CN115463534A - Method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production - Google Patents
Method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production Download PDFInfo
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- CN115463534A CN115463534A CN202211341520.XA CN202211341520A CN115463534A CN 115463534 A CN115463534 A CN 115463534A CN 202211341520 A CN202211341520 A CN 202211341520A CN 115463534 A CN115463534 A CN 115463534A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 121
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 63
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000007789 gas Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 95
- 239000003513 alkali Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012266 salt solution Substances 0.000 claims abstract description 45
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000011282 treatment Methods 0.000 claims abstract description 34
- 239000002912 waste gas Substances 0.000 claims abstract description 22
- 238000000909 electrodialysis Methods 0.000 claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000002250 absorbent Substances 0.000 claims abstract description 18
- 230000002745 absorbent Effects 0.000 claims abstract description 18
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000000919 ceramic Substances 0.000 claims description 27
- 238000000108 ultra-filtration Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003011 anion exchange membrane Substances 0.000 claims description 9
- 238000005341 cation exchange Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010819 recyclable waste Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production, belongs to the technical field of waste gas treatment, and can solve the problems of high production cost and environmental pollution in the prior art. The technical scheme is that residual hydrogen chloride waste gas which is not absorbed by water and is generated by preparing m/p-phthaloyl chloride is introduced into an alkali absorption tower, and an inorganic alkali solution is taken as an absorbent to obtain a salt solution I; carrying out solid-liquid separation on the salt solution I to remove solids to obtain a salt solution II; concentrating the salt solution II by reverse osmosis to obtain concentrated salt water; carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain dilute hydrochloric acid and an alkali solution; transferring the dilute hydrochloric acid to an absorption pool of byproduct hydrochloric acid, and transferring the alkali solution to an alkali absorption tower containing residual hydrogen chloride. The method can be applied to the treatment of residual hydrogen chloride in the synthesis of m/p-phthaloyl chloride, realizes salt-free and near-zero emission, reduces the waste gas treatment cost and relieves the environmental protection pressure.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a treatment method of residual hydrogen chloride gas which is not absorbed after hydrogen chloride generated in m/p-phthaloyl chloride production is subjected to primary treatment to prepare hydrochloric acid.
Background
At present, in the production process of m/p-phthaloyl chloride, m/p-phthaloyl chloride is mostly prepared from m/p-phthalic acid and thionyl chloride as raw materials through an acyl chlorination reaction, wherein the obtained by-products are a large amount of mixed gas of hydrogen chloride and sulfur dioxide, although the treated sulfur dioxide can be used as a synthesis raw material of the thionyl chloride, most of hydrogen chloride produces hydrochloric acid after being absorbed by water, but part of hydrogen chloride cannot be absorbed and needs to be discharged into an alkali absorption tower for subsequent treatment, and the part of hydrogen chloride entering the alkali absorption tower can be neutralized with alkali to produce brine, but the process consumes a large amount of alkali, and the production cost is increased; furthermore, the obtained brine is generally treated by an evaporation crystallization mode, so that the treatment cost is high, a large amount of sodium chloride waste residues are obtained by evaporation and are usually transported to a hazardous waste treatment center to be treated by a landfill mode, the high treatment cost is generated, and the huge pressure is brought to the environmental protection.
Therefore, there is a need in the art to provide a new way to treat residual hydrogen chloride gas that is not absorbed after the hydrogen chloride produced in the production of m/p-phthaloyl chloride is initially treated to produce hydrochloric acid.
Disclosure of Invention
Aiming at the technical problems of high treatment cost and environmental pollution of waste gas generated in the production of the m/p-phthaloyl chloride, the invention provides the method for treating the residual hydrogen chloride gas in the production of the m/p-phthaloyl chloride, which has the advantages of reducing the treatment cost of the waste gas and lightening the environmental protection pressure.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production comprises the following steps:
introducing residual hydrogen chloride waste gas which is not absorbed by water and is generated by preparing m/p-phthaloyl chloride into an alkali absorption tower, and taking an inorganic alkali solution as an absorbent to obtain a salt solution I;
carrying out solid-liquid separation on the salt solution I to remove solids to obtain a salt solution II;
concentrating the salt solution II by reverse osmosis to obtain concentrated salt water;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain dilute hydrochloric acid and an alkali solution;
transferring the dilute hydrochloric acid to an absorption pool of byproduct hydrochloric acid, and transferring the alkali solution to an alkali absorption tower containing residual hydrogen chloride.
