CN108250114B - Sodium methyl mercaptide production process and device - Google Patents
Sodium methyl mercaptide production process and device Download PDFInfo
- Publication number
- CN108250114B CN108250114B CN201810171741.4A CN201810171741A CN108250114B CN 108250114 B CN108250114 B CN 108250114B CN 201810171741 A CN201810171741 A CN 201810171741A CN 108250114 B CN108250114 B CN 108250114B
- Authority
- CN
- China
- Prior art keywords
- methyl mercaptan
- absorption tower
- sodium
- methyl
- heat exchanger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 206
- 238000010521 absorption reaction Methods 0.000 claims abstract description 120
- 239000003513 alkali Substances 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000003860 storage Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 sodium hydroxide-sodium methyl mercaptan Chemical compound 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 18
- XHXXWWGGXFUMAJ-UHFFFAOYSA-N methanethiol;sodium Chemical compound [Na].SC XHXXWWGGXFUMAJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008016 vaporization Effects 0.000 claims abstract description 13
- 238000009834 vaporization Methods 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000012071 phase Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000006096 absorbing agent Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 56
- 239000011257 shell material Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 3
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000000543 intermediate Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- YDBYJHTYSHBBAU-YFKPBYRVSA-N S-methyl-L-methioninate Chemical compound C[S+](C)CC[C@H](N)C([O-])=O YDBYJHTYSHBBAU-YFKPBYRVSA-N 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 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
- 239000008234 soft water Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a process and a device for producing sodium methyl mercaptan solution, wherein refined methyl mercaptan enters a tube side of a primary heat exchanger through a methyl mercaptan storage tank, and sodium hydroxide-sodium methyl mercaptan mixed solution extracted from the bottom of a secondary absorption tower enters a shell layer of the primary heat exchanger; after heat exchange, methyl mercaptan is vaporized and enters a primary absorption tower; sodium hydroxide-methyl mercaptan sodium mixed solution is prepared from the upper part of the primary absorption tower enters the absorption tower; methyl sodium mercaptide the finished product is formed by a first stage extracting from the bottom of the absorption tower; methyl mercaptan from the top of the primary absorber, the liquid enters the tower from a feed inlet at the lower part of the secondary absorption tower; the liquid alkali from the liquid alkali storage tank enters the absorption tower from the upper part of the secondary absorption tower, and the gas phase and the liquid phase are reversely contacted and mixed in the tower to obtain the sodium hydroxide-methyl sodium mercaptide mixed solution. The process and the device produce the sodium methyl mercaptide, the exothermic heat of reaction can be used as a heat source for methyl mercaptan vaporization, the free adjustment of the concentration of the sodium methyl mercaptide is realized, and meanwhile, the logistics transportation cost is saved for manufacturers using the sodium methyl mercaptide as a production raw material.
Description
Technical Field
The invention belongs to the field of production and preparation of sodium methyl mercaptide, and particularly relates to a process for producing sodium methyl mercaptide solution by using refined methyl mercaptide and a corresponding device.
Background
Sodium methyl mercaptide is a colorless transparent strong alkaline liquid, has special odor, and can be used as raw materials of pesticides, medicines and pigment intermediates, such as pesticide simetryn, methomyl and organic intermediate raw materials; raw materials of food additives methionine, vitamin U and rubber vulcanizing agent; antidote to hydrogen sulfide poisoning; gas, natural gas odorizing agent, etc. The common raw material of sodium methyl mercaptide used by domestic manufacturers is 20% sodium methyl mercaptide aqua, and the sodium methyl mercaptide is transported to the factories through tank trucks. Because the content of the effective component sodium methyl mercaptide is only about 20%, and the balance is water, when the raw material is transported far, the transportation is equivalent to the transportation of a large amount of water in a long distance, the logistics cost is greatly increased, and the production cost is obviously increased.
At present, sodium methyl mercaptide products in China are mostly prepared by taking sodium hydrosulfide as a raw material, reacting with dimethyl sulfate or methyl chloride to generate methyl mercaptide, and then absorbing with liquid alkali to obtain the sodium methyl mercaptide products. Wherein, dimethyl sulfate is a highly toxic raw material, and has great potential safety hazard in the processes of use, storage and transportation. The final yield of methyl sodium mercaptide in the dimethyl sulfate-sodium hydrosulfide process is only about 75% -80%, and a large amount of wastewater containing organic matters is generated in the production process, so that the environmental impact is large. The byproduct thioether of the chloromethane-sodium hydrosulfide process and a large amount of wastewater containing sodium chloride and organic matters are difficult to treat subsequently.
