CN108325492B - Nitration technology and device for preparing H acid - Google Patents
Nitration technology and device for preparing H acid Download PDFInfo
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- CN108325492B CN108325492B CN201810211193.3A CN201810211193A CN108325492B CN 108325492 B CN108325492 B CN 108325492B CN 201810211193 A CN201810211193 A CN 201810211193A CN 108325492 B CN108325492 B CN 108325492B
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- 238000006396 nitration reaction Methods 0.000 title claims abstract description 223
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000005516 engineering process Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 243
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 148
- 238000006277 sulfonation reaction Methods 0.000 claims description 147
- 229910017604 nitric acid Inorganic materials 0.000 claims description 144
- 238000002156 mixing Methods 0.000 claims description 103
- 238000001816 cooling Methods 0.000 claims description 45
- 230000001546 nitrifying effect Effects 0.000 claims description 31
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 230000035484 reaction time Effects 0.000 abstract description 13
- 230000017525 heat dissipation Effects 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 230000029087 digestion Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 13
- 239000002826 coolant Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/007—Aspects relating to the heat-exchange of the feed or outlet devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/0009—Coils
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a nitration process and a device for preparing H acid, which fully combine the characteristics and the requirements of the H acid nitration process, redesign the digestion process and the device in a targeted manner, select and optimize key process parameters and device structures, fully mix the raw materials of the H acid nitration reaction, timely release reaction heat release through increasing heat dissipation area, and correspondingly obtain the H acid nitration process and the device with high production efficiency and greatly improved yield and conversion rate, thereby solving the technical problems of long H acid nitration reaction time and influence on the H acid production efficiency in the prior art.
Description
Technical Field
The invention belongs to the technical field of H acid production, and particularly relates to a nitration process and a device for preparing H acid.
Background
H acid is a special intermediate for manufacturing dye, and is widely applied to industries such as printing and dyeing, spinning, chemical industry and the like. The H-acid is mainly used for producing reactive dyes, direct dyes and acid dyes, and can also be used for producing products such as color-changing acid and the like. The chemical name of H-acid is: 1-amino-8-naphthol-3, 6-disulfonic acid, the dry product is white to gray crystalline powder. Slightly soluble in cold water, easily soluble in hot water, soluble in alkaline solution such as sodium carbonate or caustic soda, etc., and has a reddish brown purple color with ferric trichloride, and is dark green in alkaline solution. At present, the domestic production of H-acid mainly adopts an intermittent method, and the process adopted for producing H-acid by the intermittent method takes refined naphthalene as a main raw material and is prepared through the steps of sulfonation, nitration, denitration, neutralization, reduction, filter pressing, segregation, filtration, dissolution, alkali fusion, segregation, filtration, drying and the like.
The continuous nitrification and denitrification process is an important step in the existing H acid preparation production process, and nitric acid and a sulfonation liquid are required to be fully mixed in the nitrification reaction so as to carry out the reaction. At present, the mixing and nitration reaction is mainly carried out in a reaction kettle, namely nitric acid and sulfonated liquid raw materials are introduced into the reaction kettle, and then are stirred by a stirring device in the reaction kettle so as to achieve full mixing and reaction. However, since the nitration reaction is a strong exothermic process, a large amount of heat is released, the reaction kettle is directly used for mixing reaction, a large amount of heat is generated by mixing a large amount of nitric acid and sulfonated liquid in a short time, the feeding speed of nitric acid cannot be timely released due to the fact that the heat generated by mixing cannot be timely released, the feeding amount of nitric acid per hour is only 60 liters/hour, the reaction time of the final nitration reaction process is as long as 4-5 hours, the production efficiency of the nitration process is affected, the yield and the yield of final H acid are further affected, and the safety of a reaction system may be affected under serious conditions.
In order to overcome the defects, the prior art adopts a process of pre-mixing and then entering a reaction kettle for reaction. For example, patent document CN206082490U discloses a tubular continuous nitrification system, which includes a plurality of overflow nitrifiers connected in series and a plurality of pipeline mixers connected in series, the plurality of pipeline mixers connected in series and the plurality of overflow nitrifiers connected in series are sequentially communicated, a tubular heat exchanger is connected between the plurality of pipeline mixers connected in series, and the overflow nitrifier of the last stage is connected with a storage tank. The tubular continuous nitrification system can fully mix materials and concentrated nitric acid in advance and can radiate heat in time.
Although the scheme releases the reaction heat by mixing reaction in advance and arranging an independent heat dissipation device, the heat generated by mixing in a mixer still gathers in the mixed liquid and cannot be released in time, and the heat needs to flow into a subsequent radiator for release, which can affect the mixing efficiency of the mixing reaction; particularly, nitric acid and sulfonated liquid enter the mixer from the feed inlet, and cannot be fully contacted in a short time to achieve the purposes of rapid large-area contact and accelerating the mixing effect, and the nitric acid and sulfonated liquid need to be in disperse contact with each other through structural members in the mixer in the later mixing stage, so that the mixing effect and efficiency of the sulfonated liquid are affected.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a nitration process and a device for preparing H acid, which fully combine the characteristics and demands of the H acid nitration process, redesign the digestion process and the device in a targeted way, select and optimize key process parameters and device structures, fully mix the raw materials of the H acid nitration reaction, and timely release reaction heat by increasing heat dissipation area, thereby correspondingly obtaining the H acid nitration process and the device with high production efficiency, greatly improved yield and conversion rate, and further solving the technical problems of long H acid nitration reaction time and influence on the H acid production efficiency in the prior art.
