CN115672216A - Sulfonation reaction system and method for preparing resorcinol based on microchannel reactor - Google Patents
Sulfonation reaction system and method for preparing resorcinol based on microchannel reactor Download PDFInfo
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 66
- 230000020477 pH reduction Effects 0.000 claims abstract description 47
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 230000004927 fusion Effects 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 99
- 239000000047 product Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 230000004907 flux Effects 0.000 claims description 28
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000498 cooling water Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 239000008236 heating water Substances 0.000 claims description 12
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 11
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005215 recombination Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- KAVGXOKHWPNOAL-UHFFFAOYSA-N benzene-1,3-diol;sodium Chemical compound [Na].OC1=CC=CC(O)=C1 KAVGXOKHWPNOAL-UHFFFAOYSA-N 0.000 claims description 2
- WRUAHXANJKHFIL-UHFFFAOYSA-L benzene-1,3-disulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC(S([O-])(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-L 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- -1 benzene-m-xylene sulfonate Chemical compound 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000005070 sampling Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- 238000007499 fusion processing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RCEBZHWOAHATAF-UHFFFAOYSA-N [Na].C1(=CC(=CC=C1)S(=O)(=O)O)S(=O)(=O)O Chemical compound [Na].C1(=CC(=CC=C1)S(=O)(=O)O)S(=O)(=O)O RCEBZHWOAHATAF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GZCKIUIIYCBICZ-UHFFFAOYSA-L disodium;benzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC(C([O-])=O)=C1 GZCKIUIIYCBICZ-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a sulfonation reaction system and a method for preparing resorcinol based on a microchannel reactor, and aims to provide a reaction system and a method which can greatly improve the conversion rate and selectivity of sulfonation and simultaneously ensure that the heat of exothermic reaction is timely removed so as to improve the safety of the process, wherein the reaction system comprises a sulfonation reaction microchannel reactor, the sulfonation reaction microchannel reactor is communicated with a second sulfonation reaction microchannel reactor through a first product pipeline, the first product pipeline is also provided with a heat exchanger, the second sulfonation reaction microchannel reactor is communicated with a neutralization reaction tank through a second reaction channel, the neutralization reaction tank is communicated with an alkali fusion reaction tank through a pipeline, the alkali fusion reaction tank is communicated with an acidification reaction tank through a pipeline, and the acidification reaction tank is communicated with a separation reaction tank through a pipeline; the reaction process comprises the following steps: sulfonation reaction, introducing sodium sulfite serving as a neutralizing agent, alkali fusion reaction and acidification reaction; belongs to the field of chemical production.
Description
Technical Field
The invention relates to a sulfonation process for preparing resorcinol, in particular to a method for continuously preparing resorcinol by taking a microchannel reactor as a sulfonation reaction device and taking benzene and sulfur trioxide as raw materials, belonging to the field of chemical production.
Background
Resorcinol, a white crystalline powdery organic compound, is also known as 1,3-benzenediol. Because the benzene structure contains two hydroxyl substituents, the reactions such as hydrogenation, halogenation, amination, acylation and sulfonation are easy to occur, so that the benzene structure is widely used as an important fine chemical raw material in the production process of dyes, medicines, ultraviolet stabilizers of polyolefin, special waterproof adhesives, synthetic resins, cosmetics, pesticides and the like. Resorcinol-synthesized m-methyl resin is widely used as a reinforcing rubber in the preparation process of tires, adhesive tapes, rubber tubes and the like because it shows excellent durability under high temperature conditions and in the process of processing and forming products. In 2020, the first three fields of the Chinese resorcinol demand are rubber processing, wood adhesive and dye, and the demand is respectively 53%, 17% and 8%. Meanwhile, resorcinol is used as a main pigment for a clean process for synthesizing the m-aminophenol, and the demand of the upstream resorcinol raw material is increased due to the increase of the market of the pressure-sensitive and heat-sensitive information dye produced by using the m-aminophenol as the raw material.