Disclosure of Invention
The invention provides a process for producing sodium methyl mercaptide and a corresponding device thereof, which adopt refined methyl mercaptide raw materials to obtain a finished product of sodium methyl mercaptide through two-stage absorption. Through the process and the device, manufacturers who originally need to transport 20% methyl mercaptan sodium water agent in a long distance can change into transport methyl mercaptan, so that a large amount of logistics cost is saved; meanwhile, manufacturers can freely allocate the concentration of sodium methyl mercaptide, so that the production is convenient; the exothermic heat of reaction is fully utilized as the heat required by methyl mercaptan vaporization in the production process of the device, so that the production cost is further saved. The process and the device have no three wastes during the production of the sodium methyl mercaptan, and avoid the problem of environmental pollution caused by the production of the sodium methyl mercaptan by a dimethyl sulfate method and a methyl chloride method.
The process of the invention uses liquid alkali and hydrogen sulfide content H 2 S (wt%) is less than or equal to 0.01% of refined methyl mercaptan is used as raw material, and the method comprises the following technological processes:
methyl mercaptan vaporization: the refined methyl mercaptan enters a primary heat exchanger through a methyl mercaptan storage tank and exchanges heat with sodium hydroxide-methyl mercaptan sodium mixed solution extracted from the bottom of a secondary absorption tower; methyl mercaptan is vaporized and then enters a primary absorption tower; the temperature of the sodium hydroxide-sodium methyl mercaptide mixed solution is exchanged from 55-70 ℃ to 20-30 ℃;
primary absorption: the vaporized methyl mercaptan enters from the lower part of the primary absorption tower; the sodium hydroxide-sodium methyl mercaptide mixed solution from the secondary absorption tower enters the absorption tower from the upper part of the primary absorption tower after being subjected to heat exchange by a heat exchanger and cooled to 20-30 ℃; the gas phase and the liquid phase are reversely contacted and mixed in the first-stage absorption tower; absorbing the obtained finished product of sodium methyl mercaptide, and extracting the finished product of sodium methyl mercaptide from the bottom of the primary absorption tower;
secondary absorption: methyl mercaptan from the top of the primary absorption tower enters the tower from a feed inlet at the lower part of the secondary absorption tower; the liquid alkali from the liquid alkali storage tank enters the absorption tower from the upper part of the secondary absorption tower, the gas phase and the liquid phase are in reverse contact and are mixed in the tower, methyl mercaptan is completely absorbed by excessive liquid alkali, a sodium hydroxide-methyl mercaptan sodium mixed solution is obtained, the mixed solution is extracted from the tower bottom, and the mixed solution is pumped to a heat exchanger by an intermediate pump.
In the methyl mercaptan vaporization step, methyl mercaptan and sodium hydroxide-methyl mercaptan sodium mixed solution flow reversely and exchange heat on the tube side and the shell layer of the primary heat exchanger respectively, namely methyl mercaptan enters from the top of the tube side of the primary heat exchanger, and sodium hydroxide-methyl mercaptan sodium mixed solution enters from the bottom of the shell layer of the primary heat exchanger.
The methyl mercaptan is vaporized and then enters the primary absorption tower through the secondary heat exchanger.
In the methyl mercaptan vaporization step, the ratio of the feeding volume flow rate of the sodium hydroxide-methyl mercaptan sodium mixed solution to the liquid-phase methyl mercaptan is that the mixed solution: methyl mercaptan= (3.5-4.1): 1.
in the absorption process, the initial concentration of liquid caustic soda adopted in the absorption is 13-15 percent (wt%) of NaOH, wherein methyl mercaptan added into a primary absorption tower is excessive relative to sodium hydroxide in the primary absorption tower so as to ensure that a finished product extracted from the tower bottom is free of free caustic soda, and the excessive methyl mercaptan is discharged from the top of the primary absorption tower and enters a secondary absorption tower; the sodium hydroxide in the secondary absorption tower is excessive relative to methyl mercaptan so as to ensure that the methyl mercaptan is completely absorbed. The concentration of sodium hydroxide-sodium methyl mercaptide solution discharged from the secondary absorption tower is controlled to be CH during production 3 12-18% of SNa (wt%) and 1-5% of NaOH (wt%). The total mass ratio of methyl mercaptan to sodium hydroxide feed in the whole absorption process is that the methyl mercaptan: sodium hydroxide= (1.20-1.22): 1.