To achieve the above object, according to one aspect of the present invention, there is provided a nitration process for producing H acid, comprising the steps of:
(1) Cooling the sulfonation liquid to 45-65 ℃ through a heat exchanger to obtain cooled sulfonation liquid;
(2) Introducing the cooled sulfonated liquid and nitric acid in the step (1) into a tubular mixing reactor, and performing nitration reaction under the cooling condition; the feeding direction of the cooled sulfonated liquid is different from that of the nitric acid, and convection is formed, so that the sulfonated liquid and the nitric acid can be subjected to primary mixing at the inlet of the tubular mixing reactor to obtain primary mixed liquid;
(3) Step (2), performing a first-stage nitration reaction on the primary mixed solution in the tubular mixing reactor under a cooling condition to obtain a first nitration solution;
(4) And (3) introducing the first nitrifying liquid in the step (3) into a reaction kettle to perform second-stage mixing and nitrifying reaction to obtain second nitrifying liquid, and realizing high-efficiency mixed nitrifying in a mode of multistage mixing and multistage heat release.
Preferably, the feeding direction of the sulfonation liquid in the step (2) forms an included angle of 180 degrees with the feeding direction of the nitric acid.
Preferably, in the step (2), the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid form an included angle of 180 degrees, and the feeding direction of the sulfonation liquid or the feeding direction of the nitric acid is opposite to the flowing direction of the feed liquid in the tubular mixed nitration reactor body.
Preferably, in the step (2), the sulfonation liquid forms an included angle of 90 degrees with the feeding direction of the nitric acid, and the feeding direction of the sulfonation liquid or the feeding direction of the nitric acid is opposite to the flowing direction of the materials in the tubular mixing reactor.
Preferably, the feeding volume ratio of the sulfonation liquid to the nitric acid in the step (2) is 8-12:1.
Preferably, the feeding volume ratio of the sulfonation liquid and the nitric acid in the step (2) is 10:1.
According to another aspect of the present invention, there is provided a nitration apparatus for producing H acid, comprising a sulfonation liquid heat exchanger, a tubular mixing nitration reactor and a nitration reaction tank connected in sequence by a pipe;
the sulfonated liquid heat exchanger is used for cooling the sulfonated liquid;
the tubular mixed nitration reactor comprises a sulfonation liquid feeding pipe, a nitric acid feeding pipe, a tubular mixed nitration reactor body, a tubular mixed nitration reactor heat exchange unit and a tubular mixed nitration reactor discharge port; one end of the sulfonation liquid feeding pipe is connected with the sulfonation liquid heat exchanger, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body and stretches into the pipe-type mixed nitration reactor; the nitric acid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body and stretches into the pipe-type mixed nitration reactor; the nitric acid feeding pipe and the sulfonation liquid feeding pipe are positioned on the feeding side of the tubular mixed nitration reactor together; the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid are different and form a certain included angle; the heat exchange unit of the tubular mixed nitration reactor is integrated with the tubular mixed nitration reactor body, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body is released simultaneously;
and the discharge port of the tubular mixed nitration reactor is communicated with the feed port of the nitration reactor.
Preferably, the sulfonation liquid heat exchanger is used for cooling the sulfonation liquid, and the temperature of the sulfonation liquid can be controlled within the range of 45-65 ℃.
Preferably, the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that an included angle of 180 degrees is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid.
Preferably, the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that an included angle of 180 degrees or 90 degrees is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid, and the feeding direction of the sulfonation liquid or the feeding direction of the nitric acid is opposite to the flowing direction of the feed liquid in the tubular mixed nitration reactor body.
Preferably, the heat exchange unit of the tubular mixed nitration reactor is an external jacket arranged at the periphery of the tubular mixed nitration reactor body, or a serpentine condenser tube is arranged at the periphery or inside of the tubular mixed nitration reactor body.
In general, the above technical solution conceived by the present invention can achieve the following advantageous effects compared to the prior art.
(1) The invention provides a nitration process for preparing H acid, which comprises the steps of firstly cooling sulfonation liquid produced by the sulfonation process to a certain temperature, then introducing the sulfonation liquid cooled to a certain temperature range and nitric acid into a tubular mixing reactor for mixing, controlling respective feeding directions of the sulfonation liquid and the nitric acid, and ensuring that a certain included angle is formed between the feeding directions of the sulfonation liquid and the nitric acid so as to ensure that the two materials form a certain degree of convection, so that primary mixing is firstly carried out when the two materials are fed, and heat generated by mixing is released in time under the action of a heat exchange unit integrated with the tubular mixing reactor while primary mixing is carried out; then further carrying out second-stage mixing and nitration reaction in a tubular mixing reactor under the cooling effect of a heat exchange unit, and finally, introducing the mixture into a nitration reaction kettle for third-stage nitration. The process divides the traditional one-step nitrification into three steps, realizes the efficient mixed nitrification by means of multistage mixing and multistage heat release through ingenious control of the feeding direction, selection of a tubular mixing reactor with large heat dissipation area and timely cooling of an integrated heat exchange unit, and shortens the reaction time from 5-6 hours of the traditional one-step kettle type nitrification reaction to 2-3 hours because the heat can be timely released and the feeding amount of nitric acid in unit time can be increased to 100-150 liters/hour.
