic acid and the balance of desalted water. Wherein, the feeding amount ratio of the desulfurization purified dry gas and the regenerant solution is 550 by volume.
The dealkalization refining bed demister is a wire mesh demister, the separation precision is 5 micrometers, and the thickness is 100 millimeters.
The propylene removing agent in the propylene removing contact tower is benzene. The condition of contacting the raw material dry gas with the propylene removing agent is that the temperature is 24 ℃, the pressure is 1000kPa according to the gauge pressure, and the theoretical plate number of the propylene removing contact tower is 9. The dosage ratio of the raw material dry gas to the propylene removing agent is 85 by volume.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 7.5ppm.
[ Example 15]
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization preparation. The dealkalizing refined agent adopted in this example is different from that in example 3 only in that the modifier and the modification method are different, and the first modification component is selected from 2,2', 5-trichlorobiphenyl, specifically, 2', 5-trichlorobiphenyl, zinc chloride and toluene, wherein the weight portion of the 2,2', 5-trichlorobiphenyl is zinc chloride and toluene=10.3:21:207. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 1.7, the treatment temperature is 36 ℃ and the treatment time is 2.8 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate.
The prepared dealkalization refining agent has the content of modified groups (biphenyl groups) introduced into the dealkalization refining agent through a modifying agent of 0.14mol/m 2, the thickness of a modified layer of 46 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.47mol/m 2, the content of secondary amino groups of 0.18mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 18mmol/m 2, the content of secondary amino groups of 26mmol/m 2 and the content of methoxy groups of 48mmol/m 2.
The dry gas feed described in this example is the same as in example 3. The separation procedure of this example is the same as that of example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 5.2ppm.
[ Example 16]
The preparation method of the dealkalization preparation comprises the steps of firstly carrying out silanization treatment on filler to obtain silanized filler, then treating the silanized filler with a modifier, then carrying out modification post-treatment, sequentially carrying out treatment with a first activator and a second activator, and then carrying out activation post-treatment to obtain the dealkalization preparation. The dealkalizing refined agent adopted in this example is different from that in example 3 only in that the modifier and the modification method are different, and the first modification component is selected from 3,3', 5' -tetrachlorodiphenyl disulfide, specifically, 3', 5' -tetrachlorodiphenyl disulfide, zinc chloride and toluene, and the weight portion of 3,3', 5' -tetrachlorodiphenyl disulfide is zinc chloride and toluene=14:23:204. The zinc chloride is anhydrous zinc chloride. The modifier is treated under the following conditions that the volume ratio of the modifier to the silanized filler is 2.1, the treatment temperature is 38 ℃ and the treatment time is 3.2 hours. And after the filler is treated by the modifier, obtaining a modified silanized filler intermediate.
The prepared dealkalization refining agent has the content of modification groups (disulfide groups) introduced into the dealkalization refining agent through a modifying agent of 0.14mol/m 2, the thickness of a modified layer of 52 microns, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a first activating agent of 0.45mol/m 2, the content of secondary amino groups of 0.17mol/m 2, the content of sulfonic acid groups introduced into the dealkalization refining agent through the treatment of a second activating agent of 17mmol/m 2, the content of secondary amino groups of 25mmol/m 2 and the content of methoxy groups of 46mmol/m 2.
The dry gas feed described in this example is the same as in example 3. The separation procedure of this example is the same as that of example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 5.7ppm.
Comparative example 1
The dealkalized concentrate of this comparative example was prepared in comparison with example 3 by directly using a commercially available corrugated wire mesh structured packing (model 1100Y, porosity 84%) having a specific surface area of 1100m 2/m3. The dry gas feed used in this comparative example was the same as in example 3, and the separation process for the dry gas feed was the same as in example 3.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 23ppm.
Comparative example 2
The dry gas feed used in this comparative example was the same as in example 3 and the desulfurization and dealkylation was the same as in example 3, and the dealkalization was carried out by eluting with water using a packed column (model 250Y, porosity 96%). The operation conditions of the water scrubber and the process are that the temperature is 35 ℃, the pressure (gauge pressure) is 1000kPa, the theoretical plate number is 18, the dilute sulfuric acid aqueous solution with pH value of 3 is adopted, and the gas-liquid volume ratio is 40.
