[go: up one dir, main page]

CN113231036A - Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof - Google Patents

Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof Download PDF

Info

Publication number
CN113231036A
CN113231036A CN202110555689.4A CN202110555689A CN113231036A CN 113231036 A CN113231036 A CN 113231036A CN 202110555689 A CN202110555689 A CN 202110555689A CN 113231036 A CN113231036 A CN 113231036A
Authority
CN
China
Prior art keywords
tertiary amine
activated carbon
alkali
solution
adsorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110555689.4A
Other languages
Chinese (zh)
Inventor
管国锋
王伯航
万辉
王磊
赵鹏
冯能杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN202110555689.4A priority Critical patent/CN113231036A/en
Publication of CN113231036A publication Critical patent/CN113231036A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28064Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28066Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/304Hydrogen sulfide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a load type adsorbent for removing ultralow-concentration hydrogen sulfide and a preparation method thereof. Alkali treatment is carried out on the activated carbon through alkali solution, and then an impregnation method is adopted to load the active component on the activated carbon subjected to the alkali treatment. The active components of the supported adsorbent can be uniformly dispersed on the surface of the active carbon, and the supported adsorbent has strong capability of removing ultralow-concentration hydrogen sulfide from coal gas tail gas.

Description

Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogen sulfide adsorption, and particularly relates to a supported adsorbent for removing ultralow-concentration hydrogen sulfide and a preparation method thereof.
Background
After the waste gas generated by coal gas is washed and purified by low-temperature methanol, more than 90 percent of the waste gas is carbon dioxide, and meanwhile, hydrogen sulfide with ultralow concentration exists. The hydrogen sulfide is a highly toxic gas with the odor of the rotten eggs and has strong irritation. Poisoning and even death can occur when humans come into contact with certain concentrations of hydrogen sulfide, which, in addition, can corrode piping and equipment, resulting in catalyst poisoning. The removal of the hydrogen sulfide with ultra-low concentration in the coal gas tail gas is beneficial to the health of human bodies and the safe production. Because the conventional normal-temperature desulfurization method is mostly based on acid-base reaction to remove hydrogen sulfide, and carbon dioxide and hydrogen sulfide are both acid gases, the inhibition effect of carbon dioxide in the desulfurization process cannot be avoided, and the desulfurization selectivity is poor. Therefore, the development of a high-selectivity desulfurizing agent for removing ultralow-concentration hydrogen sulfide in coal gas tail gas is needed.
At present, the common industrial normal temperature desulfurization methods are mainly classified into absorption methods and adsorption methods. The absorption process is mainly to absorb hydrogen sulfide into the liquid phase by using an alcohol amine solution. The absorption method has large treatment capacity, but has low desulfurization precision, and the treated gas has high content of hydrogen sulfide and can cause equipment corrosion. The adsorption method mainly utilizes molecular sieves (Steijns M, MarsP. Industrial & Engineering chemical Product Research & Development,2017,16(1):103-10.), activated carbon (Mochizuki T, Kubota M, Matsuda H, et al. Fuel Processing Technology,2016,144: 164. quadrature. 169.) and the like to adsorb hydrogen sulfide, overcomes the defect of low desulfurization precision of the absorption method, and is one of the common fine desulfurization technologies. Among them, the activated carbon adsorbent is widely used due to its advantages of low cost, easy regeneration, etc. However, the common activated carbon has poor adsorption selectivity, for example, patent CN202010648368.4 discloses a preparation method of activated carbon with basic functional groups, but it is only suitable for removing hydrogen sulfide in air environment, and cannot effectively remove ultralow concentration hydrogen sulfide in coal gas tail gas.