At present, the main methods for industrially producing resorcinol are as follows: benzene sulfonation alkali fusion method, phenol hydroxylation method, m-diisopropylbenzene oxidation method and arylation method. The benzene sulfonation alkali fusion method is a main method for industrially producing resorcinol in China due to simple process and mature technology. Benzene sulfonation alkali fusion method takes benzene as raw material, fuming sulfuric acid as sulfonating agent, after two steps of sulfonation reaction, the generated material is neutralized and alkali fused with sodium hydroxide, then is acidified to obtain resorcinol, and is extracted by adding ether, isopropyl ether or n-butyl alcohol, and the resorcinol product is obtained by distillation. In the whole process, a large amount of sodium sulfate is generated in the neutralization acid and chemical process, and sodium sulfite generated in the alkali fusion process increases the difficulty of subsequent byproduct treatment and increases the treatment cost, and in order to solve the problems that the concentration of sulfuric acid is reduced and the reaction rate is slowed down in the water generated in the sulfonation process, excessive fuming sulfuric acid is used, and sodium hydroxide, sulfuric acid and the like used in the sulfonation, alkali fusion and acidification processes are strong acid and strong base, so that the danger coefficient is high and the environment is greatly damaged. For example: 1 ton of resorcinol is generated, the amount of sodium sulfate which is a byproduct generated in the neutralization acidification step is 7.6 tons, the amount of sodium sulfite which is a byproduct generated in the alkali fusion process is 3.4 tons, and the subsequent treatment of the byproducts is a troublesome problem.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the sulfonation reaction system based on the microchannel reactor system is provided, the reaction system can greatly improve the conversion rate and selectivity of sulfonation, and simultaneously ensures that the heat of exothermic reaction is removed in time, so that the safety of the process is improved.
It is a second object of the present invention to provide a reaction method of the above reaction.
Therefore, the first technical scheme provided by the invention is as follows:
a sulfonation reaction system for preparing resorcinol based on a microchannel reactor comprises a sulfonation reaction microchannel reactor, wherein the sulfonation reaction microchannel reactor is communicated with a secondary sulfonation reaction microchannel reactor through a first product pipeline, the first product pipeline is also provided with a heat exchanger, the secondary sulfonation reaction microchannel reactor is communicated with a neutralization reaction tank through a second reaction channel, the neutralization reaction tank is communicated with an alkali fusion reaction tank through a pipeline, the alkali fusion reaction tank is communicated with an acidification reaction tank through a pipeline, and the acidification reaction tank is communicated with a separation reaction tank through a pipeline;
the upper part of the sulfonation reaction microchannel reactor is provided with a benzene feeding pipe, a sulfonating agent first sample inlet pipe and a cooling water feeding pipe;
the upper part of the disulfonation reaction microchannel reactor is provided with a sulfonating agent second sample inlet pipe and a heating water feeding pipe;
the separation reaction tank is provided with a resorcinol discharge pipe.
Furthermore, in the sulfonation reaction system for preparing resorcinol based on the microchannel reactor, a first thermometer is arranged on the sulfonation reaction microchannel reactor; and a second thermometer is arranged on the disulfonation reaction microchannel reactor.
Further, foretell a sulfonation reaction system based on microchannel reactor preparation resorcinol, separation retort top through sodium sulfite pipeline intercommunication neutralization reaction jar, the sodium sulfite pipeline on still be equipped with the sodium sulfite blender.
Furthermore, in the sulfonation reaction system for preparing resorcinol based on the microchannel reactor, the neutralization reaction tank is sequentially connected with the acidification mixer and the acidification reaction tank through pipelines, and a compressor is arranged on the pipeline between the reaction tank and the acidification mixer.
Furthermore, in the sulfonation reaction system for preparing resorcinol based on the microchannel reactor, the lower part of the sulfonation reaction microchannel reactor is provided with a cooling water discharge pipe, and discharged cooling water passes through the heat exchanger and then is introduced into the sulfonation reaction microchannel reactor through a heating water feed pipe;
the lower part of the disulfonation reaction microchannel reactor is provided with a heated water discharge pipeline.
Furthermore, in the sulfonation reaction system for preparing resorcinol based on the microchannel reactor, the interiors of the first sulfonation reaction microchannel reactor and the second sulfonation reaction microchannel reactor are respectively composed of a micro mixer and a microchannel.