The total nitrogen volume content in the obtained propylene-removed purified dry gas was 35ppm.
[ Comparative example 3]
The dry gas raw material used in this comparative example was the same as in example 3, and the desulfurization and dealkylation were carried out in the same manner as in example 3, and the dealkalized impurities were obtained by using a commercial NKC-9 resin (H type) (Nanka resin Co.) as an adsorbent under the conditions of 100 cubic meters of resin packing, 30℃of adsorption temperature and 50H -1 of volume space velocity by using a conventional fixed bed adsorption process.
At the initial stage of application, the total nitrogen volume content in the obtained propylene-removing purified dry gas is 4ppm, the adsorbent penetrates in about 10 days, the regeneration is required to be performed by adopting sulfuric acid with the mass concentration of 4% -6%, and the volume consumption of the regeneration liquid of the adsorbent per unit volume is 4-5 times.
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (39)
1. The dealkalization refining agent is characterized by comprising a filler, a silane layer, a modified layer and a first activation layer from inside to outside, wherein the modified group contained in the modified layer is at least one selected from biphenyl, diphenyl ether group or disulfide group, and the first activation layer contains sulfonic acid groups and secondary amine groups.
2. The dealkalizing agent as defined in claim 1, wherein the silane layer has a molar ratio of silyl ether group to silicon carbon group of 0.8 to 1.2 and a thickness of 50 to 300 μm.
3. The dealkalizing agent as defined in claim 1, wherein the modifying group content in the modifying layer is 0.13-0.27 mol/m 2, and the modifying layer thickness is 40-80 μm.
4. The dealkalizing agent according to claim 1, wherein the content of sulfonic acid groups in the first activation layer is 0.4 to 0.8mol/m 2, and the content of secondary amine groups is 0.16 to 0.56mol/m 2.
5. The dealkalizing concentrate of claim 1, wherein the filler is at least one of a grid structured filler and a corrugated structured filler, and the filler is made of metal, plastic or ceramic.
6. The dealkalizing concentrate of claim 5, wherein the filler is a corrugated wire mesh structured filler.
7. The dealkalizing concentrate of claim 5, wherein the filler has a specific surface area of 1000-2600 mm 2/m3 and a porosity of 74-85%.
8. The dealkalizing preparation according to any one of claims 1 to 7, further comprising a second activation layer on the outer surface of the first activation layer, wherein the second activation layer has a sulfonic acid group content of 10 to 50mmol/m 2, a secondary amine group content of 16 to 90mmol/m 2, and a methoxy group content of 40 to 270mmol/m 2.
9. A process for the preparation of the dealkalized concentrate of any one of claims 1-7 comprising:
(1) The filler is subjected to silanization treatment to obtain silanized filler;
(2) Treating the silanized filler obtained in step (1) with a modifier;
(3) Treating the filler obtained in the step (2) with a first activator to obtain a dealkalized refined preparation.
10. The process according to claim 9, wherein the silylating agent used in the silylation of step (1) is at least one member selected from the group consisting of phenylmethyltriethoxysilane and phenylmethyltrimethoxysilane.
11. The process according to claim 9, wherein the modifier in the step (2) comprises a first modifying component selected from at least one of 2,2', 5-trichlorobiphenyl, 2, 4' -trichloro-2-hydroxydiphenyl ether, 3', 5' -tetrachlorodiphenyl disulfide, a catalyst selected from one of Lewis acid or Lewis base, and a solvent selected from at least one of toluene, para-xylene, meta-xylene, ortho-xylene.
12. The method according to claim 11, wherein in the step (2), the first modifying component is 2, 4' -trichloro-2-hydroxydiphenyl ether, and the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride.
13. The preparation method of claim 11, wherein in the step (2), the first modification component comprises, by mass, catalyst solvent= (10-20): (20-30): (200-300).
14. The preparation method of the modified glass fiber reinforced plastic material, which is characterized in that the modifier is soaked in the step (2), the modification treatment is carried out under the conditions that the liquid-solid volume ratio is 1-4, the treatment temperature is 30-50 ℃, and the treatment time is 2-4 hours.