Preferably, the concentration of the inorganic alkali solution is 5-30%, and the inorganic alkali is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.
Preferably, the solid-liquid separation method is at least one of centrifugal separation, squeezing separation, ceramic membrane separation, floatation separation and sedimentation separation.
Preferably, the solid-liquid separation is performed by ceramic membrane separation.
Preferably, the filtering temperature of a ceramic filter membrane separator used for ceramic filter membrane separation is set to be 30-60 ℃, the membrane surface flow rate is set to be 0.5-10 m/s, the operating pressure is set to be 0.1Mpa-1Mpa, a ceramic ultrafiltration membrane is adopted, and the average pore diameter is 0.01-1 mu m.
Preferably, the reverse osmosis concentration temperature is set to be 30-60 ℃, and the operation pressure is set to be 1.0-8.0 Mpa.
Preferably, the bipolar membrane electrodialysis treatment adopts a three-chamber electrodialysis membrane structure device, which comprises three chamber structures of a bipolar membrane, a cation exchange membrane and an anion exchange membrane.
Preferably, the bipolar membrane, the cation exchange membrane and the anion exchange membrane are all homogeneous membranes.
Preferably, in the bipolar membrane electrodialysis treatment, the stack voltage of the bipolar membrane is set to be 20V-35V, the current is set to be 2A-4.4A, the water inlet temperature is set to be 30-50 ℃, and the pH value of inlet water is set to be 3-9.
Preferably, the concentration of the dilute hydrochloric acid is 5-15%, and the concentration of the alkali solution is 5-30%.
Compared with the prior art, the invention has the advantages and positive effects that: the invention provides a method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production, which is a recyclable waste gas treatment method and is used as an integral technical scheme, wherein the whole process is only added with partial alkali during the first treatment, and the subsequent treatment process is almost not added with alkali, so that the collection and reutilization of hydrogen chloride waste gas are realized by completely depending on the self circulation of the reaction, near zero emission is realized, the environment is protected, and the recovery rate of hydrogen chloride is improved; the consumption of alkali is reduced, and the production cost is further reduced; the amount of the generated hazardous waste is obviously reduced, and further the cost for hazardous waste treatment is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a method for treating residual hydrogen chloride gas in production of m/p-phthaloyl chloride, in particular to a method for treating residual hydrogen chloride waste gas which is not absorbed by water after hydrochloric acid is prepared by primarily treating hydrogen chloride gas generated in the reaction process by using m/p-phthalic acid and thionyl chloride as raw materials, which specifically comprises the following steps:
introducing residual hydrogen chloride waste gas which is generated by preparing m/p-phthaloyl chloride and is not absorbed by water into an alkali absorption tower, and reacting to obtain a salt solution I by taking 5-30% of inorganic alkali solution as an absorbent, wherein the inorganic alkali is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate;
performing solid-liquid separation on the first salt solution to remove solids to obtain a second salt solution, wherein the solid-liquid separation mode adopts at least one of centrifugal separation, squeezing separation, ceramic filter membrane separation, floating separation and settling separation;
concentrating the salt solution II by reverse osmosis to obtain concentrated salt water, wherein the reverse osmosis concentration temperature is set to be 30-60 ℃, and the operation pressure is set to be 1.0Mpa to 8.0Mpa;
carrying out electrodialysis treatment on concentrated saline water through a bipolar membrane to obtain dilute hydrochloric acid and alkaline solution, wherein bipolar membrane electrodialysis equipment comprises a bipolar membrane, a cation exchange membrane and an anion exchange membrane, the bipolar membrane, the cation exchange membrane and the anion exchange membrane are homogeneous membranes, the stack voltage of the bipolar membrane is set to be 20V to 35V, the current is set to be 2A to 4.4A, the water inlet temperature is set to be 30-50 ℃, and the pH of inlet water is set to be 3 to 9;
transferring dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring an alkali solution into a residual hydrogen chloride alkali absorption tower to be used as an absorbent of subsequent residual hydrogen chloride, wherein the concentration of the dilute hydrochloric acid is 5-15%, and the concentration of the alkali solution is 5-30%, preferably 5-25%.