Furthermore, in the sulfonation reaction system for preparing resorcinol based on the microchannel reactor, the sulfonation reaction microchannel reactor and the sulfonation reaction microchannel reactor are all one of a T-shaped microchannel reactor, a W-shaped microchannel reactor, a Y-shaped microchannel reactor and a segmentation-recombination microchannel reactor.
Furthermore, the sulfonation reaction system for preparing resorcinol based on the microchannel reactor has a tube diameter of 0.5-5mm.
The second technical scheme provided by the invention is as follows:
a method for preparing resorcinol by a sulfonation reaction system based on a microchannel reactor for preparing resorcinol comprises the following steps in sequence:
1) Sulfonation reaction
Benzene is fed into a sulfonation reaction microchannel reactor at a feeding rate of 78-160kg/h, and SO is fed into the reactor at a feeding rate of 80-240kg/h 3 Benzene and SO 3 The molar ratio of (1-1) to (1.5), controlling the reaction temperature of sulfonation reaction to be 20-50 ℃ by regulating and controlling cooling water, and controlling the retention time of reaction materials in a microchannel reactor to be 0.5-2h to obtain a product, namely benzenesulfonic acid;
2) Disulfonation reaction
Introducing SO into the disulfonation reaction microchannel reactor at a feed flux of 40-300kg/h 3 The feed rate of the benzene sulfonic acid as a product is 150-320kg/h, SO that benzene and SO are mixed 3 The molar ratio of the (1-1) to the (1.7) is that the temperature of the heating material is adjusted by a heater to ensure that the reaction temperature of the disulfonation reaction is 140-250 ℃, and the retention time of the material in a microchannel reactor is 0.5-3h to obtain a bis-product m-benzenedisulfonic acid;
3) Neutralization reaction
And (3) introducing sodium sulfite serving as a neutralizing agent into the neutralization reaction tank at a feeding flux of 64-360kg/h, wherein the feeding flux of a isophthalic acid dimer product is 230-480 kg/h, and the molar ratio of benzene to sodium sulfite is 1-1:1.4, obtaining a neutralization reaction product of sodium m-benzenedisulfonate, sulfur dioxide and water;
4) Alkali fusion reaction
And (2) introducing molten sodium hydroxide into the alkali fusion reaction tank at a feeding flux of 160-560kg/h, wherein the feeding flux of the neutralization reaction product is 250-565kg/h, and the molar ratio of benzene to sodium hydroxide is controlled to be 1:4-1:7, performing alkali fusion reaction at 320-380 ℃ for 0.5-2h to obtain alkali fusion products of sodium resorcinol, sodium sulfite and water;
5) Acidification reaction
SO is introduced into the acidification reaction tank at a total feed flux of 35-340kg/h 2 The feeding flux of the alkali fusion reaction product is 155-560kg/h, the flux of water is 10-90kg/h, when the pH =4.3-5.4, the acidification reaction is stopped, and then the product is led into a separation reaction tank to be separated to obtain the resorcinol product.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses the microchannel reactor as a sulfonation reaction site, greatly improves the conversion rate and selectivity of the sulfonation reaction by utilizing the advantages of high mixing degree, high mass and heat transfer efficiency and high reaction area caused by the reduction of the linear dimension in the microchannel reactor, ensures the timely removal of the heat of the exothermic reaction, improves the safety of the process, and can quickly realize industrial production by increasing the number of the microchannel reactors.
2. In the invention, SO is used 3 As the sulfonating agent, a microchannel reactor is selected as a sulfonation reaction site. Compared with the traditional benzene sulfonation alkali fusion process, the traditional process takes fuming sulfuric acid as a sulfonating agent, and the concentration of the sulfuric acid is reduced and the reaction rate is slowed down by water generated in the reaction, so that excessive sulfonating agent is used, and the process is not energy-saving, economical and unsafe. With SO 3 When used as sulfonating agent, it is due to SO 3 Too active as SO 3 When the amount of the catalyst is excessive, byproducts such as sulfones and the like are easily generated, so that the method is not beneficial to the traditional large-scale industrial production method, and the invention selects the traceThe channel reactor is used as a sulfonation reaction place, and due to the special structure of the microchannel reactor, the effect of accurately adjusting the proportion of reaction materials can be achieved by controlling the flow rate of the feeding material and the retention time of the material of the microchannel reactor, SO that excessive SO is not generated in unit area of reaction 3 Accumulation, and solves the problem of the generation of sulfone byproducts during sulfonation.