Disclosure of Invention
Aiming at the defect of poor selectivity of the existing hydrogen sulfide adsorbent, the invention provides a method for removing a load type adsorbent. The adsorbent prepared by the invention has the synergistic effect of the tertiary amine ionic liquid, the tertiary amine and the activated carbon carrier, has higher hydrogen sulfide adsorption capacity and adsorption selectivity, is simple in preparation process, and does not corrode equipment. The invention also provides a preparation method of the supported adsorbent.
The technical scheme of the invention is as follows: a load type adsorbent for removing ultralow-concentration hydrogen sulfide is characterized in that activated carbon treated by alkali is used as a carrier, and tertiary amine ionic liquid and tertiary amine are used as active components; wherein the loading capacity of the tertiary amine ionic liquid is 1-10% of the mass of the activated carbon subjected to alkali treatment; the loading amount of the tertiary amine is 10-40% of the mass of the alkali-treated activated carbon; the specific surface area of the activated carbon after alkali treatment is 680-1010m2Per g, pore volume of 0.32-0.49cm3/g。
Preferably, the cation of the tertiary amine ionic liquid is any one of triethanolamine, N-methyldiethanolamine or N, N, N ', N' -tetramethylhexamethylenediamine in tertiary amine, and the anion is any one of formic acid, acetic acid or benzoic acid in organic acid; the tertiary amine is one of triethanolamine, N-methyldiethanolamine or N, N, N ', N' -tetramethyl hexanediamine.
The invention also provides a method for preparing the supported adsorbent, which comprises the following steps:
(1) preparation of tertiary amine ionic liquid: respectively dissolving tertiary amine and organic acid in water, adding the organic acid solution into the tertiary amine solution at 40-80 ℃, stirring for 12-24h, evaporating to remove water, and drying in vacuum to obtain tertiary amine ionic liquid;
(2) preparation of alkali-treated activated carbon: adding activated carbon into the alkali solution, stirring for alkali treatment, washing the stirred activated carbon until the filtrate is neutral, and drying to obtain alkali-treated activated carbon;
(3) preparation of the supported adsorbent: weighing a certain mass of tertiary amine and tertiary amine ionic liquid according to the loading capacity, dissolving the tertiary amine and tertiary amine ionic liquid in an organic solvent, adding the alkali-treated active carbon obtained in the step (2) into the solution, stirring, and drying to obtain the supported adsorbent.
Preferably, the molar ratio of the tertiary amine to the organic acid in the step (1) is (1-1.5): 1. Preferably, the evaporation temperature in the step (1) is 70-100 ℃; the vacuum drying temperature is 80-120 deg.C, and the drying time is 12-24 h.
Preferably, the alkali solution in the step (2) is NaOH solution or NaHCO solution3One of a solution or ammonia; the mass concentration of the alkali solution is 5-15%; the ratio of the volume of the alkali solution to the mass of the activated carbon is (10-50) mL/g. Preferably, the stirring temperature in the step (2) is 25-85 ℃, and the stirring time is 6-12 h; the drying temperature is 80-120 ℃, and the drying time is 8-12 h.
Preferably, the organic solvent in the step (3) is one of methanol, ethanol or ethylene glycol; the ratio of the volume of the organic solvent to the mass of the alkali-treated activated carbon carrier is (10-30) mL/g.
Preferably, the stirring time in the step (3) is 4-8h, and the stirring temperature is 20-70 ℃; the drying temperature is 70-100 deg.C, and the drying time is 3-9 h.
The invention provides a method for removing trace hydrogen sulfide in coal gas tail gas by using the adsorbent, which comprises the following steps: mixing carbon dioxide and hydrogen sulfide according to a certain proportion to prepare mixed gas, filling an adsorbent into an adsorption tube of a fixed bed device, introducing the mixed gas to carry out an adsorption experiment, and calculating the penetration adsorption amount when the concentration of a hydrogen sulfide outlet reaches a penetration point of 0.5 ppm; wherein the concentration of hydrogen sulfide in the mixed gas is 3-20 ppm; the adsorption temperature is 20-60 ℃; the space velocity is 8000-20000 mL/g.h.