In the step of introducing the residual hydrogen chloride waste gas which is not absorbed by water and is generated in the preparation of m/p-phthaloyl chloride into the alkali absorption tower, the absorbent is preferably sodium hydroxide, and the sodium hydroxide and the hydrogen chloride react to generate water and sodium chloride, so that the product is safe and pollution-free; in actual production, the concentration of the inorganic alkali solution can be 10% -30% or 5% -25%, and the concentration is different, so that the final total absorption amount is different, and the whole reaction process is not influenced.
The method comprises the step of removing crystallized and precipitated solids in the solid-liquid separation step of a salt solution I, wherein the solid-liquid separation mode is preferably ceramic filter membrane separation, a ceramic filter membrane separator adopts a ceramic ultrafiltration membrane, the average pore diameter is 0.01-1 mu m, the filtration temperature is 30-60 ℃, the membrane surface flow rate is 0.5-10 m/s, and the operation pressure is 0.1Mpa to 1Mpa. It can be understood that, in the technical scheme of the invention, the ceramic filter membrane separation adopts a dynamic cross-flow filtration mode different from the traditional filtration method, under the driving of pressure, the feed liquid moves at a high speed at a certain flow speed on the outer surface of the membrane layer at the inner side of the membrane tube, small molecular substances or liquid pass through the microporous membrane along the direction which is straight with the small molecular substances or liquid, and large molecular substances or solid particles are intercepted by the membrane, so that the fluid achieves the purposes of separation, concentration and purification.
After reverse osmosis concentration, the concentration of concentrated saline water is increased to be 1 to 3 times of the second concentration of the saline solution. It can be understood that, compared with the traditional concentration treatment technology, the reverse osmosis concentration process can maintain the original properties of the substances to a greater extent due to no phase change, improve the concentration efficiency and reduce the energy consumption.
In the invention, the concentrated saline water is processed by the bipolar membrane electrodialysis, and the bipolar membrane electrodialysis can separate the ion species in the solution by using an ion exchange membrane under the driving force of an electric field, thereby providing the opportunity of directly acidifying or alkalizing the process material without adding acid or alkali, and avoiding byproducts or waste liquid and expensive downstream purification steps. According to the technical scheme, the bipolar membrane is positioned on any one side of the anion exchange membrane and the cation exchange membrane to form three compartments, wherein acid liquor is arranged between the bipolar membrane and the anion exchange membrane, alkali liquor is arranged between the bipolar membrane and the cation exchange membrane, and salt liquor is arranged between the cation exchange membrane and the anion exchange membrane. Therefore, the salt solution enters the salt chamber, the water enters the acid chamber and the alkali chamber, and the salt water solution can be converted into alkali and acid through the direct current electric field. According to the invention, the salt solution obtained by absorbing the residual tail gas with the alkali liquor is put into the bipolar membrane electrodialysis equipment, the salt solution is converted into the alkali liquor and dilute hydrochloric acid, the alkali liquor returns to the absorption tower and is used as tail gas absorption liquid, the dilute hydrochloric acid returns to the hydrogen chloride absorption tower, and hydrogen chloride gas is continuously absorbed to prepare hydrochloric acid, so that the residual waste gas of hydrogen chloride in the synthesis of m/p-phthaloyl chloride realizes salt-free and near-zero emission, the waste gas treatment cost is effectively reduced, and the environmental protection pressure is relieved. Due to the characteristics of the bipolar membrane, the bipolar membrane feels cotton to solid matters, solid particles easily cause membrane blockage and influence the service life of the bipolar membrane, possible solids in a salt solution are removed through solid-liquid separation before the bipolar membrane electrodialysis treatment step, and the treatment efficiency of the bipolar membrane is improved through the concentration step. Compared with the existing processing method of evaporative crystallization, the long-term use of the equipment has the advantage of obviously reducing the cost.