3. In the invention, neutralizing agent and acidifying agent used in the neutralization reaction and the acidification reaction are both byproducts recycled in the production process, the neutralizing agent is sodium sulfite, sodium isophthalate, byproduct water and sulfur dioxide are generated after neutralization, and the sulfur dioxide can be used as raw material of acidulant hydrogen sulfite. The sodium sulfite used in the neutralization reaction is a byproduct in the alkali fusion process and the acidification process, and after the separation reaction, the extraction of resorcinol is completed, and the recycling of sulfite is completed. The method recycles a large amount of byproducts, solves the problem of post-treatment of the byproducts, and is a resorcinol production process which reduces the cost and is green and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of a resorcinol sulfonation reaction system based on a microchannel reactor according to the present invention.
The attached drawings represent the names of elements as follows:
a sulfonation reaction microchannel reactor 1, a first product pipeline 2, a heat exchanger 3, a disulfonation reaction microchannel reactor 4, a second reaction channel 5, a neutralization reaction tank 6, an alkali fusion reaction tank 7, an acidification reaction tank 8, a separation reaction tank 9, a benzene feed pipe 10, a sulfonating agent first sample inlet pipe 11 and a cooling water feed pipe 12; a sulfonating agent second sample inlet pipe 13, a heating water feeding pipe 14, a first thermometer 15, a second thermometer 16, a resorcinol discharging pipe 17, a sodium sulfite mixer 18, a sodium sulfite pipeline 19, a compressor 20, an acidification mixer 21, a cooling water discharging pipe 22 and a heating water discharging pipe 23.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The invention provides a sulfonation reaction system for preparing resorcinol based on a microchannel reactor, which comprises a sulfonation reaction microchannel reactor 1, wherein the sulfonation reaction microchannel reactor 1 is used for reacting benzene and sulfur trioxide at low temperature to generate benzenesulfonic acid, and the sulfonation reaction microchannel reactor 1 is communicated with a sulfonation reaction microchannel reactor 4 through a first product pipeline 2, so that the benzenesulfonic acid product after reaction in the sulfonation reaction microchannel reactor 1 is introduced into the sulfonation reaction microchannel reactor 4;
the disulfonation reaction microchannel reactor 4 is used for the substitution reaction of benzenesulfonic acid and sulfur trioxide at high temperature to generate m-benzenedisulfonic acid, the first product pipeline 2 is also provided with a heat exchanger 3, the heat exchanger 3 is connected with a cooling water discharge pipe 22 and is used for heating discharge cooling water and then introducing the heated water into the disulfonation reaction microchannel reactor 4 through a heated water feed pipe 14, and the lower part of the disulfonation reaction microchannel reactor 4 is provided with a heated water discharge pipeline 23;
the disulfonation reaction microchannel reactor 4 is communicated with a neutralization reaction tank 6 through a second reaction channel 5, the neutralization reaction tank 6 is communicated with an alkali fusion reaction tank 7 through a pipeline, the alkali fusion reaction tank 7 is communicated with an acidification reaction tank 8 through a pipeline, and the acidification reaction tank 8 is communicated with a separation reaction tank 9 through a pipeline;
the neutralization reaction tank 6 is sequentially connected with the acidification mixer 21 and the acidification reaction tank 8 through pipelines, and a compressor 20 is arranged on the pipeline between the neutralization reaction tank 6 and the acidification mixer 21 to generate SO 2 Compressed by a compressor 20 through a pipeline, enters an acidification mixer 21 and is directly filled with SO 2 Mixing, and then entering an acidification reaction tank 8 for acidification reaction;
the separation reaction tank 9 is provided with a resorcinol discharge pipe 17. 9 tops of separation retort communicate neutralization reaction jar 6 through sodium sulfite pipeline 19, sodium sulfite pipeline 19 on still be equipped with sodium sulfite blender 18 for sodium sulfite in the separation retort passes through the pipeline and gets into sodium sulfite blender 18, mixes with the sulfurous acid that directly lets in, gets into neutralization reaction jar 5 through sodium sulfite pipeline 19 after mixing, carries out neutralization reaction.
