CN114558533A - Sodium methyl mercaptide and dimethyl disulfide joint production system and process - Google Patents
Sodium methyl mercaptide and dimethyl disulfide joint production system and process Download PDFInfo
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 title claims abstract description 199
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 38
- 230000008569 process Effects 0.000 title claims description 21
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 239000006200 vaporizer Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 93
- 239000007788 liquid Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- ZZTMMVAAULUFCS-UHFFFAOYSA-L disodium;methanedisulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CS([O-])(=O)=O ZZTMMVAAULUFCS-UHFFFAOYSA-L 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- XHXXWWGGXFUMAJ-UHFFFAOYSA-N methanethiol;sodium Chemical compound [Na].SC XHXXWWGGXFUMAJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 7
- 229960002163 hydrogen peroxide Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 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
- XYAWUFGTUSOGEY-UHFFFAOYSA-N [S].SC Chemical compound [S].SC XYAWUFGTUSOGEY-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- MXKIASVYJZPUMJ-UHFFFAOYSA-N S.SC Chemical compound S.SC MXKIASVYJZPUMJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- 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
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- 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
Abstract
The invention relates to the field of chemical product manufacturing, in particular to a sodium methyl mercaptide and dimethyl disulfide combined production system which comprises a methyl mercaptan feeding tank and a methyl mercaptan vaporizer, wherein the outlet end of the methyl mercaptan feeding tank is communicated with the inlet end of the methyl mercaptan vaporizer, the outlet end of the methyl mercaptan vaporizer is communicated with the inlet end of a sodium methyl mercaptide reaction tower, the outlet end of the sodium methyl mercaptide reaction tower is communicated with the inlet end of an oxidation reactor, the inlet end at the top of the sodium methyl mercaptide reaction tower is also communicated with an alkali liquor supply device, the inlet end of the oxidation reactor is also communicated with an oxygen buffer tank, and the outlet end of the oxidation reactor is communicated with a light removal unit; the invention also relates to a combined production process of sodium methyl mercaptide and dimethyl disulfide; the invention has the advantages of high yield, high utilization rate of equipment, low production cost, no side reaction, high safety and high conversion rate of raw materials by jointly producing two products by one set of equipment.
Description
Technical Field
The invention relates to the technical field of chemical product manufacturing, in particular to a system and a process for jointly producing sodium methyl mercaptide and dimethyl disulfide.
Background
At present, a plurality of methods for synthesizing dimethyl disulfide (DMDS) are available, and the methods mainly comprise a dimethyl sulfate method, a methyl mercaptan oxidation method, a methyl mercaptan sulfur method, a methyl mercaptan hydrogen sulfide method and a sodium methyl mercaptide hydrogen peroxide method.
1. Dimethyl sulfate method: sodium sulfide and sulfur are used as raw materials to prepare sodium disulfide, and the newly prepared sodium disulfide is reacted with dimethyl sulfate to prepare dimethyl disulfide. The dimethyl sulfate method is technically mature, but the raw material dimethyl sulfate is extremely toxic, serious in environmental pollution, high in consumption quota and gradually eliminated.
2. Methyl mercaptan oxidation method: methyl mercaptan and oxygen (or air) are used as raw materials, rare earth metal or rare earth and alkali metal oxide loaded carrier is used as a catalyst, the reaction temperature is 200 ℃, and the pressure is 11 bar. Cooling, separating, and washing with alkali. The yield of the finished product is 74-81%, and the conversion rate is 86-96% (calculated by methyl mercaptan). The route has industrial reports, but because of oxidation reaction, the explosion limit is wide, the danger is large, the process condition is not well controlled, and the purification of the methyl mercaptan in the product is difficult.
3. Methyl mercaptan sulfur method: under the action of a catalyst, the liquid raw material is subjected to two-stage heterogeneous reaction and two-stage rectification to obtain a finished product with the purity of 99%. However, the process materials need to be added in a melting mode or in a powder state, so that the process is not beneficial to environmental control, hydrogen sulfide gas needs to be discharged in the reaction stage, the process is complex, and the environmental control difficulty is high.