(2) According to the scheme, through the design and improvement of the structure of the tubular mixer, particularly the feeding direction of the feeding pipe, nitric acid and sulfonated liquid can be fed from different directions, so that convection and violent opposite flushing are formed in the flowing direction, and large-area contact can be achieved between the nitric acid and the sulfonated liquid before mixing, and the mixing efficiency and effect are enhanced;
(3) In the scheme, the heat exchange unit is integrated on the tubular mixing reactor body, so that the heat generated by the nitric acid and the sulfonated liquid can be released simultaneously when the nitric acid and the sulfonated liquid are mixed in the tubular mixing reactor body, and the heat in the mixing process can be released rapidly in time without being accumulated in the mixed liquid, thereby limiting the improvement of the mixing efficiency and effect;
(4) In this scheme, the heat transfer unit of integration on the body on the one hand can release the heat that produces because of the convection current mixes when the feeding fast, on the other hand can release the heat of its production when this internal mixing simultaneously, through tubular blender structural optimization and heat transfer unit's integration, form two-stage mixing and twice thermal mode of release simultaneously, can improve mixing effect and mixing efficiency greatly.
(5) The nitration technology and the device provided by the invention are simple and feasible and have low cost, but the reaction efficiency of the traditional nitration reaction is improved to a great extent.
Drawings
FIG. 1 is a flow chart of the nitration process of H acid according to the invention;
FIG. 2 is a schematic diagram showing the arrangement of the feed pipes for the sulfonation liquid and nitric acid on the feed side of the tubular mixed nitration reactor body according to example 1 of the present invention;
FIG. 3 is a schematic view showing the arrangement of the feeding pipes for the sulfonation liquid and nitric acid on the feeding side of the tubular mixed nitration reactor body according to example 2 of the present invention;
FIG. 4 is a schematic diagram showing the arrangement of the feeding pipes for the sulfonation liquid and nitric acid on the feeding side of the tubular mixed nitration reactor body of example 3 of the present invention.
The same reference numbers are used throughout the drawings to reference like elements or structures, wherein:
1-a sulfonation liquid heat exchanger; 2-a tubular mixed nitration reactor; 21-a sulfonation liquid feeding pipe; 22-nitric acid feed pipe; the device comprises a 23-tubular mixed nitration reactor body, a 24-tubular mixed nitration reactor heat exchange unit, a 241-heat exchange unit cooling medium inlet, a 242-heat exchange unit cooling medium outlet and a 25-tubular mixed nitration reactor discharge outlet; 3-nitration reaction kettle.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a nitration process for preparing H acid, which is prepared by using refined naphthalene as a main raw material and through the steps of sulfonation, nitration, denitration, neutralization, reduction, press filtration, segregation, filtration, dissolution, alkali fusion, segregation, filtration, drying and the like. Specifically, the method comprises the following steps:
(1) Cooling the sulfonated liquid to below 65 ℃ by a heat exchanger, such as 45-65 ℃, preferably about 55 ℃, to obtain cooled sulfonated liquid.
(2) Introducing the sulphonated liquid cooled in the step (1) and nitric acid into a tubular mixing reactor, and performing nitration reaction under the cooling condition, wherein the tubular mixing reactor is preferably horizontal; the feeding direction of the cooled sulfonation liquid is different from that of the nitric acid, and convection is formed, so that the sulfonation liquid and the nitric acid are subjected to primary mixing at the feeding end of the tubular mixing reactor, and a primary mixed liquid is obtained. In order to better promote the mixing of raw materials and simultaneously release heat in time during mixing and reaction, the invention adopts the preferable mode that the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid form an included angle of 180 degrees or an included angle of 90 degrees, so that the sulfonation liquid and the nitric acid can form opposite impact and impact to a certain degree after entering a mixer to obtain primary mixing; meanwhile, the feeding direction of the sulfonated liquid or the feeding direction of the nitric acid is opposite to the flow direction of the feed liquid in the tubular mixed nitration reactor body, so that one of the raw materials forms a folding disturbance after feeding due to the opposite flow direction of the raw materials in the tubular mixed nitration reactor, and the mixing of the raw material liquid is further promoted; the feed inlet height of the sulfonation liquid with high density is as much as possible higher than the feed inlet height of the nitric acid with relatively small density, so that the mixing of the sulfonation liquid and the nitric acid can be further promoted under the action of gravity when the nitrification reaction is carried out in the horizontal tubular mixer. The heat generated in the primary mixing process flows along with the flow in the tubular mixing nitration reactor, and the heat can be released in time under the action of a cooling system of the reactor. The feeding volume ratio of the sulfonation liquid to the nitric acid is 8-12:1, preferably 10:1.
(3) The primary mixed solution in the step (2) is subjected to primary nitration reaction in a tubular mixing reactor under the cooling condition of a cooling system, wherein the reaction time is 10-60 seconds, generally about 30 seconds, and the reaction temperature is about 55 ℃ to obtain a primary nitration solution;
(4) Introducing the first nitrifying liquid obtained in the step (3) into a reaction kettle with a cooling jacket to perform secondary mixing and nitrifying reaction, wherein the reaction time is 2-3 hours, the reaction temperature is 40-60 ℃, preferably 50 ℃, and the second nitrifying liquid is obtained, so that efficient mixing and nitrifying are realized through multistage mixing and multistage heat release.