The upper part of the sulfonation reaction microchannel reactor 1 is provided with a benzene feeding pipe 10, a sulfonating agent first sample inlet pipe 11 and a cooling water feeding pipe 12;
the upper part of the disulfonating agent microchannel reactor 4 is provided with a sulfonating agent second sample inlet pipe 13 and a heating water feeding pipe 14;
in order to facilitate the detection of the temperature in the microchannel reactor, a first thermometer 15 is arranged on the sulfonation reaction microchannel reactor; the second sulfonation reaction micro-channel reactor is provided with a second thermometer 16.
More specifically, the inside of the sulfonation reaction microchannel reactor 1 and the inside of the sulfonation reaction microchannel reactor 3 both comprise a micro mixer and a microchannel, and the pipe diameter of the microchannel reactor is 0.5-5mm, preferably 2mm.
The first sulfonation reaction microchannel reactor and the second sulfonation reaction microchannel reactor are all one of a T-shaped microchannel reactor, a W-shaped microchannel reactor, a Y-shaped microchannel reactor and a segmentation-recombination microchannel reactor.
Example 2
The invention provides a resorcinol sulfonation reaction process based on a microchannel reactor, which adopts a sulfonation reaction system for preparing resorcinol based on the microchannel reactor, and comprises the following specific processes:
1) Selecting a Y-shaped structure six-interface microchannel reactor, wherein the pipe diameter of the microchannel is 2.5mm, and the raw material benzene passes through a benzene inlet pipe 10 and a sulfonating agent SO 3 Introducing the benzene into a sulfonation microchannel reactor 1 through a sulfonating agent first sample inlet pipe 11, wherein the feeding flux of the benzene is 78kg/h, and the SO 3 The feed flux of (2) was 96kg/h, benzene and SO 3 1.2, the cooling water feed is introduced into a sulfonation microchannel reactor via a cooling water feed conduit 12, and the reaction temperature is controlled at 30 ℃ by monitoring a first thermometer 15 on a sulfonation microreactor 1. After the reaction materials are mixed in a sulfonation micro-mixer, the reaction materials enter a sulfonation micro-channel for sulfonation reaction, and the residence time in the micro-channel for the reaction is 1h, so that a product of benzenesulfonic acid is generated.
2) One product of benzenesulfonic acid and sulfonating agent SO 3 Respectively introducing the mixture into a disulfonating microchannel reactor 4 through a first product pipeline 2 and a sulfonating agent second sample inlet pipe 13, mixing in the disulfonating microchannel reactor 4, and then carrying out a disulfonating reaction, wherein SO is 3 The feed throughput of (2) was 112kg/h and the one-product feed throughput was 158kg/h. The cooling water discharging pipe 22 is connected with the heat exchanger 3, the discharged cooling water is heated in the heat exchanger 3 and then is introduced into the disulfonation reaction microchannel reactor 4 through the heating water feeding pipe 14, the reaction temperature of the disulfonation reaction is adjusted to be 160 ℃ by monitoring the second thermometer 16 on the disulfonation reaction microchannel reactor 4, the residence time of the reaction material in the disulfonation reaction microchannel reactor is 2 hours, the generated di-product m-phthalic disulfonic acid is introduced into the neutralization reaction tank 6 through the second reaction channel 5, and the heated water after the reaction flows out through the heating water discharging pipe 23 at the lower part of the disulfonation reaction microchannel reactor 4.
3) The di-product m-benzene disulfonic acid is introduced into a neutralization reaction tank 6, a neutralizer is introduced into the neutralization reaction tank 6 through a sodium sulfite pipeline 19 after sodium sulfite produced in a separation reaction tank and sodium sulfite directly added are mixed by a sodium sulfite mixer 18, the feeding flux of the neutralizer is 177kg/h, the reaction is stopped when the neutralization is carried out until the pH = 6-7, so that tri-products of m-benzene disulfonic acid sodium, sulfur dioxide and water are generated, and the rest products are introduced into an alkali fusion reaction tank 7 except that the generated sulfur dioxide is introduced into an acidification reaction tank 8.