4. Sodium methyl mercaptide hydrogen peroxide oxidation method: according to the introduction of the United states Yabao company patent, a sodium methyl mercaptide solution with the concentration of 20% is prepared by absorption with sodium hydroxide with the concentration of 15%, dimethyl disulfide can be prepared by reaction of the sodium methyl mercaptide solution with hydrogen peroxide solution with the concentration of 20-70%, the absorption reaction temperature of the sodium methyl mercaptide can be controlled to be 45-60 ℃, the reaction temperature of the dimethyl disulfide is controlled to be 50-75 ℃, the pressure is controlled to be 18.7-24 kpa, and negative pressure operation is carried out. The reaction is carried out under alkaline conditions, the oxidation of methyl mercaptan into methanesulfonic acid is avoided, liquid-liquid reaction is carried out, and the operating conditions are low, but the method comprises the following steps:
(1) the oxydol has strong oxidizing ability, and the oxidation reaction is too violent and is not well controlled;
(2) the technology uses dilute hydrogen peroxide, so that the concentration of alkali liquor is lower and lower, concentration is needed, the cost is increased, the cost of the used hydrogen peroxide is higher, and the industrial cost is too high;
(3) the yield of the finished product is only about 70-80%.
The sodium methyl mercaptide synthesis technology comprises the following steps: the main flow process is that sodium hydrosulfide reacts with dimethyl sulfate, dimethyl sulfate is generally dripped into sodium hydrosulfide solution at certain temperature to carry out chemical reaction, the temperature is controlled to be about 60 ℃, and exhausted gas is absorbed by liquid alkali after purification. The system is under negative pressure. The content reaches about 20 percent after the saturation. In this process, mirabilite is produced as a by-product, and dimethyl ether is sometimes produced as a by-product.
However, the wastewater inevitably contains a large amount of NaHS solution and mirabilite, and a large amount of sodium hydrosulfide more easily causes air pollution and causes diffusion of surrounding odor.
Therefore, the traditional process for preparing sodium methyl mercaptide or the process for preparing dimethyl disulfide are single products, the market coverage is small, the production cost is high, the main methods generally have the problems of high toxicity of raw materials, serious environmental pollution, high safety control difficulty, high industrialization cost and the like, and the method for jointly producing sodium methyl mercaptide and dimethyl disulfide with safety, high efficiency, low cost and environmental protection is urgently needed.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art and to date no process has been developed which solves the above problems by the combined production of sodium methanethiolate and dimethyldisulfide. The combined production process of sodium methyl mercaptide and dimethyl disulfide is characterized in that one set of equipment is shared, the feeding amount of methyl mercaptan is adjusted to control the yield of two products, the production efficiency is greatly improved, the yield of the products is controllably adjusted according to market needs, so that the production cost is greatly reduced, high benefits are obtained, a new process is sought for developing sodium methyl mercaptide and dimethyl disulfide, and a way is sought for the survival and the market of enterprises. And solves the problems of the prior mainstream production process of sodium methyl mercaptide or dimethyl disulfide that the raw materials have high toxicity, the environmental pollution is serious, the safety control difficulty is large, the continuous combined production can not be realized, and the like,
the invention is realized by the following technical scheme: the sodium methyl mercaptide and dimethyl disulfide joint production system comprises a methyl mercaptan vaporizer, wherein the outlet end of the methyl mercaptan vaporizer is communicated with the inlet end of a sodium methyl mercaptide reaction tower, the outlet end of the sodium methyl mercaptide reaction tower is communicated with the inlet end of an oxidation reactor, and the inlet end at the top of the sodium methyl mercaptide reaction tower is also communicated with an alkali liquor supply device;
the inlet end of the oxidation reactor is also communicated with an oxygen buffer tank, and the outlet end of the oxidation reactor is communicated with a light component removal unit.