In order to more clearly and specifically describe the method for treating residual hydrogen chloride gas in the production of m/p-phthaloyl chloride provided in the examples of the present invention, the following description will be given with reference to specific examples.
Example 1
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 30% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic ultrafiltration membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic ultrafiltration membrane is 1 mu m, the filtration temperature is set to be 60 ℃, the membrane surface flow rate is set to be 5m/s, and the operation pressure is set to be 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain concentrated saline water with concentration of 35%, wherein the temperature is set to 60 ℃, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 15% dilute hydrochloric acid and 15% sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 35V, the current is set to be 4.4A, the water inlet temperature is set to be 50 ℃, and the water inlet pH is set to be 7;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
Example 2
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 20% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic ultrafiltration membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic ultrafiltration membrane is 0.5 mu m, the filtration temperature is set to be 30 ℃, the membrane surface flow velocity is set to be 5m/s, and the operation pressure is 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain concentrated salt water with concentration of 35%, wherein the temperature is set to 30 ℃, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 10% dilute hydrochloric acid and 10% sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 20V, the current is set to be 2A, the water inlet temperature is set to be 40 ℃, and the water inlet pH is set to be 7;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
Example 3
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 10% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic ultrafiltration membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic ultrafiltration membrane is 0.1 mu m, the filtration temperature is set to 40 ℃, the membrane surface flow velocity is set to 5m/s, and the operation pressure is set to 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain concentrated saline water with concentration of 35%, wherein the temperature is set to 60 ℃, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 5% dilute hydrochloric acid and 5% sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 35V, the current is set to be 4.4A, the water inlet temperature is set to be 30 ℃, and the water inlet pH is set to be 7;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
Example 4
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 30% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic ultrafiltration membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic ultrafiltration membrane is 0.01 mu m, the filtration temperature is set to be 60 ℃, the membrane surface flow velocity is set to be 0.5m/s, and the operation pressure is set to be 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain 50% concentrated salt water, wherein the temperature is set to 60 deg.C, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 15% of dilute hydrochloric acid and 25% of sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 35V, the current is set to be 4.4A, the water inlet temperature is set to be 50 ℃, and the water inlet pH is set to be 9;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
Example 5
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 30% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic ultrafiltration membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic ultrafiltration membrane is 0.3 mu m, the filtration temperature is set to be 60 ℃, the membrane surface flow velocity is set to be 10m/s, and the operation pressure is set to be 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain 50% concentrated salt water, wherein the temperature is set to 60 deg.C, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 10% dilute hydrochloric acid and 20% sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 35V, the current is set to be 2A, the water inlet temperature is set to be 40 ℃, and the water inlet pH is set to be 5;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
Example 6
Introducing the residual hydrogen chloride waste gas into an alkali absorption tower, and taking a 30% sodium hydroxide solution as an absorbent to obtain a salt solution I;
separating the salt solution I by using a ceramic filter membrane to remove solids to obtain a salt solution II, wherein the average pore diameter of the ceramic filter membrane is 0.7 mu m, the filtering temperature is set to be 60 ℃, the membrane surface flow rate is set to be 5m/s, and the operating pressure is set to be 1Mpa;
concentrating the second salt solution by reverse osmosis to obtain 50% concentrated salt water, wherein the temperature is set to 60 deg.C, and the operating pressure is set to 5.0Mpa;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain 14% of dilute hydrochloric acid and 23% of sodium hydroxide solution, wherein the bipolar membrane stack voltage is set to be 35V, the current is set to be 4.4A, the water inlet temperature is set to be 50 ℃, and the water inlet pH is set to be 3;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the sodium hydroxide solution into an alkali absorption tower containing residual hydrogen chloride to be used as an absorbent of the subsequent residual hydrogen chloride.
In conclusion, the method can realize the salt-free and near-zero emission treatment of the residual waste gas of the hydrogen chloride in the synthesis of the m/p-phthaloyl chloride, the alkali liquor generated in the reaction can return to the absorption tower to be used as tail gas absorption liquid, and the dilute hydrochloric acid can return to the hydrogen chloride absorption tower, so that the hydrogen chloride gas is required to be absorbed to prepare the hydrochloric acid, the waste gas treatment cost is effectively reduced, and the environmental protection pressure is reduced.