4) Molten sodium hydroxide is introduced into an alkali fusion reaction tank 7, the feeding flux of the sodium hydroxide is 220kg/h, the molar ratio of benzene to the sodium hydroxide is 1.
5) Mixing the four products, sulfur dioxide and water, and introducing into an acidification reaction tank 8. Sulfur dioxide generated by the neutralization reaction tank is compressed by a compressor 20 through a pipeline and then enters an acidification mixer 21, and SO is directly introduced into the acidification mixer 2 Mixing, feeding into an acidification reaction tank 8 2 The total flux of the feed of (1) was 64kg/h and the flux of water was 20kg/h, and when pH =4.5, the acidification reaction was stopped and after the acidification was completed, it was passed to a separation reaction tank9, extracting and separating by using ether to obtain a resorcinol product, and discharging the extracted resorcinol out of a resorcinol discharge pipe 17.
Example 3
The invention provides a resorcinol sulfonation reaction process based on a microchannel reactor, which adopts a sulfonation reaction system for preparing resorcinol based on the microchannel reactor, and comprises the following specific processes:
1) Selecting a Y-shaped structure six-interface microchannel reactor, wherein the pipe diameter of the microchannel is 3mm, and the raw material benzene passes through a benzene feeding pipe 10 and a sulfonating agent SO 3 Introducing the benzene into a sulfonation microchannel reactor 1 through a sulfonating agent first sample inlet pipe 11, wherein the feeding flux of the benzene is 100kg/h, and the SO 3 With a feed flux of 140kg/h of benzene and SO 3 1.4, the cooling water feed is introduced into a sulfonation microchannel reactor via a cooling water feed conduit 12, and the reaction temperature is controlled at 40 ℃ by monitoring a first thermometer 15 on a sulfonation microreactor 1. After the reaction materials are mixed in a sulfonation micro-mixer, the reaction materials enter a sulfonation micro-channel for sulfonation reaction, and the residence time in the micro-channel for the reaction is 0.5h, so that a product of benzenesulfonic acid is generated.
2) One product of benzenesulfonic acid and sulfonating agent SO 3 Respectively introducing the mixture into a disulfonating microchannel reactor 4 through a first product pipeline 2 and a sulfonating agent second sample inlet pipe 13, mixing in the disulfonating microchannel reactor 4, and then carrying out a disulfonating reaction, wherein SO is 3 The feed throughput of (2) was 130kg/h and the one-product feed throughput was 198kg/h. The cooling water discharging pipe 22 is connected with the heat exchanger 3, the discharged cooling water is heated in the heat exchanger 3 and then is introduced into the disulfonation reaction microchannel reactor 4 through the heating water feeding pipe 14, the reaction temperature of the disulfonation reaction is adjusted to be 200 ℃ by monitoring the second thermometer 16 on the disulfonation reaction microchannel reactor 4, the retention time of the reaction material in the disulfonation microchannel reactor is 1h, the generated di-product m-phthalic acid is introduced into the neutralization reaction tank 6 through the second reaction channel 5, and the heated water after the reaction flows out through the heating water discharging pipe 23 at the lower part of the disulfonation reaction microchannel reactor 4.
3) The di-product m-benzene disulfonic acid is introduced into a neutralization reaction tank 6, a neutralizer is introduced into the neutralization reaction tank 6 through a sodium sulfite pipeline 19 after sodium sulfite produced in a separation reaction tank and sodium sulfite directly added are mixed by a sodium sulfite mixer 18, the feeding flux of the neutralizer is 220kg/h, the reaction is stopped when the neutralization is carried out until the pH is = 6-7, so that a tri-product m-benzene disulfonic acid sodium, sulfur dioxide and water are generated, and the rest products are introduced into an alkali fusion reaction tank 7 except that the generated sulfur dioxide is introduced into an acidification reaction tank 8.
4) And (2) introducing the molten sodium hydroxide into an alkali fusion reaction tank 7, wherein the feeding flux of the sodium hydroxide is 325kg/h, the molar ratio of benzene to the sodium hydroxide is 1.