The invention also provides a nitrifying device for preparing the H acid, which comprises a sulfonated liquid heat exchanger, a tubular mixed nitrifying reactor and a nitrifying reaction kettle which are connected in sequence through pipelines;
the sulfonation liquid heat exchanger is used for cooling the sulfonation liquid; the sulfonation liquid heat exchanger can control the temperature of the sulfonation liquid to 65 ℃ or lower, for example, 45 to 65 ℃, preferably about 55 ℃. The sulfonated liquid heat exchanger can be a plate heat exchanger which can be purchased from the market, and through a specific material design, the heat exchanger can realize automatic temperature control of the sulfonated liquid, namely, when the temperature of the sulfonated liquid rises to a certain temperature, the cooling system is started, and when the temperature of the sulfonated liquid falls to a certain temperature, such as 50 ℃, the cooling system is automatically closed. The initial temperature of the sulfonated liquid obtained from the sulfonation process is about 70-80 ℃, the temperature of the sulfonated liquid is reduced to be favorable for the nitration reaction, but too low temperature of the sulfonated liquid can lead to the increase of the viscosity of the feed liquid, the fluidity is poor and the nitration is unfavorable, so that the temperature range-controllable plate heat exchanger is selected to cool the sulfonated liquid and control the temperature.
The tubular mixed nitration reactor comprises a sulfonation liquid feeding pipe, a nitric acid feeding pipe, a tubular mixed nitration reactor body, a tubular mixed nitration reactor heat exchange unit and a tubular mixed nitration reactor discharge port; one end of a sulfonation liquid feeding pipe is connected with the sulfonation liquid heat exchanger, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body and stretches into the pipe-type mixed nitration reactor; the nitric acid feed pipe penetrates through the pipe wall of the pipe type mixed nitration reactor body and stretches into the pipe type mixed nitration reactor; the nitric acid feeding pipe and the sulfonation liquid feeding pipe are positioned on the feeding side of the tubular mixed nitration reactor together; the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that a certain included angle is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid and the two raw materials are different, and the two raw materials form convection, so that the sulfonation liquid and the nitric acid are primarily mixed at the feeding side of the tubular mixed nitration reactor; the heat exchange unit of the tubular mixed nitration reactor is integrated with the tubular mixed nitration reactor body, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body is released simultaneously. The discharge port of the tubular mixed nitration reactor is communicated with the feed port of the nitration reactor.
The sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, and the preferable setting mode is that the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid form an included angle of 180 degrees or 90 degrees, so that the two raw materials can form impact, opposite impact and convection to a certain extent after being fed, and primary mixing is obtained. Further preferably, under the condition that an included angle is formed so that the feeding directions of the two materials are different, the feeding direction of the sulfonated liquid or the feeding direction of the nitric acid is opposite to the flow direction of the material liquid in the tubular mixed nitration reactor body, so that one of the materials forms a folding disturbance after feeding due to the opposite direction to the material flow direction in the tubular mixed nitration reactor, and the mixing of the material liquid is further promoted; in addition, the height of the feed inlet of the sulfonation liquid with high density is as much as possible higher than that of the feed inlet of the nitric acid with relatively small density, so that the mixture of the sulfonation liquid and the nitric acid can be further promoted under the action of gravity when the nitrification reaction is carried out in the horizontal tubular mixer. Of course, baffles may be provided inside the tubular mixing nitration reactor, as well as to promote further mixing of the two.
The heat exchange unit of the tubular mixed nitration reactor is an external jacket arranged at the periphery of the tubular mixed nitration reactor body, and the jacket can be a straight jacket, a serpentine condenser tube jacket or a serpentine condenser tube arranged in the tubular mixed nitration reactor body. Preferably, the serpentine condenser tube is sleeved on the periphery, so that the flow of liquid in the reactor body, namely the reaction condition, can be observed from the outside, and the device is safer if the liquid penetrates into the condenser tube and other extreme conditions are met.
According to the invention, through preliminary cooling of the sulfonation liquid, then through preliminary mixing of the sulfonation liquid and nitric acid in the tubular mixed nitration reactor, the amount of preliminary mixed heat is small and timely released by means of the special shape and structure of the tubular mixed nitration reactor in cooperation with an integrated heat exchange unit; the heat dissipation area of the tubular mixed nitration reactor is large, and the problem of heat release of the nitration reaction is solved step by step; particularly, the heat exchanger unit is integrally arranged on the tubular mixed nitration reactor, so that heat released in the mixing reaction process is truly and timely released, the nitration reaction temperature can be controlled to be about 55 ℃, and the nitration reaction is particularly beneficial to being carried out; on the other hand, due to the special design, the heat of the nitration reaction can be released in time, the feeding rate of nitric acid, namely the feeding amount of nitric acid in unit time, is greatly increased compared with that of the traditional nitration reaction, and the direct result is that the nitration reaction efficiency is greatly improved.
The following are examples:
example 1
The invention provides a nitration process of H acid, which is shown in figure 1 and comprises the following steps:
(1) Cooling the sulfonation liquid to 55 ℃ through a heat exchanger to obtain cooled sulfonation liquid.
(2) Introducing the sulfonated liquid cooled in the step (1) and nitric acid into a tubular mixing reactor, and performing nitration reaction under the cooling condition, wherein the tubular mixing reactor is horizontal; the feeding direction of the cooled sulfonation liquid is different from that of the nitric acid, and convection is formed, so that the sulfonation liquid and the nitric acid are subjected to primary mixing at the feeding end of the tubular mixing reactor, and a primary mixed liquid is obtained. Wherein the feeding volume ratio of the sulfonation liquid to the nitric acid is 10:1.