Further, the lightness-removing unit comprises a liquid separation tank communicated with the outlet end of the oxidation reactor through a second cooler, the outlet end of the liquid separation tank is communicated with the inlet end of a decoloring tank, and the outlet end of the decoloring tank is communicated with the lightness-removing tower through a filter;
the outlet end of the light component removing tower is communicated with the middle inlet end of the heavy component removing tower, the top outlet end of the heavy component removing tower is communicated with the top inlet end of the heavy component removing tower and a finished product storage tank respectively after passing through a third cooler, and the bottom outlet end of the heavy component removing tower is communicated with the inlet end of a steam vaporizer.
The joint production process of sodium methyl mercaptide and dimethyl disulfide comprises the following steps:
s1, heating and vaporizing methyl mercaptan by a methyl mercaptan vaporizer and then reacting with a sodium hydroxide solution to generate a sodium methyl mercaptan solution, wherein the reaction equation is CH3SH+NaOH＝CH3SNa+H2O；
S2, carrying out oxidation reaction on the sodium methyl mercaptide solution and oxygen-containing gas in the oxidation reactor to generate dimethyl disulfide and sodium hydroxide aqueous solution, wherein the reaction equation is 2CH3SNa+0.5O2+H2O→CH3SSCH3+2NaOH；
S3, separating the dimethyl disulfide and the sodium hydroxide aqueous solution to obtain the dimethyl disulfide.
Further, the step S3 includes the following steps:
(1) after the dimethyl disulfide and the sodium hydroxide aqueous solution are condensed, separating the sodium hydroxide aqueous solution by a liquid separation tank to obtain crude dimethyl disulfide and water;
(2) and dehydrating the crude dimethyl disulfide containing water by a light component removal tower to obtain the crude dimethyl disulfide.
Further, a first reboiler is arranged in the light component removal tower, the tower pressure of the light component removal tower is controlled to be 0.2Mpa, the temperature is 125 ℃, and water in the tower kettle is completely vaporized and flows out from the tower top to enter a tower top cooler for cooling, and then the water is sent to a wastewater recovery system.
Further, the step S3 further includes the following steps:
(3) and rectifying the crude dimethyl disulfide subjected to moisture removal by a de-weighting tower to form a dimethyl disulfide finished product.
And further, a second reboiler is arranged in the de-heavy tower, the tower pressure of the de-heavy tower is 0.25Mpa, the temperature of the de-heavy tower is 135 ℃, refined dimethyl disulfide at the tower top enters a cooler for cooling and condensation, liquid is recycled to a dimethyl disulfide intermediate tank, the liquid is pumped back into the tower through a reflux pump at the tower top, and a dimethyl disulfide finished product is fed into a tank area through flow rate control after the other path of the refined dimethyl disulfide is analyzed to be qualified.
Further, the liquid level of the tower kettle is controlled, the liquid is discharged discontinuously, and trace components heavier than dimethyl disulfide are pumped out by the tower kettle pump, vaporized by a heater and sent to a burning system for treatment.
Further, the oxidation reactor in the step S1 is a shell-and-tube reactor, the shell side of the shell-and-tube reactor is controlled by hot water at 80 ℃ in a circulating manner, and the tube side is formed by mixing sodium methyl mercaptide with oxygen and then reacting with a catalyst.
Further, the oxidation reaction conditions are as follows: the reaction pressure is 0.6-0.8 Mpa, and the reaction temperature is 80-90 ℃.