5) Mixing the four products, sulfur dioxide and water, and introducing into an acidification reaction tank 8. Sulfur dioxide generated by the neutralization reaction tank is compressed by a compressor 20 through a pipeline and then enters an acidification mixer 21, and SO is directly introduced into the acidification mixer 2 Mixing, feeding into an acidification reaction tank 8 2 The total feeding flux of the reaction kettle is 70kg/h, the water flux of the reaction kettle is 30kg/h, when the pH value is =5.2, the acidification reaction is stopped, the reaction kettle is introduced into a separation reaction tank 9 after the acidification is finished, n-butyl alcohol is used for extraction and separation to obtain resorcinol products, and the resorcinol after the extraction is finished flows out through a resorcinol discharge pipe 17.
It should be noted that the microchannel reactor adopted in the present application is purchased directly through a commercial channel, and the six-interface microchannel reactor with the Y-shaped structure is purchased from kunshiji engineering technology limited.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The sulfonation reaction system for preparing resorcinol based on the microchannel reactor is characterized by comprising a sulfonation reaction microchannel reactor (1), wherein the sulfonation reaction microchannel reactor (1) is communicated with a sulfonation reaction microchannel reactor (4) through a first product pipeline (2), the first product pipeline (2) is further provided with a heat exchanger (3), the sulfonation reaction microchannel reactor (4) is communicated with a neutralization reaction tank (6) through a second reaction channel (5), the neutralization reaction tank (6) is communicated with an alkali fusion reaction tank (7) through a pipeline, the alkali fusion reaction tank (7) is communicated with an acidification reaction tank (8) through a pipeline, and the acidification reaction tank (8) is communicated with a separation reaction tank (9) through a pipeline;
the upper part of the sulfonation reaction microchannel reactor (1) is provided with a benzene feeding pipe (10), a sulfonating agent first sampling pipe (11) and a cooling water feeding pipe (12);
the upper part of the disulfonating agent microchannel reactor (4) is provided with a sulfonating agent second sample inlet pipe (13) and a heating water feeding pipe (14);
the separation reaction tank (9) is provided with a resorcinol discharge pipe (17).
2. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor, according to claim 1, wherein a first thermometer (15) is provided on the microchannel reactor for sulfonation reaction; the second sulfonation reaction microchannel reactor is provided with a second thermometer (16).
3. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor according to claim 1, wherein the top of the separation reaction tank (9) is communicated with the neutralization reaction tank (6) through a sodium sulfite pipeline (19), and a sodium sulfite mixer (18) is further arranged on the sodium sulfite pipeline (19).
4. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor according to claim 1, wherein the neutralization reaction tank (6) is sequentially connected with the acidification mixer (21) and the acidification reaction tank (8) through pipelines, and a compressor (20) is arranged in the pipeline between the reaction tank (6) and the acidification mixer (21).
5. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor according to claim 1, wherein a cooling water outlet pipe (22) is arranged at the lower part of the primary sulfonation reaction microchannel reactor (1), and the outlet cooling water passes through the heat exchanger (3) and then is introduced into the secondary sulfonation reaction microchannel reactor (4) through a heating water inlet pipe (14);
the lower part of the disulfonation reaction microchannel reactor (4) is provided with a heating water discharge pipeline (23).
6. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor according to claim 1, wherein the inside of the mono-sulfonation reaction microchannel reactor (1) and the inside of the di-sulfonation reaction microchannel reactor (3) are both composed of a micromixer and a microchannel.
7. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor according to claim 1, wherein the first sulfonation reaction microchannel reactor and the second sulfonation reaction microchannel reactor are all one of a T-type microchannel reactor, a W-type microchannel reactor, a Y-type microchannel reactor and a split-and-recombination microchannel reactor.
8. The sulfonation reaction system for preparing resorcinol based on a microchannel reactor, according to claim 1, wherein the tube diameter of the microchannel reactor is 0.5-5mm.