The supported adsorbent prepared by the invention has rich pore channel structures of the active carbon, is beneficial to the loading of active components, and can also reduce the mass transfer resistance of hydrogen sulfide. The alkali treated active carbon carrier increases the number of alkaline sites on the surface of the active carbon. The tertiary amine group does not have active hydrogen ions and does not react with carbon dioxide in a dry environment, so that the removal of ultralow-concentration hydrogen sulfide in the coal gas tail gas can be realized by introducing the tertiary amine group into the adsorbent. The tertiary amine and the tertiary amine ionic liquid are loaded into the pore channel of the activated carbon, so that the tertiary amine groups are uniformly dispersed, the contact probability of the tertiary amine groups and hydrogen sulfide is increased, and the adsorption capacity and selectivity of the adsorbent are improved. And the addition of the tertiary amine ionic liquid improves the thermal stability of the adsorbent. The active carbon is pretreated by the alkali solution, and the tertiary amine and tertiary amine ionic liquid are loaded into the active carbon pore channel by adopting an impregnation method, so that the adsorption capacity and the adsorption selectivity of the adsorbent are improved, and the adsorbent has the advantages of easiness in preparation, good stability and the like.
Has the advantages that:
(1) the adsorbent prepared by the invention has high tertiary amine group content, uniform dispersion, good desulfurization efficiency and high selectivity.
(2) The invention adopts alkali solution to modify the active carbon, and increases the number of surface alkaline functional groups.
(3) The tertiary amine ionic liquid is prepared and loaded into the pore channel of the alkali-treated active carbon, and the thermal stability of the adsorbent is favorably improved.
(4) The invention adopts an impregnation method to load the active components on the active carbon, and the preparation process is simple.
Detailed Description
In order that the objects and advantages of the invention will become more apparent, the invention is further illustrated by the following specific examples. The specific embodiments described herein are merely illustrative of the present invention and do not specifically limit the scope of the invention.
Example 1
(1) 11.916g of N-methyldiethanolamine (0.1mol) and 4.603g of formic acid (0.1mol) are weighed and respectively dissolved in 100mL of water, the formic acid solution is added into the N-methyldiethanolamine solution, the mixture is continuously stirred for 12h at 40 ℃, water is removed by evaporation at 70 ℃, and the tertiary amine ionic liquid is obtained by vacuum drying at 80 ℃ for 12 h.
(2) 4g of activated carbon was weighed into 200mL of 15 wt% ammonia water and stirred at 25 ℃ for 12 hours. And (4) filtering and washing the stirred activated carbon to be neutral, and drying at 120 ℃ for 8h to obtain the alkali-treated activated carbon. The specific surface area of the activated carbon after alkali treatment is 680m2G, pore volume 0.32cm3/g。
(3) 0.15g of the tertiary amine ionic liquid obtained in the step (1) and 0.45g of triethanolamine are weighed and dissolved in 15mL of ethanol, 1.5g of the solid obtained in the step (2) is weighed and added into the solution, stirred for 4h at 20 ℃, and dried for 3h at 100 ℃ to obtain the adsorbent 1.
(4) Weighing 1.114g of the adsorbent 1 for removing trace hydrogen sulfide in the coal gas tail gas, wherein the adsorption temperature is 30 ℃, the concentration of the hydrogen sulfide is 5ppm, and the space velocity is 14000 mL/g.h. When the outlet concentration reached 0.5ppm, the breakthrough adsorption capacity of finished adsorbent 1 was 2.233 mg/g.
Example 2