The invention has the beneficial effects that: the invention uses liquid alkali absorption method and oxidation method to realize the joint production of sodium methyl mercaptide and dimethyl disulfide in a set of equipment, firstly, methyl mercaptan reacts with alkali liquor to generate sodium methyl mercaptide finished product, then the sodium methyl mercaptide finished product reacts with oxygen-containing gas to generate dimethyl disulfide and sodium hydroxide aqueous solution, sodium hydroxide is separated and dehydrated to obtain dimethyl disulfide finished product, therefore, after raw materials are put into the scheme, two products of sodium methyl mercaptide and dimethyl disulfide can be simultaneously generated in the sequential reaction process, and the output ratio of the two products can be adjusted according to actual needs, thereby realizing the continuous joint production of sodium methyl mercaptide and dimethyl disulfide, avoiding the explosion risk caused by adopting the direct oxidation of methyl mercaptan and oxygen/air, ensuring the reaction to be safer and smoother, ensuring no side reaction, and leading the conversion rate of the raw materials to be more than 97 percent, the dimethyl disulfide product directly prepared by oxidation reaction is yellow liquid and has no floccule, the product is simply decolored and filtered, the yield of the final dimethyl disulfide product is up to 96%, the product is purified by a dimethyl disulfide de-weighting tower, the purity of the finished product is up to more than 99.5%, the market requirement and industrial production are met, in the whole reaction, unreacted aqueous phase materials such as sodium methyl mercaptide and sodium hydroxide solution can be recycled, trace pressure relief gas enters a tail gas treatment process for incineration treatment, and waste gas is organized and discharged, so that the environment is friendly.
Drawings
FIG. 1 is a schematic process flow diagram of example 1.
Wherein: 1. a methyl mercaptan feed tank; 2. a methyl mercaptan vaporizer; 3. a sodium methyl mercaptide reaction tower; 4. a sodium methyl mercaptide intermediate tank; 5. an alkali liquor supply device; 6. an oxygen buffer tank; 7. an oxidation reactor; 8. a mixer; 9. liquid separating tank; 10. a decolorizing tank; 11. a filter; 12. a light component removal tower feeding tank; 13. a light component removal tower; 14. a de-heavy tower; 15. a first cooler; 16. a second cooler; 17. a third cooler.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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.
Example 1
As shown in fig. 1, a sodium methyl mercaptide and dimethyl disulfide combined production system comprises a methyl mercaptan feeding tank 1 and a methyl mercaptan vaporizer 2, wherein methyl mercaptan with the content of 99.8 percent and the temperature of 7 ℃ is conveyed to the methyl mercaptan feeding tank 1 through a pump to be buffered, the methyl mercaptan is conveyed to the methyl mercaptan vaporizer 2 through a pump under pressure to be vaporized, the methyl mercaptan is heated and vaporized by a 0.4Mpa steam heat exchanger in the methyl mercaptan vaporizer 2 to obtain methyl mercaptan gas, the outlet end of the methyl mercaptan vaporizer 2 is communicated with the inlet end of the bottom of a sodium methyl mercaptide reaction tower 3, the temperature is controlled to be 70-75 ℃, the pressure is controlled to be 0.2Mpa, and the flow rate is controlled by a flow regulating valve to be 1200kg/h (the content of the methyl mercaptan is 1197.6kg, the content of the methyl sulfide is 0.8kg, and the other 1.6kg) to enter the bottom of the sodium methyl mercaptide reaction tower 3;
the bottom outlet end of the sodium methyl mercaptide reaction tower 3 is respectively communicated with the top inlet end of the reaction tower, the inlet end of an oxidation reactor 7 and the inlet end of a sodium methyl mercaptide intermediate tank 4 through a delivery pump, the top inlet end of the sodium methyl mercaptide reaction tower 3 is also communicated with an alkali liquor supply device 5, the alkali liquor supply device 5 provides a sodium hydroxide solution, concretely, the sodium hydroxide is pumped out of a 16-18% sodium hydroxide aqueous solution through a pump according to a configured proportion, the temperature is 40 ℃, the flow is 1400kg/h (the sodium hydroxide content is 238kg water content is 1162kg), methyl mercaptan gas and the 16-18% sodium hydroxide aqueous solution are in reverse contact with each other through a tower filler for reaction, the reaction stage belongs to exothermic reaction, a circulating water heat exchange system is arranged at the bottom of the reaction tower, the 32 ℃ circulating water takes away reaction heat, the temperature of the reaction tower is controlled to be 70-75 ℃, the pressure is 0.1-0.15Mpa, and the sodium methyl mercaptide solution with the content of 20 percent is obtained;