15. The process according to claim 9, wherein in the step (2), the modified silylated filler obtained in the step (1) is treated with a modifying agent and then subjected to a modifying post-treatment to obtain a preactivated modified silylated filler intermediate, wherein the preactivating agent used in the modifying post-treatment is one or more of anhydrous methanol, anhydrous ethanol and anhydrous acetone.
16. The process according to claim 15, wherein in the step (2), the preactivating agent used for the post-modification treatment is absolute ethanol.
17. The preparation method according to claim 15, wherein the post-modification treatment is soaking, and the post-modification treatment conditions are that the liquid-solid volume ratio is 1-4, the temperature is 60-80 ℃, the treatment time is 0.5-1.0 hour each time, the treatment times are 2-3 times, and the drying is carried out in an inert atmosphere at 110-130 ℃ for 0.5-1.0 hour after the treatment.
18. The process according to claim 9, wherein in the step (3), the first activator comprises sulfonic acid group-containing aromatic hydrocarbon, a catalyst selected from one of Lewis acid or Lewis base, and a solvent selected from at least one of toluene, para-xylene, meta-xylene, ortho-xylene.
19. The process according to claim 18, wherein in the step (3), the sulfonic acid group-containing aromatic hydrocarbon is one or more of 3-sulfonic acid aniline, 4-amino-1, 3-benzenedisulfonic acid, and 4-aniline sulfonic acid.
20. The process according to claim 18, wherein in the step (3), the sulfonic acid group-containing aromatic hydrocarbon is 4-amino-1, 3-benzenedisulfonic acid.
21. The method according to claim 18, wherein in the step (3), the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride and anhydrous aluminum chloride.
22. The preparation method of the catalyst according to claim 18, wherein in the step (3), the aromatic hydrocarbon containing the sulfonic acid group comprises, by mass, a catalyst solvent= (20-30): (10-20): (200-300).
23. The method according to claim 18, wherein in the step (3), the first activator is used for soaking, and the treatment condition of the first activator is that the liquid-solid volume ratio is 1-4, the treatment temperature of the first activator is 40-60 ℃, and the treatment time is 3-6 hours.
24. The method according to any one of claims 9 to 23, wherein in the step (3), after the treatment with the first activator, solid-liquid separation is performed, the obtained solid is contacted with the second activator to perform a second activation treatment, thereby obtaining a dealkalized preparation, wherein the content of sulfonic acid groups introduced into the dealkalized preparation by the treatment with the second activator is 10 to 50mmol/m 2, the content of secondary amine groups is 16 to 90mmol/m 2, and the content of methoxy groups is 40 to 270mmol/m 2.
25. The process according to claim 24, wherein in the step (3), the second activator comprises sulfonic acid group-containing aliphatic hydrocarbon, 3, 5-dichloro-2-methoxyaniline, a catalyst and a solvent, wherein the sulfonic acid group-containing aliphatic hydrocarbon is N- (carbamoylmethyl) -2-aminoethanesulfonic acid, the catalyst is one selected from Lewis acid and Lewis base, and the solvent is at least one selected from toluene, para-xylene, meta-xylene and ortho-xylene.
26. The method according to claim 25, wherein in the step (3), the catalyst is at least one of anhydrous zinc chloride, anhydrous tin tetrachloride, and anhydrous aluminum chloride.
27. The preparation method according to claim 25, wherein in the step (3), 3, 5-dichloro-2-methoxyaniline is used as a catalyst, and solvent= (10-20): (30-50): (15-30): (200-300) is used as a catalyst, in parts by mass.
28. The method according to claim 25, wherein in the step (3), the second activator is used for soaking, and the second activator is used under the conditions that the liquid-solid volume ratio is 1-1.8, the treatment temperature is 30-45 ℃, and the treatment time is 20-50 minutes.
29. The process according to claim 24, wherein in the step (3), the dealkalized concentrate is obtained by subjecting the filler obtained by the first activation treatment and/or the filler obtained by the second activation treatment to an activation post-treatment, and the agent used for the activation post-treatment is at least one of absolute ethyl alcohol and benzene.
30. The method according to claim 29, wherein in the step (3), the post-activation treatment is soaking, and the post-activation treatment is carried out under the conditions that the liquid-solid volume ratio is 1-4, the temperature is 65-100 ℃, the gauge pressure is 200-400 kPa, the treatment time is 1.0-2.0 hours each time, the treatment times are 2-3 times, and the post-activation treatment is carried out for 0.5-1.0 hour in an inert atmosphere at 100-120 ℃.