The above list of examples is merely a detailed explanation of possible embodiments of the invention and does not impose any limitation on the scope of the invention, and those skilled in the art can make equivalent embodiments or modifications without departing from the scope of the invention.
Claims (8)
1. A method for treating residual hydrogen chloride gas in m/p-phthaloyl chloride production is characterized by comprising the following steps:
introducing residual hydrogen chloride waste gas which is not absorbed by water and is generated by preparing m/p-phthaloyl chloride into an alkali absorption tower, and taking an inorganic alkali solution as an absorbent to obtain a salt solution I;
carrying out solid-liquid separation on the salt solution I to remove solids to obtain a salt solution II;
concentrating the salt solution II by reverse osmosis to obtain concentrated salt water;
carrying out bipolar membrane electrodialysis treatment on the concentrated saline water to obtain dilute hydrochloric acid and an alkali solution;
transferring the dilute hydrochloric acid into an absorption pool of byproduct hydrochloric acid, and transferring the alkali solution into an alkali absorption tower containing residual hydrogen chloride;
the bipolar membrane electrodialysis treatment adopts three-chamber electrodialysis membrane structure equipment, including three chamber structures of a bipolar membrane, a cation exchange membrane and an anion exchange membrane;
in the bipolar membrane electrodialysis treatment, the stack voltage of the bipolar membrane is set to be 20V to 35V, the current is set to be 2A to 4.4A, the water inlet temperature is set to be 30-50 ℃, and the pH value of inlet water is set to be 3 to 9.
2. The method for treating residual hydrogen chloride gas in the m/p-phthaloyl chloride production according to claim 1, wherein the concentration of the inorganic alkali solution is 5-30%, and the inorganic alkali is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.
3. The method for treating residual hydrogen chloride gas in the production of m/p-phthaloyl chloride according to claim 1, characterized in that the solid-liquid separation mode adopts at least one of centrifugal separation, squeezing separation, ceramic filter membrane separation, floating separation and settling separation.
4. The method for treating residual hydrogen chloride gas in the production of m/p-phthaloyl chloride according to claim 3, characterized in that the solid-liquid separation mode adopts ceramic filter membrane separation.
5. The method for treating the residual hydrogen chloride gas in the m/p-phthaloyl chloride production according to claim 4, wherein the filtering temperature of a ceramic filter membrane separator for ceramic filter membrane separation is set to be 30-60 ℃, the membrane surface flow rate is set to be 0.5-10 m/s, the operating pressure is set to be 0.1Mpa-1Mpa, a ceramic ultrafiltration membrane is adopted, and the average pore diameter is 0.01-1 μm.
6. The method for treating residual hydrogen chloride gas in the m/p-phthaloyl chloride production according to claim 1, wherein the reverse osmosis concentration temperature is set to be 30-60 ℃, and the operating pressure is set to be 1.0-8.0 mpa.
7. The method of claim 1, wherein the bipolar membrane, the cation exchange membrane and the anion exchange membrane are homogeneous membranes.
8. The method for treating residual hydrogen chloride gas in the production of m/p-phthaloyl chloride according to claim 1, wherein the concentration of the dilute hydrochloric acid is 5-15%, and the concentration of the alkali solution is 5-30%.
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| CN105671587A (en) * | 2015-12-10 | 2016-06-15 | 浙江工业大学 | Method and device for preparing methionine and recovering by-product-carbon dioxide |
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| CN114632787A (en) * | 2022-05-18 | 2022-06-17 | 中化(浙江)膜产业发展有限公司 | Industrial salt carbon trapping process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006131982A (en) * | 2004-11-09 | 2006-05-25 | Jfe Steel Kk | Processing method for pickling waste liquid and processing equipment for pickling waste liquid |
| CN105671587A (en) * | 2015-12-10 | 2016-06-15 | 浙江工业大学 | Method and device for preparing methionine and recovering by-product-carbon dioxide |
| CN107469485A (en) * | 2017-09-11 | 2017-12-15 | 郭玉连 | A kind of method for industrial waste gas processing |
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