9. A method for preparing resorcinol by a sulfonation reaction system based on a microchannel reactor for preparing resorcinol is characterized by sequentially comprising the following steps of:
1) Sulfonation reaction
Benzene is fed into a sulfonation reaction microchannel reactor at a feeding rate of 78-160kg/h, and SO is fed into the reactor at a feeding rate of 80-240kg/h 3 Benzene and SO 3 The molar ratio of 1-1:1.5, the reaction temperature of the sulfonation reaction is controlled between 20 and 50 ℃ by regulating and controlling cooling water, and the reaction materials are in the microchannel reactorThe retention time is 0.5-2h, and a product benzenesulfonic acid is obtained;
2) Disulfonation reaction
S0 is introduced into the disulfonation reaction microchannel reactor at a feed flux of 40-300kg/h 3 The feed rate of the benzene sulfonic acid as a product is 150-320kg/h, SO that benzene and SO are mixed 3 The molar ratio of the benzene-m-xylene sulfonate to the isophthalic acid is 1-1:1.7, the temperature of the heated materials is adjusted by a heater to ensure that the reaction temperature of the disulfonation reaction is 140-250 ℃, and the retention time of the materials in a microchannel reactor is 0.5-3h to obtain a bis-product of the isophthalic acid;
3) Neutralization reaction
Introducing sodium sulfite as a neutralizing agent into a neutralization reaction tank at a feeding flux of 64-360kg/h, wherein the feeding flux of a di-product m-benzenedisulfonic acid segment is 230-480 kg/h, and the molar ratio of benzene to sodium sulfite is 1-1:1.4, so as to obtain sodium m-benzenedisulfonate, sulfur dioxide and water as neutralization reaction products;
4) Alkali fusion reaction
Introducing molten sodium hydroxide into an alkali fusion reaction tank at a feeding flux of 160-560kg/h, wherein the feeding flux of a neutralization reaction product is 250-565kg/h, the molar ratio of benzene to sodium hydroxide is controlled to be 1:4-1:7, the reaction temperature is 320-380 ℃, and the alkali fusion reaction time is 0.5-2h, so as to obtain alkali fusion products of sodium resorcinol, sodium sulfite and water;
5) Acidification reaction
SO is introduced into the acidification reaction tank at a total feed flux of 35-340kg/h 2 The feeding flux of the alkali fusion reaction product is 155-560kg/h, the flux of water is 10-90kg/h, when the pH =4.3-5.4, the acidification reaction is stopped, and then the product is led into a separation reaction tank to be separated to obtain the resorcinol product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018676A (en) * | 2019-12-11 | 2020-04-17 | 乌海时联环保科技有限责任公司 | Method for preventing resorcinol from discoloring |
| CN111100040A (en) * | 2019-12-23 | 2020-05-05 | 沈阳化工研究院有限公司 | Micro-channel continuous heterogeneous sulfonation reaction device and method |
| CN111362780A (en) * | 2020-04-21 | 2020-07-03 | 哈密盛典科技有限公司 | Method for producing resorcinol by using sulfur trioxide |
| CN111558352A (en) * | 2020-06-12 | 2020-08-21 | 哈密盛典科技有限公司 | Resorcinol alkali fused tube type reactor and method for continuously producing resorcinol by using sulfur trioxide |
| CN112225642A (en) * | 2020-10-19 | 2021-01-15 | 内蒙古盛唐国际蒙医药研究院有限公司 | Method for preparing resorcinol through microchannel reaction |
| CN212610358U (en) * | 2020-05-25 | 2021-02-26 | 哈密盛典科技有限公司 | Resorcinol production system |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018676A (en) * | 2019-12-11 | 2020-04-17 | 乌海时联环保科技有限责任公司 | Method for preventing resorcinol from discoloring |
| CN111100040A (en) * | 2019-12-23 | 2020-05-05 | 沈阳化工研究院有限公司 | Micro-channel continuous heterogeneous sulfonation reaction device and method |
| CN111362780A (en) * | 2020-04-21 | 2020-07-03 | 哈密盛典科技有限公司 | Method for producing resorcinol by using sulfur trioxide |
| CN212610358U (en) * | 2020-05-25 | 2021-02-26 | 哈密盛典科技有限公司 | Resorcinol production system |
| CN111558352A (en) * | 2020-06-12 | 2020-08-21 | 哈密盛典科技有限公司 | Resorcinol alkali fused tube type reactor and method for continuously producing resorcinol by using sulfur trioxide |
| CN112225642A (en) * | 2020-10-19 | 2021-01-15 | 内蒙古盛唐国际蒙医药研究院有限公司 | Method for preparing resorcinol through microchannel reaction |
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