(3) Performing primary nitration reaction on the primary mixed solution in the step (2) in a tubular mixing reactor under the cooling condition of a cooling system, wherein the reaction time is 30 seconds, and the reaction temperature is 55 ℃ to obtain a first nitration solution;
(4) And (3) introducing the first nitrifying liquid in the step (3) into a reaction kettle with a cooling jacket for carrying out secondary mixing and nitrifying reaction, wherein the reaction time is 2 hours, the reaction temperature is 50 ℃, and the second nitrifying liquid is obtained, and the nitric acid feeding amount per hour is 150L.
FIG. 2 is a view showing a nitrification apparatus according to the present invention, as shown in FIG. 1, the nitrification apparatus of the present invention according to a preferred embodiment of the present invention includes a sulfonation liquid heat exchanger 1, a tubular hybrid nitrification reactor 2, and a nitrification reactor 3, which are sequentially connected by pipes. Wherein 21-sulfonation liquid feeding pipe; 22-nitric acid feed pipe; the device comprises a 23-tubular mixed nitration reactor body, a 24-tubular mixed nitration reactor heat exchange unit, a 241-heat exchange unit cooling medium inlet, a 242-heat exchange unit cooling medium outlet and a 25-tubular mixed nitration reactor discharge outlet; 3-nitration reaction kettle.
The sulfonated liquid heat exchanger 21 is a plate heat exchanger and is used for cooling the sulfonated liquid, and the temperature of the sulfonated liquid is controlled to be 55 ℃. Plate heat exchangers are commercially available, which can be automatically controlled according to the temperature of the sulphonated liquid, i.e. when the temperature of the sulphonated liquid rises to 65 ℃, the cooling system is turned on, and when the temperature drops to 45 ℃, the cooling system is automatically turned off.
The tubular mixed nitration reactor 2 comprises a sulfonation liquid feeding pipe 21, a nitric acid feeding pipe 22, a tubular mixed nitration reactor body 23, a tubular mixed nitration reactor heat exchange unit 24 and a tubular mixed nitration reactor discharge port 25; one end of a sulfonation liquid feeding pipe 21 is connected with the sulfonation liquid heat exchanger 1, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body 23 and stretches into the pipe-type mixed nitration reactor 2, so that the sulfonation liquid cooled by the heat exchanger is conveyed into the pipe-type mixed nitration reactor body; one end of a nitric acid feeding pipe 22 is connected with a nitric acid storage tank, and the other end of the nitric acid feeding pipe passes through the pipe wall of the pipe type mixed nitration reactor body 23 and stretches into the pipe type mixed nitration reactor 2 so as to convey nitric acid into the pipe type mixed nitration reactor body 23, and the nitric acid feeding pipe 22 and a sulfonation liquid feeding pipe 21 are positioned on the feeding side of the pipe type mixed nitration reactor 2 together; the sulfonation liquid feeding pipe 21 and the nitric acid feeding pipe 22 are correspondingly arranged, the feeding direction of the nitric acid feeding pipe 22 is rightward, the feeding direction of the sulfonation liquid feeding pipe 21 is leftward, the material flowing direction in the tubular mixed nitration reactor body 23 is rightward, an included angle of 180 ℃ is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid, the feeding direction of the nitric acid is opposite to the material flowing direction in the tubular mixed nitration reactor 2, the specific arrangement is as shown in fig. 2, the sulfonation liquid and the concentrated nitric acid form convection after entering, and primary mixing is carried out on the feeding side of the tubular mixed nitration reactor 2; after the sulfonation liquid flows leftwards and is impacted and mixed with the nitric acid, the left-flowing feed liquid which is primarily mixed flows backwards and rightwards due to the influence of the flowing direction of the main body material, the primary mixing effect is good, and the uniform mixing of the two feed liquids can be basically realized. The heat exchange unit 24 of the tubular mixed nitration reactor is a serpentine condenser pipe integrally arranged on the periphery of the tubular mixed nitration reactor body, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body is released simultaneously; the discharge hole 25 of the tubular mixed nitration reactor is communicated with the feed hole of the nitration reaction kettle 3 and is used for introducing the mixed solution into the reaction kettle for the next nitration reaction.
In this scheme, the nitric acid feeding pipe 22 and the sulfonation liquid feeding pipe 21 are correspondingly arranged on the feeding side of the tubular mixed nitration reactor body 23, that is, the outlets of the two are in a certain position corresponding relation, preferably, the central axis of the pipe body of the nitric acid feeding pipe is at a certain angle, so that the feeding directions of nitric acid and the sulfonation liquid entering the mixer body are different. Specifically, the nitric acid feed pipe 22 and the sulfonation liquid feed pipe 21 are preferably at an angle, for example, between 90 and 180 degrees, and more preferably 180 degrees, to the central axes of the mixer body 10, such that the central axes of the nitric acid feed pipe 22 and the sulfonation liquid feed pipe 21 are axially parallel to the mixer body, and such that one of the nitric acid feed direction or the sulfonation liquid feed direction therein is opposite to the flow direction of the mixed liquid in the mixer body. Of course, the two feeding directions are not limited to 180 degrees or axially parallel, and practically any angle is sufficient, so long as the two feeding directions are different, for example, the central axes of the outlets of the nitric acid feeding pipe 22 and the sulfonation liquid feeding pipe 21 in the mixer body may be 90 degrees, that is, the feeding directions are mutually perpendicular, etc.