the outlet end of the bottom of the sodium methyl mercaptide reaction tower 3 is communicated with the inlet end of an oxidation reactor 7 through a delivery pump, the inlet end of the oxidation reactor 7 is also communicated with an oxygen buffer tank 6, 20% of sodium methyl mercaptide solution is heated by a 0.4Mpa steam heat exchanger before entering the oxidation reactor 7, then the temperature is controlled to be 70 ℃ +/-5 ℃ flow rate 995kg/h and the pressure is 0.7Mpa, oxygen with the content of 80% and the flow rate of 215kg/h flowing out of the oxygen buffer tank 6 and the pressure of 0.7Mpa, the temperature is 90 ℃ +/-5 ℃ is mixed by a mixer 8 and then enters the oxidation reaction tower 7 for reaction to generate dimethyl disulfide and sodium hydroxide aqueous solution, the outlet end of the oxidation reactor is communicated with a light removal unit, and the dimethyl disulfide and the sodium hydroxide aqueous solution enter the light removal unit for dehydration to remove sodium hydroxide and water, and obtain a dimethyl disulfide finished product;
the bottom outlet end and the top inlet end of the sodium methyl mercaptide reaction tower 3 are communicated through a first cooler 15, 20% sodium methyl mercaptide solution is cooled by circulating water through the first cooler 15 and then is sent to the top inlet end of the sodium methyl mercaptide reaction tower 3 to carry out reflux control for backflow quantity of 600kg/h, sodium methyl mercaptide reacts again after passing through the first cooler 15, the quality of a finished product can be ensured, and the temperature of the reaction tower can be regulated and controlled after the sodium methyl mercaptide passes through the cooler, so that rising methyl mercaptide gas is completely absorbed, and the utilization rate of raw materials is improved;
the outlet end at the bottom of the sodium methyl mercaptide reaction tower 3 is communicated with the inlet end of the sodium methyl mercaptide intermediate tank 4 through a delivery pump, so that 20 percent sodium methyl mercaptide solution enters the sodium methyl mercaptide intermediate tank 4 for finished product storage;
the outlet end of the oxidation reactor 7 is communicated with the inlet end of the liquid separating tank 9 through a second cooler 16, the generated dimethyl disulfide and sodium hydroxide aqueous solution enters the liquid separating tank 9 after being cooled by the second cooler 16, gas separated by the liquid separating tank 9 is discharged to an incineration system under the control of a regulating valve, aqueous phase wastewater and alkali liquor separated by the liquid separating tank 9 are discharged to a collection system, the alkali liquor is recycled after treatment, the outlet end of the liquid separating tank 9 is communicated with the inlet end of a decoloring tank 10, the decoloring tank 10 is a carbon bed decoloring tank filled with active carbon for adsorption decoloring, a collection tank is also arranged between the liquid separating tank 9 and the decoloring tank 10, the dimethyl disulfide separated by the liquid separating tank 9 is sent to the collection tank and is pumped to the decoloring tank 10 for decoloring, the decoloring treatment is carried out, the decoloring tank 10 is an active carbon decoloring tank, the outlet end of the decoloring tank 10 is communicated with a light component removing tower 13 through a filter 11, the light component removing tower 13 is a light component removing tower, wherein the filter 11 is a security filter, a light component removal tower feeding tank 12 is further arranged between the filter 11 and the light component removal tower 13, the light component removal tower feeding tank 12 supplies materials into the light component removal tower 13, the materials are filtered by the filter 11 and then enter the light component removal tower feeding tank 12 to be pumped to the light component removal tower 13 for dehydration, the outlet end of the top of the light component removal tower 13 is further communicated with a tower top reflux tank, the tower top reflux tank is used for separating water from part of incompletely dehydrated dimethyl disulfide and then sending the water back to the light component removal tower feeding tank 12 for re-dehydration, meanwhile, water phase treated in the tower top reflux tank is sent to an alkali distribution tank for alkali distribution, the recovery utilization rate is improved, and waste gas treated by the tower top reflux tank is sent to an incineration system for treatment.