(1) 22.378g of triethanolamine (0.15mol) and 6.005g of acetic acid (0.1mol) are weighed and respectively dissolved in 100mL of water, the acetic acid solution is added into the triethanolamine solution, the stirring is continued for 24h at 80 ℃, the water is removed by evaporation at 80 ℃, and the tertiary amine ionic liquid is obtained after vacuum drying for 24h at 120 ℃.
(2) 4g of activated carbon were weighed into 40mL of 10 wt% NaOH solution and stirred at 85 ℃ for 6 h. And (4) filtering and washing the stirred activated carbon to be neutral, and drying at 80 ℃ for 12h to obtain the alkali-treated activated carbon. The specific surface area of the activated carbon after alkali treatment is 1010m2Per g, pore volume 0.49cm3/g。
(3) 0.015g of the tertiary amine ionic liquid obtained in the step (1) and 0.6g of N, N, N ', N' -tetramethylhexamethylenediamine are weighed and dissolved in 45mL of methanol, 1.5g of the solid obtained in the step (2) is weighed and added into the solution, the mixture is stirred for 8h at 70 ℃, and the mixture is dried for 9h at 70 ℃ to obtain the adsorbent 2.
(4) 0.78g of adsorbent 2 is weighed to remove trace hydrogen sulfide in the coal gas tail gas, the adsorption temperature is 20 ℃, the concentration of the hydrogen sulfide is 3ppm, and the space velocity is 20000 mL/g.h. When the exit concentration reached 0.5ppm, the breakthrough adsorption capacity of finished adsorbent 2 was 3.429 mg/g.
Example 3
(1) 17.231g of N, N, N ', N' -tetramethylhexanediamine (0.1mol) and 12.212g of benzoic acid (0.1mol) are weighed and respectively dissolved in 100mL, the benzoic acid solution is added into the N, N, N ', N' -tetramethylhexanediamine solution, the mixture is continuously stirred for 18h at the temperature of 60 ℃, water is removed by evaporation at the temperature of 90 ℃, and the tertiary amine ionic liquid is obtained by vacuum drying for 20h at the temperature of 100 ℃.
(2) 4g of activated charcoal was weighed into 100mL of 5 wt% NaHCO3Stirring the solution at 65 ℃ for 9h, filtering and washing the stirred activated carbon to be neutral, and drying the activated carbon at 100 ℃ for 10h to obtain the alkali-treated activated carbon. The specific surface area of the activated carbon after alkali treatment is 769m2G, pore volume 0.36cm3/g。
(3) 0.1g of the tertiary amine ionic liquid obtained in the step (1) and 0.2g of methyldiethanolamine are weighed and dissolved in 30mL of ethylene glycol, 2g of the solid obtained in the step (2) is weighed and added into the solution, the mixture is stirred for 6h at 40 ℃, and the mixture is dried for 6h at 90 ℃ to obtain the adsorbent 3.
(4) Weighing 1.95g of the adsorbent 3 for removing trace hydrogen sulfide in the coal gas tail gas, wherein the adsorption temperature is 40 ℃, the concentration of the hydrogen sulfide is 20ppm, and the space velocity is 8000 mL/g.h. When the outlet concentration reached 0.5ppm, the breakthrough adsorption capacity of finished adsorbent 3 was 1.840 mg/g.
Example 4
(1) 17.874g of N-methyldiethanolamine (0.15mol) and 6.005g of acetic acid (0.1mol) are weighed and respectively dissolved in 100mL of water, the acetic acid solution is added into the N-methyldiethanolamine solution, the mixture is continuously stirred for 15h at 70 ℃, water is removed by evaporation at 100 ℃, and the tertiary amine ionic liquid is obtained by vacuum drying at 90 ℃ for 18 h.
(2) Weighing 4g of activated carbon, adding the activated carbon into 50mL of 10 wt% ammonia water, stirring at 45 ℃ for 12h, filtering and washing the stirred activated carbon to be neutral, and drying at 90 ℃ for 12h to obtain the alkali-treated activated carbon. The specific surface area of the activated carbon after alkali treatment is 835m2Per g, pore volume 0.43cm3/g。
(3) 0.075g of the tertiary amine ionic liquid obtained in the step (1) and 0.3g of triethanolamine are weighed and dissolved in 25mL of ethanol, 1.5g of the solid obtained in the step (2) is weighed and added into the solution, stirred for 7h at 40 ℃, and dried for 5h at 80 ℃ to obtain the adsorbent 4.
(4) Weighing 1.3g of adsorbent 4 for removing trace hydrogen sulfide in the coal gas tail gas, wherein the adsorption temperature is 50 ℃, the concentration of the hydrogen sulfide is 15ppm, the space velocity is 12000 mL/g.h, and when the outlet concentration reaches 0.5ppm, the penetrating adsorption capacity of the finished adsorbent 4 is 2.804 mg/g.