In the scheme, through the optimized improvement of the structure of the tubular mixed nitration reactor 2, particularly the feeding direction of a feeding port, nitric acid and sulfonated liquid can be fed from different directions, so that convection and violent opposite flushing are formed in the flowing direction, and the two can be contacted in a large area before mixing, thereby enhancing the mixing efficiency and effect.
As shown in fig. 2, the heat exchange unit 24 of the tubular hybrid nitration reactor in this embodiment is integrally provided on the tubular hybrid nitration reactor body 22, so as to allow the heat generated by the nitric acid and the sulfonation liquid to be simultaneously released when they are mixed in the body.
In this embodiment, the heat exchange unit 24 of the tubular hybrid nitration reactor may be a serpentine heat exchange tube or a straight heat exchange tube jacket disposed at the periphery of the mixer body, or may be a serpentine condenser tube disposed inside, and the jacket or the condenser tube is filled with a cooling medium, and both a heat exchange unit cooling medium inlet 241 and a heat exchange unit cooling medium outlet 242 are disposed.
In the scheme, the heat exchange unit is integrated on the mixer body, so that the heat generated by the nitric acid and the sulfonated liquid during mixing in the mixer body is released simultaneously, the heat during mixing can be released rapidly in time, and the heat cannot be accumulated in the mixed liquid, so that the mixing efficiency and the effect are limited and improved;
moreover, through the heat exchange unit integrated on the body, on the one hand, the heat generated by convection mixing during feeding can be quickly released, on the other hand, the heat generated during the mixing in the body can be simultaneously released, and the two-stage mixing and twice heat simultaneous release mode is formed through the structural optimization of the tubular mixer and the integration of the heat exchange unit, so that the mixing effect and the mixing efficiency can be greatly improved.
The tubular mixed nitration reactor 2 of the scheme can enable the sulfonation liquid and the nitric acid to be subjected to primary mixing at the feeding side of the sulfonation liquid and the nitric acid, then flow through the mixed nitration reactor 2, and finally flow out of the discharge port 25 of the tubular mixed nitration reactor and enter the nitration reaction kettle 3.
The scheme fully combines the characteristics and the requirements of the H acid nitration technology, optimizes and improves the mixer involved in the nitration technology in a targeted manner, can fully mix the raw materials of the H acid nitration reaction, and can remove the reaction heat in time, thereby correspondingly obtaining the H acid nitration with high production efficiency and greatly improved yield and conversion rate, and further solving the technical problems of long H acid nitration reaction time and influence on the production efficiency of the H acid in the prior art.
Example 2
The invention provides a nitration process of H acid, which comprises the following steps:
(1) Cooling the sulfonation liquid to 62 ℃ through a heat exchanger to obtain cooled sulfonation liquid.
(2) Introducing the sulfonated liquid cooled in the step (1) and nitric acid into a tubular mixing reactor, and performing nitration reaction under the cooling condition, wherein the tubular mixing reactor is horizontal; the feeding direction of the cooled sulfonation liquid is different from that of the nitric acid, and convection is formed, so that the sulfonation liquid and the nitric acid are subjected to primary mixing at the feeding end of the tubular mixing reactor, and a primary mixed liquid is obtained. Wherein the feeding volume ratio of the sulfonation liquid to the nitric acid is 8:1.
(3) Performing primary nitration reaction on the primary mixed solution in the step (2) in a tubular mixing reactor under the cooling condition of a cooling system, wherein the reaction time is 50 seconds, and the reaction temperature is 60 ℃ to obtain a first nitration solution;
(4) And (3) introducing the first nitrifying liquid in the step (3) into a reaction kettle with a cooling jacket for carrying out secondary mixing and nitrifying reaction, wherein the reaction time is 3 hours, the reaction temperature is 55 ℃, and the second nitrifying liquid is obtained, and the nitric acid feeding amount per hour is 100L.
The nitrifying device of the embodiment is shown in fig. 3, and comprises a sulfonated liquid heat exchanger 1, a tubular mixed nitrifying reactor 2 and a nitrifying reaction kettle 3 which are connected in sequence through pipelines.
The sulfonated liquid heat exchanger 1 is a plate heat exchanger and is used for cooling the sulfonated liquid, and the temperature of the sulfonated liquid is controlled to be 62 ℃.