The device for producing the sodium methyl mercaptide at least comprises the following equipment: the liquid alkali storage tank, the methyl mercaptan storage tank, the heat exchanger, the absorption tower and the pump are connected in the following manner:
the liquid alkali storage tank a is connected with an alkali feed inlet at the upper part of the secondary absorption tower i through an alkali feed pump c; the bottom extraction port of the second-stage absorption tower i is connected with the shell feed inlet of the first-stage heat exchanger e through an intermediate pump g; the shell discharge port of the primary heat exchanger e is connected with the upper feed inlet of the primary absorption tower h through a pipeline;
the methyl mercaptan storage tank b is connected with a tube side feed inlet of the primary heat exchanger e of the methyl mercaptan feed pump d; the e tube side discharge port of the primary heat exchanger is connected with the f tube side feed port of the secondary heat exchanger through a pipeline; the tube side discharge port of the second-level heat exchanger f is connected with the air inlet at the lower part of the first-level absorption tower h through a pipeline; and a discharge port at the top of the first-stage absorption tower h is connected with an air inlet at the lower part of the second-stage absorption tower through a pipeline, so that the sodium methyl mercaptan production device can be obtained.
And in normal operation of the primary heat exchanger e, the tube side material is methyl mercaptan, and the shell material is sodium hydroxide-methyl sodium mercaptide mixed solution extracted from the secondary absorption tower i.
The secondary heat exchanger f is a standby heat exchanger, and the vaporized methyl mercaptan can not pass through the secondary heat exchanger during production in hot seasons, directly connecting a tube side discharge port of the primary heat exchanger e with an air inlet of the primary absorption tower h; the heat required by the vaporization of methyl mercaptan is insufficient in cold production, and the heat is supplied by the steam through the secondary heat exchanger.
The primary heat exchanger e adopts the specific connection mode, the methyl mercaptan material is adopted as the tube side during production, the sodium hydroxide-methyl sodium mercaptide mixed solution extracted by the secondary absorption tower i is adopted as the shell layer, the reaction heat release is used for vaporizing the methyl mercaptan, and a large amount of energy consumption is saved. The second-stage absorption tower is adopted to collect the material instead of the first-stage absorption tower, and the reaction and heat release are mainly carried out in the second-stage absorption tower, so that the concentration of sodium methyl mercaptide in the first-stage absorption tower is high, and low-temperature crystallization blocking equipment can occur after the material is used for heat exchange.
The secondary heat exchanger f can be used as a standby heat exchanger, and can only serve as a buffer function when the ambient temperature and the liquid alkali temperature are higher in summer; when the ambient temperature and the liquid alkali temperature are low in winter, the secondary heat exchanger can be used as a methyl mercaptan vaporization supplementary heat source.
The primary absorption tower h and the secondary absorption tower i adopt an absorption mode that a liquid phase is a continuous phase, a methyl mercaptan gas phase is a disperse phase, and saddle ring packing is arranged in the tower so as to be favorable for the methyl mercaptan to be fully absorbed. In the first-stage absorption tower, methyl mercaptan is excessive relative to sodium hydroxide so as to ensure that the bottom of the first-stage absorption tower h is saturated in absorption of finished products; the excessive methyl mercaptan gas is discharged from the top of the first-stage absorption tower and enters a second-stage absorption tower i for continuous absorption; the sodium hydroxide in the secondary absorption tower is excessive relative to methyl mercaptan so as to ensure that the residual methyl mercaptan is completely absorbed.
In the liquid alkali storage tank a, liquid alkali with concentration of 13-15% of NaOH (wt%) is stored in normal production, and a manufacturer can properly adjust the concentration of the alkali liquid according to the self requirement so as to produce the sodium methyl mercaptide solution with the required specific concentration.
The methyl mercaptan storage tank b is used for storing refined methyl mercaptan and requires the content H of hydrogen sulfide in methyl mercaptan materials 2 S (wt%) is less than or equal to 0.01%, so as to ensure that the sodium sulfide content of the produced sodium methyl mercaptan solution is qualified.
The production process and the corresponding device provided by the invention can adopt refined methyl mercaptan, 48% industrial liquid alkali and soft water as raw materials to prepare methyl sodium mercaptide solutions with different concentrations, and the product concentration can be independently regulated by manufacturers; the method avoids the long-distance transportation of 20% sodium methyl mercaptide water agent by manufacturers needing sodium methyl mercaptide raw materials, and saves a large amount of logistics cost; the methyl mercaptan is utilized to absorb the exothermic heat of the reaction, so that the production energy consumption is reduced; the obtained product has low content of sulfide impurities and good product quality.