Claims (9)

1.一种用于脱除超低浓度硫化氢的负载型吸附剂,其特征在于以碱处理的活性炭为载体,叔胺类离子液体和叔胺为活性组分;其中所述叔胺类离子液体的负载量为碱处理的活性炭质量的1-10%;所述叔胺的负载量为碱处理的活性炭质量的10-40%;碱处理后的活性炭比表面积为680-1010m2/g,孔容0.32-0.49cm3/g。1. a loaded adsorbent for removing ultra-low concentration hydrogen sulfide, is characterized in that taking the activated carbon of alkali treatment as carrier, tertiary amine ionic liquid and tertiary amine are active components; wherein said tertiary amine ion The loading amount of the liquid is 1-10% of the mass of the activated carbon treated with alkali; the loading amount of the tertiary amine is 10-40% of the mass of the activated carbon treated with the alkali; the specific surface area of the activated carbon after the alkali treatment is 680-1010 m 2 /g, Pore volume 0.32-0.49 cm 3 /g. 2.根据权利要求1所述的负载型吸附剂,其特征在于所述叔胺类离子液体的阳离子为叔胺中的三乙醇胺、N-甲基二乙醇胺或N,N,N’,N’-四甲基己二胺中的任一种,阴离子为有机酸中的甲酸、乙酸或苯甲酸的任一种;所述叔胺为三乙醇胺、N-甲基二乙醇胺或N,N,N’,N’-四甲基己二胺中的一种。2. The loaded adsorbent according to claim 1, wherein the cation of the tertiary amine ionic liquid is triethanolamine, N-methyldiethanolamine or N,N,N',N' in the tertiary amine - any one in tetramethylhexamethylene diamine, the anion is any one of formic acid, acetic acid or benzoic acid in the organic acid; the tertiary amine is triethanolamine, N-methyldiethanolamine or N,N,N ', N'-tetramethylhexamethylenediamine in one. 3.一种制备如权利要求1所述的负载型吸附剂的方法,其具体步骤如下:3. a method for preparing the loaded adsorbent as claimed in claim 1, its concrete steps are as follows: (1)叔胺类离子液体的制备:将叔胺和有机酸分别溶于水中,在40-80℃下将有机酸溶液加入到叔胺溶液中搅拌12-24h,再蒸发去除水,真空干燥得到叔胺类离子液体;(1) Preparation of tertiary amine ionic liquid: Dissolve the tertiary amine and organic acid in water respectively, add the organic acid solution to the tertiary amine solution at 40-80°C and stir for 12-24 h, then evaporate the water and vacuum dry to obtain tertiary amine ionic liquid; (2)碱处理的活性炭的制备:在碱溶液中加入活性炭,搅拌进行碱处理,将搅拌后的活性炭洗涤至滤液中性,干燥,得到碱处理的活性炭;(2) preparation of the activated carbon of alkali treatment: add activated carbon to alkali solution, stir to carry out alkali treatment, the activated carbon after stirring is washed until the filtrate is neutral, and dried to obtain the activated carbon of alkali treatment; (3)负载型吸附剂的制备:按照负载量称取一定质量叔胺和叔胺类离子液体溶于有机溶剂中,将步骤(2)中得到的碱处理的活性炭加入到溶液中,搅拌,干燥得到负载型吸附剂。(3) preparation of loaded adsorbent: weigh a certain mass of tertiary amine and tertiary amine ionic liquid according to the load and dissolve in an organic solvent, add the alkali-treated activated carbon obtained in step (2) into the solution, stir, Dry to obtain a supported adsorbent. 4.根据权利要求3所述的方法,其特征在于步骤(1)中所述的叔胺与有机酸的摩尔比为(1-1.5)∶1。4. The method according to claim 3, wherein the molar ratio of the tertiary amine described in the step (1) to the organic acid is (1-1.5):1. 5.根据权利要求3所述的方法,其特征在于步骤(1)中所述的蒸发温度为70-100℃;真空干燥温度为80-120℃,时间为12-24h。5 . The method according to claim 3 , wherein the evaporation temperature in step (1) is 70-100° C.; the vacuum drying temperature is 80-120° C. and the time is 12-24 h. 6 . 6.根据权利要求3所述的方法,其特征在于步骤(2)中所述的碱溶液为NaOH溶液、NaHCO3溶液或氨水中的一种;所述的碱溶液的质量浓度为5-15%;所述的碱溶液体积与活性炭质量之比为10-50mL/g。6. method according to claim 3, is characterized in that the alkali solution described in step ( 2 ) is a kind of NaOH solution, NaHCO solution or ammoniacal liquor; The mass concentration of described alkali solution is 5-15 %; the ratio of the volume of the alkaline solution to the mass of the activated carbon is 10-50 mL/g. 7.根据权利要求3所述的方法,其特征在于步骤(2)中所述的搅拌温度为25-85℃,搅拌时间为6-12h;干燥温度为80-120℃,干燥时间为8-12h。7. The method according to claim 3, wherein the stirring temperature described in step (2) is 25-85 °C, and the stirring time is 6-12 h; the drying temperature is 80-120 °C, and the drying time is 8-12 h. 12h. 8.根据权利要求3所述的方法,其特征在于步骤(3)中所述的有机溶剂为甲醇、乙醇或乙二醇中的一种;所述有机溶剂体积与碱处理的活性炭载体质量之比为10-30mL/g。8. method according to claim 3 is characterized in that the organic solvent described in step (3) is a kind of in methanol, ethanol or ethylene glycol; The difference between the volume of described organic solvent and the activated carbon carrier quality of alkali treatment The ratio is 10-30 mL/g. 9.根据权利要求3所述的方法,其特征在于步骤(3)中所述的搅拌时间为4-8h,搅拌温度为20-70℃;干燥温度为70-100℃,干燥时间为3-9h。9. The method according to claim 3, wherein the stirring time described in step (3) is 4-8h, and the stirring temperature is 20-70°C; the drying temperature is 70-100°C, and the drying time is 3- 9h.
CN202110555689.4A 2021-05-21 2021-05-21 Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof Pending CN113231036A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110555689.4A CN113231036A (en) 2021-05-21 2021-05-21 Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110555689.4A CN113231036A (en) 2021-05-21 2021-05-21 Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113231036A true CN113231036A (en) 2021-08-10