The tubular mixed nitration reactor 2 comprises a sulfonation liquid feeding pipe 21, a nitric acid feeding pipe 22, a tubular mixed nitration reactor body 23, a tubular mixed nitration reactor heat exchange unit 24 and a tubular mixed nitration reactor discharge port 25; one end of a sulfonation liquid feeding pipe 21 is connected with the sulfonation liquid heat exchanger 1, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body 23 and stretches into the pipe-type mixed nitration reactor 2, so that the sulfonation liquid cooled by the heat exchanger is conveyed into the pipe-type mixed nitration reactor body 23; one end of a nitric acid feeding pipe 22 is connected with a nitric acid storage tank, and the other end of the nitric acid feeding pipe passes through the pipe wall of the pipe type mixed nitration reactor body 23 and stretches into the pipe type mixed nitration reactor 2 so as to convey nitric acid into the pipe type mixed nitration reactor body 23, and the nitric acid feeding pipe 22 and a sulfonation liquid feeding pipe 21 are positioned on the feeding side of the pipe type mixed nitration reactor 2 together; the sulfonation liquid feeding pipe 21 and the nitric acid feeding pipe 22 are correspondingly arranged, the feeding direction of the nitric acid feeding pipe 22 is from bottom to top, the feeding direction of the sulfonation liquid feeding pipe 21 is leftward, the material flowing direction in the tubular mixed nitration reactor body 23 is rightward, an included angle of 90 ℃ is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid, the feeding direction of the sulfonation liquid is opposite to the material flowing direction in the tubular mixed nitration reactor 2, and as shown in figure 3, convection is formed after the sulfonation liquid and the concentrated nitric acid enter, and primary mixing is carried out on the feeding side of the tubular mixed nitration reactor 2; after the sulfonation liquid flows leftwards and is impacted and mixed with the nitric acid, the left-flowing feed liquid which is primarily mixed flows backwards and rightwards due to the influence of the flowing direction of the main body material, the primary mixing effect is good, and the uniform mixing of the two feed liquids can be basically realized. The heat exchange unit 24 of the tubular mixed nitration reactor is a serpentine condenser pipe integrally arranged on the periphery of the tubular mixed nitration reactor body 23, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body 23 is released simultaneously; the discharge hole 25 of the tubular mixed nitration reactor is communicated with the feed hole of the nitration reaction kettle 3 and is used for introducing the mixed solution into the reaction kettle for the next nitration reaction.
Example 3
The invention provides a nitration process of H acid, which comprises the following steps:
(1) Cooling the sulfonation liquid to 48 ℃ through a heat exchanger to obtain cooled sulfonation liquid.
(2) Introducing the sulfonated liquid cooled in the step (1) and nitric acid into a tubular mixing reactor, and performing nitration reaction under the cooling condition, wherein the tubular mixing reactor is horizontal; the feeding direction of the cooled sulfonation liquid is different from that of the nitric acid, and convection is formed, so that the sulfonation liquid and the nitric acid are subjected to primary mixing at the feeding end of the tubular mixing reactor, and a primary mixed liquid is obtained. Wherein the feeding volume ratio of the sulfonation liquid to the nitric acid is 12:1.
(3) Performing primary nitration reaction on the primary mixed solution in the step (2) in a tubular mixing reactor under the cooling condition of a cooling system, wherein the reaction time is 60 seconds, and the reaction temperature is 55 ℃ to obtain a first nitration solution;
(4) And (3) introducing the first nitrifying liquid in the step (3) into a reaction kettle with a cooling jacket for carrying out secondary mixing and nitrifying reaction, wherein the reaction time is 2.5 hours, the reaction temperature is 50 ℃, and the second nitrifying liquid is obtained, and the nitric acid feeding amount per hour is 120L.
FIG. 4 is a view showing a nitrification apparatus according to the present invention, as shown in FIG. 1, the nitrification apparatus of the present invention according to a preferred embodiment of the present invention includes a sulfonation liquid heat exchanger 1, a tubular hybrid nitrification reactor 2, and a nitrification reactor 3, which are sequentially connected by pipes.
The sulfonated liquid heat exchanger 1 is a plate heat exchanger and is used for cooling the sulfonated liquid, and the temperature of the sulfonated liquid is controlled to be 48 ℃. Plate heat exchangers are commercially available, which can be automatically controlled according to the temperature of the sulphonated liquid, i.e. when the temperature of the sulphonated liquid rises to 65 ℃, the cooling system is turned on, and when the temperature drops to 45 ℃, the cooling system is automatically turned off.
The tubular mixed nitration reactor 2 comprises a sulfonation liquid feeding pipe 21, a nitric acid feeding pipe 22, a tubular mixed nitration reactor body 23, a tubular mixed nitration reactor heat exchange unit 24 and a tubular mixed nitration reactor discharge port 25; one end of a sulfonation liquid feeding pipe 21 is connected with the sulfonation liquid heat exchanger 1, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body 23 and stretches into the pipe-type mixed nitration reactor 2, so that the sulfonation liquid cooled by the heat exchanger is conveyed into the pipe-type mixed nitration reactor body 23; one end of a nitric acid feeding pipe 21 is connected with a nitric acid storage tank, and the other end of the nitric acid feeding pipe passes through the pipe wall of the pipe type mixed nitration reactor body 23 and stretches into the pipe type mixed nitration reactor 2 so as to convey nitric acid into the pipe type mixed nitration reactor body 23, and a nitric acid feeding pipe 22 and a sulfonation liquid feeding pipe 21 are positioned on the feeding side of the pipe type mixed nitration reactor 2 together; the sulfonation liquid feeding pipe 21 and the nitric acid feeding pipe 22 are correspondingly arranged, the feeding direction of the sulfonation liquid feeding pipe 21 is rightward, the feeding direction of the nitric acid feeding pipe 22 is leftward, the material flowing direction in the tubular mixed nitration reactor body 23 is rightward, an included angle of 180 ℃ is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid, the feeding direction of the nitric acid is opposite to the material flowing direction in the