31. Use of the dealkalized concentrate of any one of claims 1-8 or the dealkalized concentrate of any one of claims 9-30 in the dealkalization of dry gas.
32. The use according to claim 31, wherein a dealkalization refiner is used, wherein a dealkalization refiner bed is arranged, a static regenerant central axis distributor is arranged at the axial center position of the dealkalization refiner, a gas collecting pipe is arranged at the outer side of the regenerant central axis distributor, a raw material dry gas feed port is arranged on the side wall of the dealkalization refiner, the upper part is provided with a regenerant feed port and is communicated with the regenerant central axis distributor, a regenerant discharge port is arranged on the lower part, a purified dry gas discharge port is arranged on the top, and the dry gas discharge port is communicated with the gas collecting pipe, wherein the raw material dry gas flows from the wall side to the axis through the dealkalization refiner, and simultaneously the regenerant flows to the dealkalization refiner under the action of power through the regenerant central axis distributor, and adsorption and regeneration are realized, so that purified dry gas and a regenerant solution after working are obtained.
33. The use according to claim 31 or 32, wherein the dealkalization refining is carried out at a temperature of 20 to 50 ℃, a pressure of 500 to 1200kpa, a dry gas feed volume space velocity of 300 to 1500h -1, and a feed rate ratio of dry gas to regenerant solution of 400 to 600 by volume.
34. The use according to claim 32, wherein the regenerant is selected from at least one of citric acid, tartaric acid, acetoxysuccinic acid, methanesulfonic acid, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, acetic acid.
35. The use according to claim 34, wherein the regenerant solution comprises, by mass, 10% -30% tartaric acid, 2% -4% acetic acid-based succinic acid, 1% -3% methanesulfonic acid and the balance desalted water.
36. The use according to claim 31, wherein the basic impurities contained in the raw dry gas comprise at least one of ammonia, aminomethane, N-methyl methylamine, cyclopropanemethylamine, N-dimethyl methylamine, monoethanolamine, diethanolamine, aminocyclobutane, diisopropanolamine, N-methyldiethanolamine;
And/or, the volume content of the raw material dry gas is not less than 5ppm based on the total nitrogen element, and the volume content of the raw material dry gas is not more than 2000ppm based on the total nitrogen element.
37. The use according to claim 36, wherein the dry gas of the raw material has a volume content of not less than 50ppm based on total nitrogen elements and not more than 1000ppm based on total nitrogen elements.
38. The use according to claim 36, wherein the dry gas of the raw material has a volume content of not less than 500ppm based on the total nitrogen element.
39. The use according to claim 31, wherein the raw dry gas is contacted with a desulfurizing agent to remove sulfide before being contacted with the dealkalizing refining agent, thereby obtaining a desulfurized purified dry gas;
And/or contacting the purified dry gas from which the alkaline impurities are removed with a propylene removal agent to obtain a propylene-removed purified dry gas.
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| CA1292477C (en) * | 1987-01-08 | 1991-11-26 | Robert A. Kirchhoff | Arylcyclobutenyl amido alkenoic acids and salts thereof |
| CN105612211A (en) * | 2013-10-09 | 2016-05-25 | 日本合成化学工业株式会社 | Saponified ethylene-vinyl ester copolymer composition, and multilayer structure using said composition |
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| US8193270B2 (en) * | 2004-12-14 | 2012-06-05 | 3M Innovative Properties Company | Method of making composites and nanocomposites |
| WO2016045026A1 (en) * | 2014-09-25 | 2016-03-31 | The Procter & Gamble Company | Laundry detergents and cleaning compositions comprising sulfonate group-containing polymers |
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| CA1292477C (en) * | 1987-01-08 | 1991-11-26 | Robert A. Kirchhoff | Arylcyclobutenyl amido alkenoic acids and salts thereof |
| CN105612211A (en) * | 2013-10-09 | 2016-05-25 | 日本合成化学工业株式会社 | Saponified ethylene-vinyl ester copolymer composition, and multilayer structure using said composition |
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