Family

ID=77138331

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110555689.4A Pending CN113231036A (en) 2021-05-21 2021-05-21 Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113231036A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1698929A (en) * 2005-05-09 2005-11-23 中国科学院过程工程研究所 Alcoholamine carboxylate functionalized ionic liquid
CN101671259A (en) * 2009-09-28 2010-03-17 中国科学院过程工程研究所 Synthesis of alcoholamines functionalized ionic liquid
CN101716496A (en) * 2009-11-24 2010-06-02 南京农业大学 Method for surface modification processing on biomass environmental adsorbing material by KOH
CN101993378A (en) * 2010-09-10 2011-03-30 中国石油大学(北京) Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof
CN102099095A (en) * 2008-05-21 2011-06-15 科罗拉多大学校董事会,法人 Ionic liquids and methods for using the same
CN102451653A (en) * 2010-10-27 2012-05-16 中国科学院大连化学物理研究所 Micro reaction method for realizing efficient absorption of acid gas
CN103301807A (en) * 2013-06-07 2013-09-18 常州大学 Preparation method of high-efficiency composite attapulgite/rice hull activated carbon purified water material
CN103958029A (en) * 2011-12-08 2014-07-30 川崎重工业株式会社 Method and apparatus for separating hydrogen sulfide, and hydrogen production system using same
CN104474846A (en) * 2014-09-01 2015-04-01 常州大学 A desulfurizer for removing H2S in natural gas and its preparation method
CN109589949A (en) * 2018-12-21 2019-04-09 齐鲁工业大学 A kind of synthetic method and application of ionic liquid loaded porous material