A first reboiler is arranged in the light component removal tower 13, the temperature is raised by steam heating, the tower pressure of the light component removal tower 13 is controlled to be 0.2Mpa, the temperature is 125 ℃, and all moisture in the light component removal tower 13 is vaporized and flows out from the top of the tower to enter a tower top cooler for cooling, and the temperature is reduced to a wastewater recovery system;
the outlet end of a light component removing tower 13 is communicated with the middle inlet end of a heavy component removing tower 14, moisture-free dimethyl disulfide which is treated by the light component removing tower 13 is pumped out by a tower kettle pump and sent to the middle of the dimethyl disulfide heavy component removing tower 14, the top outlet end of the heavy component removing tower 14 is respectively communicated with the top inlet end of the heavy component removing tower and a finished product storage tank after passing through a third cooler 17, a second reboiler is arranged in the dimethyl disulfide heavy component removing tower 14 and is heated by steam, the tower pressure is controlled to be 0.25Mpa and the temperature is controlled to be 135 ℃, refined dimethyl disulfide is produced at the tower top of the heavy component removing tower 14, the refined dimethyl disulfide enters the third cooler 17 for cooling and condensation to form dimethyl disulfide liquid, wherein one part of the dimethyl disulfide liquid is recycled to a dimethyl disulfide intermediate tank and is pumped back to enter the tower for multiple times of rectification by a reflux pump at the tower top to improve the rectification effect, and the other part of the dimethyl disulfide liquid is analyzed and qualified to form a dimethyl disulfide finished product, controlling the flow rate to be 980kg/h, and sending the product into a finished product storage tank for storage, wherein the dimethyl disulfide intermediate tank is also a tower top reflux tank;
the outlet end at the bottom of the heavy component removal tower 14 is communicated with the inlet end of a steam vaporizer, the liquid level of a tower kettle in the heavy component removal tower is controlled, intermittent discharge is carried out, trace components heavier than dimethyl disulfide are pumped out by the tower kettle, vaporized by a steam heater with the pressure of 0.8Mpa to 175 ℃, and sent to an incineration system for treatment.
Namely, the sodium methyl mercaptide produced by the sodium methyl mercaptide reaction tower 3 can be used as a finished product and also can be used as a raw material for producing dimethyl disulfide, thereby realizing the joint production of two products of sodium methyl mercaptide and dimethyl disulfide, compared with the existing production method in the prior art, the equipment investment cost is effectively reduced by using one set of equipment, the yield proportion of the sodium methyl mercaptide and the dimethyl disulfide is conveniently selected and adjusted according to the actual requirement, the enterprise benefit is improved, the investment of toxic raw materials and the production of toxic byproducts are avoided, the organized discharge and recycling of waste liquid and waste gas are realized, the zero discharge is achieved, meanwhile, in the production process, the process operation temperature and the pressure are not high, the integral control difficulty is low, the equipment design pressure level is high, the safety is high, and the large-scale production of enterprises is convenient.