Drawings
Fig. 1 is a simplified block diagram of an apparatus employed in the process of the present invention.
a: a liquid alkali storage tank; b: a methyl mercaptan storage tank; c: a liquid alkali feed pump; d: methyl mercaptan feed pump; e: a primary heat exchanger; f: a secondary heat exchanger; g: an intermediate pump; h: a first-stage absorption tower; i: a secondary absorption tower.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings, but the scope of the patent claims is not limited to the scope of the examples.
Methyl mercaptan vaporization: refined methyl mercaptan in the methyl mercaptan storage tank b is pumped into a primary heat exchanger e through a methyl mercaptan feed pump d, and flows reversely with methyl mercaptan-sodium methyl mercaptan mixed materials extracted from the bottom of a secondary absorption tower i in the tube side and the shell layer of the heat exchanger e respectively for heat exchange. Methyl mercaptan is vaporized and then enters a secondary heat exchanger f; the temperature of the extracted materials of the secondary absorption tower is exchanged from 60 ℃ to 20-30 ℃. When the temperature of the materials extracted from the secondary absorption tower in cold seasons is lower, the secondary heat exchanger f supplies heat to the methyl mercaptan by steam so as to ensure that the methyl mercaptan is completely vaporized.
Primary absorption: the vaporized methyl mercaptan enters the absorption tower from the lower part of the first-stage absorption tower h; the mixed solution of liquid alkali and sodium methyl mercaptide from the secondary absorption tower is subjected to heat exchange by a heat exchanger e and cooled to 20-30 ℃, and then enters the absorption tower from the upper part of the primary absorption tower h; the gas phase and the liquid phase are reversely contacted and mixed in the tower, the excess methyl mercaptan is controlled, the complete reaction of sodium hydroxide in the solution is ensured, and the extracted product has no free alkali. Absorbing the obtained finished product of sodium methyl mercaptide, and extracting the finished product of sodium methyl mercaptide from the bottom of the primary absorption tower; the excessive methyl mercaptan is discharged from the top of the primary absorption tower and enters the secondary absorption tower i.
Secondary absorption: methyl mercaptan from the top of the primary absorption tower h enters the tower from a feed inlet at the lower part of the secondary absorption tower i; 13% -15% of liquid alkali from the liquid alkali storage tank a enters the absorption tower from the upper part of the secondary absorption tower, gas and liquid phases are reversely contacted and mixed in the tower, methyl mercaptan is completely absorbed by excessive liquid alkali, and a methyl mercaptan-methyl mercaptan sodium mixed solution is obtained, extracted from the tower bottom and sent to the primary heat exchanger e by the intermediate pump g.
When the process and the device are adopted to produce sodium methyl mercaptan, the raw materials are required to refine the methyl mercaptan, and the content H of hydrogen sulfide in the methyl mercaptan 2 S (wt%) is less than or equal to 0.01%, so as to ensure that the sulfide index of the produced product is qualified.
Summer production example: detecting the content H of hydrogen sulfide in methyl mercaptan raw material in a certain production period when the summer environmental temperature is above 25 DEG C 2 S (wt%) 0.001%; the temperature of the alkali liquor in the alkali liquor storage tank a is 28 ℃ and the concentration is 14.3%, and the alkali liquor is taken as raw material alkali to enterAfter methyl mercaptan is absorbed by a secondary absorption tower, a sodium hydroxide-methyl mercaptan sodium mixed solution is obtained, wherein the specific concentration is CH 3 SNa (wt%) 16.3%, naOH (wt%) 3.8%, and the post-absorption temperature (secondary absorption tower withdrawal temperature) was 65.3 ℃. After the mixed solution is continuously pumped into a primary heat exchanger to exchange heat with methyl mercaptan, the temperature of the mixed solution is reduced to 27.4 ℃, the methyl mercaptan is vaporized in the primary heat exchanger, and the temperature after vaporization is 16.6 ℃. At this time, methyl mercaptan is completely vaporized, and directly enters the first-stage absorption tower without being additionally heated by a second-stage heat exchanger to continuously react with the mixed solution. After the absorption reaction is finished, a finished product of sodium methyl mercaptide is obtained, the appearance of the finished product is detected to be colorless, clear and transparent, and the content (wt%) of each component is as follows: CH (CH) 3 SNa 21.3%，Na 2 S 0.01%，NaOH 0.00%.