tubular mixed nitration reactor, the specific arrangement is as shown in fig. 4, the sulfonation liquid and the concentrated nitric acid form convection after entering, and primary mixing is carried out on the feeding side of the tubular mixed nitration reactor; after the sulfonation liquid flows leftwards and is impacted and mixed with the nitric acid, the left-flowing feed liquid which is primarily mixed flows backwards and rightwards due to the influence of the flowing direction of the main body material, the primary mixing effect is good, and the uniform mixing of the two feed liquids can be basically realized. The heat exchange unit 24 of the tubular mixed nitration reactor is a serpentine condenser pipe integrally arranged on the periphery of the tubular mixed nitration reactor body, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body 23 is released simultaneously; the discharge hole 25 of the tubular mixed nitration reactor is communicated with the feed hole of the nitration reaction kettle 3 and is used for introducing the mixed solution into the reaction kettle for the next nitration reaction.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. A nitration process for preparing H acid is characterized in that the preparation of H acid is realized by a nitration device,
the nitrification device comprises a sulfonation liquid heat exchanger, a tubular mixed nitrification reactor and a nitrification reaction kettle which are sequentially connected through pipelines, wherein the tubular mixed nitrification reactor comprises a sulfonation liquid feeding pipe, a nitric acid feeding pipe, a tubular mixed nitrification reactor body and a tubular mixed nitrification reactor heat exchange unit, and the nitric acid feeding pipe and the sulfonation liquid feeding pipe are positioned on the feeding side of the tubular mixed nitrification reactor together; the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid are different and form a certain included angle, and the heat exchange unit of the tubular mixed nitration reactor is integrated with the tubular mixed nitration reactor body;
the nitration process is realized by the nitration device and comprises the following steps:
(1) Cooling the sulfonated liquid to 45-65 ℃ through a sulfonated liquid heat exchanger to obtain cooled sulfonated liquid;
(2) Introducing the cooled sulfonated liquid and nitric acid in the step (1) into a tubular mixed nitration reactor, and carrying out nitration reaction under the cooling condition; the feeding direction of the sulphonated liquid after cooling is different from the feeding direction of the nitric acid and forms convection, and the feeding direction of the sulphonated liquid or the feeding direction of the nitric acid is opposite to the flowing direction of the feed liquid in the tubular mixed nitration reactor body, so that the sulphonated liquid and the nitric acid can be subjected to primary mixing at the inlet of the tubular mixed nitration reactor to obtain primary mixed liquid, and the feeding direction of the sulphonated liquid and the feeding direction of the nitric acid form an included angle of 180 degrees or 90 degrees;
(3) Step (2), performing a first-stage nitration reaction on the primary mixed solution in the tubular mixed nitration reactor under a cooling condition to obtain a first nitration solution;
(4) And (3) introducing the first nitrifying liquid in the step (3) into the nitrifying reaction kettle to perform second-stage mixing and nitrifying reaction to obtain second nitrifying liquid, and realizing efficient mixed nitrifying in a multi-stage mixing and multi-stage heat release mode.
2. The nitration process of claim 1, wherein the sulfonation liquid and nitric acid of step (2) are fed in a volume ratio of from 8 to 12:1.
3. A nitrifying device for preparing H acid is characterized by comprising a sulfonated liquid heat exchanger, a tubular mixed nitrifying reactor and a nitrifying reaction kettle which are connected in sequence through pipelines;
the sulfonated liquid heat exchanger is used for cooling the sulfonated liquid;
the tubular mixed nitration reactor comprises a sulfonation liquid feeding pipe, a nitric acid feeding pipe, a tubular mixed nitration reactor body, a tubular mixed nitration reactor heat exchange unit and a tubular mixed nitration reactor discharge port; one end of the sulfonation liquid feeding pipe is connected with the sulfonation liquid heat exchanger, and the other end of the sulfonation liquid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body and stretches into the pipe-type mixed nitration reactor; the nitric acid feeding pipe penetrates through the pipe wall of the pipe-type mixed nitration reactor body and stretches into the pipe-type mixed nitration reactor; the nitric acid feeding pipe and the sulfonation liquid feeding pipe are positioned on the feeding side of the tubular mixed nitration reactor together; the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid are different and form a certain included angle; the heat exchange unit of the tubular mixed nitration reactor is integrated with the tubular mixed nitration reactor body, so that heat generated when the sulfonation liquid and the nitric acid are mixed in the tubular mixed nitration reactor body is released simultaneously;
the sulfonation liquid feeding pipe and the nitric acid feeding pipe are correspondingly arranged, so that an included angle of 180 degrees or 90 degrees is formed between the feeding direction of the sulfonation liquid and the feeding direction of the nitric acid, and the feeding direction of the sulfonation liquid or the feeding direction of the nitric acid is opposite to the flowing direction of the feed liquid in the tubular mixed nitration reactor body;
the discharge port of the tubular mixed nitration reactor is communicated with the feed port of the nitration reactor,
the heat exchange unit of the tubular mixed nitration reactor is an external jacket arranged at the periphery of the tubular mixed nitration reactor body, or a serpentine condenser tube is arranged at the periphery or inside of the tubular mixed nitration reactor body.
4. A nitration plant according to claim 3, characterised in that the sulphonation liquid heat exchanger is adapted to cool the sulphonation liquid and to control the temperature of the sulphonation liquid in the range 45 to 65 ℃.
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| CN113372280A (en) * | 2021-05-25 | 2021-09-10 | 黄冈银河阿迪药业有限公司 | 2-methylimidazole continuous nitration reaction system and continuous nitration process |
| CN115041119A (en) * | 2022-06-08 | 2022-09-13 | 青海施丹弗化工有限责任公司 | Thiophene continuous nitration reaction device |
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