The joint production process of sodium methyl mercaptide and dimethyl disulfide comprises the following steps:
s1, heating and vaporizing the methyl mercaptan with the content of 99.8 percent and the temperature of 7 ℃ by a methyl mercaptan vaporizer, and then reacting the methyl mercaptan with the sodium hydroxide solution with the content of 16 percent to 18 percent to generate the sodium methyl mercaptide solution, wherein the reaction equation is CH3SH+NaOH＝CH3SNa+H2O；
In the step S1, the oxidation reactor is a shell-and-tube reactor, the shell side of the shell-and-tube reactor is circularly controlled in temperature by circulating water at 80 ℃, the tube side is formed by mixing sodium methyl mercaptide with oxygen and then reacting with a catalyst, and the oxidation reaction conditions are as follows: the reaction pressure is 0.6-0.8 Mpa, and the reaction temperature is 80-90 ℃;
s2, carrying out oxidation reaction on the sodium methyl mercaptide solution with the content of 20% and oxygen-containing gas in an oxidation reactor, wherein the oxygen-containing gas is 215kg/h, the pressure is 0.7Mpa, the temperature is 90 +/-5 ℃, and the content of 80% oxygen is used for generating dimethyl disulfide and sodium hydroxide aqueous solution, and the reaction equation is 2CH3SNa+0.5O2+H2O→CH3SSCH3+2NaOH；
S3, separating the dimethyl disulfide and the sodium hydroxide aqueous solution through the following separation steps to obtain dimethyl disulfide;
step S3 includes the following separation steps:
(1) after the dimethyl disulfide and the sodium hydroxide aqueous solution are condensed, separating sodium hydroxide by a liquid separation tank to obtain crude dimethyl disulfide and a small amount of water;
(2) dehydrating the crude dimethyl disulfide containing water through a light component removal tower to remove the water of the crude dimethyl disulfide, wherein a first reboiler is arranged in the light component removal tower, the tower pressure of the light component removal tower is controlled to be 0.2Mpa, the temperature is 125 ℃, and the water in a tower kettle of the light component removal tower is completely vaporized and flows out from the tower top to enter a tower top cooler for cooling, and then the water is conveyed to a wastewater recovery system;
(3) rectifying the crude dimethyl disulfide without water content in a de-weighting tower to form a dimethyl disulfide finished product, specifically, a second reboiler in the de-weighting tower, wherein the tower pressure of the de-weighting tower is 0.25Mpa, the temperature is 135 ℃, refined dimethyl disulfide is produced at the top of the de-weighting tower, and enters a third cooler for cooling and condensation to form dimethyl disulfide liquid, wherein a part of the dimethyl disulfide liquid is recovered to a dimethyl disulfide intermediate tank and is pumped back to the tower through a reflux pump at the top of the tower to be fed into the tower, and the other part of the dimethyl disulfide liquid is qualified after analysis and is fed into a tank area through flow rate control; wherein, the liquid level of the tower kettle is controlled in the de-heavy tower, the liquid is discharged discontinuously, and trace components heavier than dimethyl disulfide are pumped out by the tower kettle, vaporized by a steam heater with the pressure of 0.8Mpa to 175 ℃, and sent to an incineration system for treatment.
The sodium methionate and dimethyl disulfide joint production system described in the above embodiment can execute the sodium methionate and dimethyl disulfide joint production process provided in the embodiment of the present invention, and the sodium methionate and dimethyl disulfide joint production process has the corresponding functional components and beneficial effects of the sodium methionate and dimethyl disulfide joint production system described in the above embodiment, and for specific reference, the above embodiment applied to the sodium methionate and dimethyl disulfide joint production system is referred to, and the embodiments of the present invention are not described herein again.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. The sodium methyl mercaptide and dimethyl disulfide joint production system is characterized by comprising a methyl mercaptan feeding tank and a methyl mercaptan vaporizer, wherein an outlet of the methyl mercaptan feeding tank is communicated with an inlet end of the methyl mercaptan vaporizer, an outlet end of the methyl mercaptan vaporizer is communicated with an inlet end of a sodium methyl mercaptide reaction tower, an outlet end of the sodium methyl mercaptide reaction tower is communicated with an inlet end of an oxidation reactor, and a top inlet end of the sodium methyl mercaptide reaction tower is also communicated with an alkali liquor supply device;
the inlet end of the oxidation reactor is also communicated with an oxygen buffer tank, and the outlet end of the oxidation reactor is communicated with a light component removal unit.