Winter production example: during a certain production period, detecting the environmental temperature of minus 2 ℃ and the content H of hydrogen sulfide in methyl mercaptan raw material 2 S (wt%) 0.002%; the temperature of the alkali liquor in the liquid alkali storage tank is 5 ℃ and the concentration is 13.7%, and after the alkali liquor is taken as the raw material alkali to be absorbed into methyl mercaptan in a secondary absorption tower, the concentration (wt%) of the obtained sodium hydroxide-methyl mercaptan sodium mixed solution is as follows: CH (CH) 3 SNa 16.7%, naOH 2.9%, temperature 42.5 ℃. After heat exchange between the mixed solution and methyl mercaptan in the primary heat exchanger, the temperature of the mixed solution is reduced to 22.1 ℃, the methyl mercaptan is incompletely vaporized, and the temperature is 7.2 ℃. At the moment, methyl mercaptan is continuously introduced into a secondary heat exchanger, 0.4MPa steam is introduced into a shell layer of the secondary heat exchanger, and the methyl mercaptan is completely vaporized and then subjected to primary absorption. After the absorption is finished, detecting a finished product of sodium methyl mercaptide extracted from the bottom of the primary absorption tower, wherein the appearance is colorless, clear and transparent, and the contents of all components are as follows: CH (CH) 3 SNa 20.5%，Na 2 S 0.01%，NaOH 0.00%.
Example 2
The device for producing the sodium methyl mercaptide at least comprises the following equipment: the liquid alkali storage tank, the methyl mercaptan storage tank, the heat exchanger, the absorption tower and the pump are connected in the following manner:
the liquid alkali storage tank a is connected with an alkali feed inlet at the upper part of the secondary absorption tower i through an alkali feed pump c; the bottom extraction port of the second-stage absorption tower i is connected with the shell feed inlet of the first-stage heat exchanger e through an intermediate pump g; the shell discharge port of the primary heat exchanger e is connected with the upper feed inlet of the primary absorption tower h through a pipeline;
the methyl mercaptan storage tank b is connected with a tube side feed inlet of the primary heat exchanger e of the methyl mercaptan feed pump d; the e tube side discharge port of the primary heat exchanger is connected with the f tube side feed port of the secondary heat exchanger through a pipeline; the tube side discharge port of the second-level heat exchanger f is connected with the air inlet at the lower part of the first-level absorption tower h through a pipeline; and a discharge port at the top of the first-stage absorption tower h is connected with an air inlet at the lower part of the second-stage absorption tower through a pipeline, so that the sodium methyl mercaptan production device can be obtained.
And in normal operation of the primary heat exchanger e, the tube side material is methyl mercaptan, and the shell material is sodium hydroxide-methyl sodium mercaptide mixed solution extracted from the secondary absorption tower i.
The second-level heat exchanger f is a standby heat exchanger, and vaporized methyl mercaptan can be directly connected with a tube side discharge port of the first-level heat exchanger e and an air inlet of the first-level absorption tower h without passing through the second-level heat exchanger during production in hot seasons; the heat required by the vaporization of methyl mercaptan is insufficient in cold production, and the heat is supplied by the steam through the secondary heat exchanger.
Claims (6)
1. A process for preparing sodium methyl mercaptide features that the liquid alkali and hydrogen sulfide content H 2 S, the refined methyl mercaptan with the weight percent of less than or equal to 0.01 percent is used as a raw material to synthesize sodium methyl mercaptan, and the method comprises the following technical processes:
methyl mercaptan vaporization: refined methyl mercaptan enters a tube pass of the primary heat exchanger through a methyl mercaptan storage tank, and sodium hydroxide-methyl mercaptan sodium mixed solution extracted from the bottom of the secondary absorption tower enters a shell layer of the primary heat exchanger; after heat exchange, methyl mercaptan is vaporized and enters a primary absorption tower; the temperature of the sodium hydroxide-sodium methyl mercaptide mixed solution is reduced from 55-70 ℃ to 20-30 ℃;
primary absorption: the vaporized methyl mercaptan enters from the lower part of the primary absorption tower; the sodium hydroxide-sodium methyl mercaptide mixed solution enters an absorption tower from the upper part of the primary absorption tower after being subjected to heat exchange by a primary heat exchanger and cooled to 20-30 ℃; the gas phase and the liquid phase are reversely contacted and mixed in the first-stage absorption tower; absorbing the obtained finished product of sodium methyl mercaptide, and extracting the finished product of sodium methyl mercaptide from the bottom of the primary absorption tower;