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1698929A (en) * 2005-05-09 2005-11-23 中国科学院过程工程研究所 Alcoholamine carboxylate functionalized ionic liquid
CN102099095A (en) * 2008-05-21 2011-06-15 科罗拉多大学校董事会,法人 Ionic liquids and methods for using the same
CN101671259A (en) * 2009-09-28 2010-03-17 中国科学院过程工程研究所 Synthesis of alcoholamines functionalized ionic liquid
CN101716496A (en) * 2009-11-24 2010-06-02 南京农业大学 Method for surface modification processing on biomass environmental adsorbing material by KOH
CN101993378A (en) * 2010-09-10 2011-03-30 中国石油大学(北京) Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof
CN102451653A (en) * 2010-10-27 2012-05-16 中国科学院大连化学物理研究所 Micro reaction method for realizing efficient absorption of acid gas
CN103958029A (en) * 2011-12-08 2014-07-30 川崎重工业株式会社 Method and apparatus for separating hydrogen sulfide, and hydrogen production system using same
CN103301807A (en) * 2013-06-07 2013-09-18 常州大学 Preparation method of high-efficiency composite attapulgite/rice hull activated carbon purified water material
CN104474846A (en) * 2014-09-01 2015-04-01 常州大学 A desulfurizer for removing H2S in natural gas and its preparation method
CN109589949A (en) * 2018-12-21 2019-04-09 齐鲁工业大学 A kind of synthetic method and application of ionic liquid loaded porous material

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A S XIAO ET AL.: "Removal of hydrogen sulfide on activated carbon supported ionic liquids", 《THE 3RD INTERNATIONAL CONFERENCE ON NEW MATERIAL AND CHEMICAL INDUSTRY》 *
F.C.里森费尔德等: "《气体净化》", 31 July 1982 *
刘新鹏: "用于硫化氢脱除与硫资源回收的绿色脱硫新体系性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *
宁平等: "《生物质活性炭催化剂的制备及脱硫应用》", 31 January 2020 *
管国锋等: "介孔分子筛固载离子液体的制备及应用研究进展", 《石油化工》 *
翟玉春: "《冶金电化学》", 31 July 2020 *
马云倩等: "离子液体和醇胺溶液复配脱硫剂吸收H2S及再生性能", 《高等学校化学学报》 *

Similar Documents

Publication Publication Date Title
CN113603087B (en) Nitrogen-rich biomass-based activated carbon with hierarchical pore microchannel structure and application thereof
Nguyen et al. A novel removal of CO2 using nitrogen doped biochar beads as a green adsorbent
Xu et al. Chemical transformation of CO2 during its capture by waste biomass derived biochars
Guo et al. A cost-effective synthesis of heteroatom-doped porous carbon by sulfur-containing waste liquid treatment: As a promising adsorbent for CO2 capture
Choo et al. Hydrogen sulfide adsorption by alkaline impregnated coconut shell activated carbon
Pan et al. Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg2+ removal from aqueous solution
CN109260896B (en) Ammonium thiocyanate eutectic solvent for absorbing ammonia gas and ammonia gas adsorption method
CN108479710B (en) Preparation method and application of porous carbon material
CN104368307A (en) Preparation method of special active carbon for ammonia adsorption
CN110605108A (en) A method for regeneration of desulfurization and denitrification waste activated carbon
CN110252255A (en) A kind of preparation method and application of gaseous mercury adsorbent
Saliba et al. Adsorption of heavy metal ions on virgin and chemically-modified lignocellulosic materials
CN104128161B (en) A kind of amino modified activated coke heavy metal absorbent and preparation method thereof
CN113231037A (en) Solid amine adsorbent for removing trace hydrogen sulfide and preparation method thereof
CN112340830A (en) Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in persulfate activation treatment of high-salt organic wastewater
Wu et al. Kinetics and thermodynamics study on low energy synthesis of porous geopolymer based solid amine sorbent for efficient CO2 capture
Li et al. Toluene and water vapor adsorption characteristics and selectivity on hydrophobic resin-based activated carbon
CN120679302A (en) Method for separating HCl from acidic gas mixture using ionic liquid
Guo et al. Magnesium modified algae biochar for phosphorus adsorption: Synthesis, experimental analysis, DFT calculations and regeneration
CN107398143A (en) Non- water absorbent for carbon dioxide removal in admixture of gas
CN114682213A (en) Flame-retardant activated carbon for adsorbing ammonia gas and preparation method thereof
CN118698501B (en) Modified mesoporous biochar adsorbent and preparation method and application thereof
WO2014056164A1 (en) Regeneration method for cu-btc material
CN119158383A (en) Preparation method and application of a marine MOF-based porous liquid carbon capture absorbent
CN113231036A (en) Supported adsorbent for removing ultralow-concentration hydrogen sulfide and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210810

RJ01 Rejection of invention patent application after publication