2. The sodium thiomethoxide and dimethyl disulfide joint production system according to claim 1, wherein the lightness-removing unit comprises a liquid separation tank communicated with the outlet end of the oxidation reactor through a second cooler, the outlet end of the liquid separation tank is communicated with the inlet end of a decoloring tank, and the outlet end of the decoloring tank is communicated with the lightness-removing column through a filter;
the outlet end of the light component removing tower is communicated with the middle inlet end of the heavy component removing tower, the top outlet end of the heavy component removing tower is communicated with the top inlet end of the heavy component removing tower and a finished product storage tank respectively after passing through a third cooler, and the bottom outlet end of the heavy component removing tower is communicated with the inlet end of a steam vaporizer.
3. A process for the co-production of sodium methionate and dimethyldisulfide using the system of claim 1 comprising the steps of:
s1, heating and vaporizing methyl mercaptan by a methyl mercaptan vaporizer, and then reacting with a sodium hydroxide solution to generate a sodium methyl mercaptan solution, wherein the reaction equation is CH3SH+NaOH＝CH3SNa+H2O；
S2, carrying out oxidation reaction on the sodium methyl mercaptide solution and oxygen-containing gas in an oxidation reactor to generate dimethyl disulfide and sodium hydroxide aqueous solution, and obtaining a reaction equationIs 2CH3SNa+0.5O2+H2O→CH3SSCH3+2NaOH；
S3, separating the dimethyl disulfide and the sodium hydroxide aqueous solution to obtain the dimethyl disulfide.
4. The process for the co-production of sodium thiomethoxide and dimethyldisulfide according to claim 2, wherein the step S3 comprises the steps of:
(1) after the dimethyl disulfide and the sodium hydroxide aqueous solution are condensed, separating the sodium hydroxide aqueous solution by a liquid separation tank to obtain crude dimethyl disulfide and water;
(2) and dehydrating the crude dimethyl disulfide containing water by a light component removal tower to remove the water of the crude dimethyl disulfide.
5. The process of claim 4, wherein the first reboiler is disposed inside the lightness-removing column, the pressure of the lightness-removing column is controlled at 0.2MPa, the temperature is 125 ℃, and the water in the column bottom is completely vaporized and flows out from the top of the light-removing column, enters the top of the light-removing column, and is cooled by the top cooler, and then enters the wastewater recovery system.
6. The process of claim 4, wherein the step S3 further comprises the steps of:
(3) and rectifying the crude dimethyl disulfide subjected to moisture removal by a de-weighting tower to form a finished product of dimethyl disulfide.
7. The process of claim 6, wherein the refined dimethyl disulfide is cooled and condensed in a cooler at the top of the tower at a tower pressure of 0.25MPa and a temperature of 135 ℃, the liquid is recovered to a dimethyl disulfide intermediate tank, pumped back into the tower by a reflux pump at the top of the tower and fed into the tower, and the dimethyl disulfide finished product is fed into a tank area after passing another analysis through flow control.
8. The process of claim 6, wherein the liquid level in the tower bottom is controlled, the liquid is discharged intermittently, and the trace of the component heavier than dimethyl disulfide is pumped out through the tower bottom and vaporized through a heater to be sent to an incineration system for disposal.
9. The process of claim 3, wherein the oxidation reactor in the step S1 is a shell-and-tube reactor, the shell side of the shell-and-tube reactor is controlled by circulating hot water at 80 ℃, and the tube side is formed by mixing sodium methionate with oxygen and then reacting with the catalyst.
10. The process of claim 9, wherein the oxidation reaction conditions are: the reaction pressure is 0.6-0.8 Mpa, and the reaction temperature is 80-90 ℃.
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