secondary absorption: methyl mercaptan from the top of the primary absorption tower enters the tower from a feed inlet at the lower part of the secondary absorption tower; the liquid alkali from the liquid alkali storage tank enters the absorption tower from the upper part of the secondary absorption tower, the gas phase and the liquid phase are reversely contacted and mixed in the tower, methyl mercaptan is completely absorbed by excessive liquid alkali to obtain sodium hydroxide-methyl sodium mercaptide mixed solution, the mixed solution is extracted from the tower bottom and is pumped to a heat exchanger by an intermediate pump;
wherein, the mass ratio of methyl mercaptan to sodium hydroxide is that methyl mercaptan: 1, wherein the alkali liquor feeding concentration of the secondary absorption tower is NaOH, the weight percent is 13-15%, and the sodium hydroxide-methyl sodium mercaptide solution concentration discharged from the secondary absorption tower is CH 3 SNa，wt% 12%～18%，NaOH，wt% 1%～5%。
2. The process for producing sodium methyl mercaptan according to claim 1, wherein in the step of vaporizing methyl mercaptan, methyl mercaptan and sodium hydroxide-sodium methyl mercaptan mixed solution are subjected to countercurrent heat exchange on a tube side and a shell layer of the primary heat exchanger respectively, namely methyl mercaptan enters from the top of the tube side of the primary heat exchanger, sodium hydroxide-sodium methyl mercaptan mixed solution enters from the bottom of the shell layer of the primary heat exchanger, and the ratio of the feed volume flow rate of the sodium hydroxide-sodium methyl mercaptan mixed solution to the feed volume flow rate of the liquid-phase methyl mercaptan mixed solution is as follows: methyl mercaptan= (3.5-4.1): 1.
3. the process for producing sodium methyl mercaptan according to claim 1, wherein methyl mercaptan is vaporized and fed to the primary absorber through the secondary heat exchanger.
4. The process for producing sodium methyl mercaptan according to claim 1, wherein in the primary absorption step, methyl mercaptan is fed in an excess amount relative to sodium hydroxide, and after the reaction is completed, the excess methyl mercaptan is discharged from the top of the primary absorption column and fed into the secondary absorption column.
5. A sodium methyl mercaptide production device, characterized in that the device adopted at least comprises the following equipment: the liquid alkali storage tank, the methyl mercaptan storage tank, the heat exchanger, the absorption tower and the pump are connected in the following manner:
the liquid alkali storage tank (a) is connected with an alkali feed inlet at the upper part of the secondary absorption tower (i) through an alkali feed pump (c); the bottom extraction port of the second-stage absorption tower (i) is connected with the shell feeding port of the first-stage heat exchanger (e) through an intermediate pump (g); the shell discharge port of the primary heat exchanger (e) is connected with the upper feed port of the primary absorption tower (h) through a pipeline;
the methyl mercaptan storage tank (b) is connected with a tube side feed inlet of the primary heat exchanger (e) through a methyl mercaptan feed pump (d); the tube side discharge port of the primary heat exchanger (e) is connected with the tube side feed port of the secondary heat exchanger (f) through a pipeline; the tube side discharge port of the secondary heat exchanger (f) is connected with the air inlet at the lower part of the primary absorption tower (h) through a pipeline; and (3) connecting a top discharge port of the first-stage absorption tower (h) with an air inlet at the lower part of the second-stage absorption tower through a pipeline to obtain the sodium methyl mercaptide production device.
6. The apparatus for producing sodium methyl mercaptan according to claim 5, wherein the primary heat exchanger (e) is operated normally, the tube side material is methyl mercaptan, and the shell material is sodium hydroxide-sodium methyl mercaptan mixed solution extracted from the secondary absorption tower (i).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810171741.4A CN108250114B (en) | 2018-03-01 | 2018-03-01 | Sodium methyl mercaptide production process and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810171741.4A CN108250114B (en) | 2018-03-01 | 2018-03-01 | Sodium methyl mercaptide production process and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108250114A CN108250114A (en) | 2018-07-06 |
| CN108250114B true CN108250114B (en) | 2023-12-29 |
Family
ID=62745643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810171741.4A Active CN108250114B (en) | 2018-03-01 | 2018-03-01 | Sodium methyl mercaptide production process and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250114B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382072A (en) * | 2018-12-14 | 2019-02-26 | 重庆紫光化工股份有限公司 | A kind of system and method for continuous preparation high concentration high-quality sodium methyl mercaptide |
| CN109433144A (en) * | 2019-01-04 | 2019-03-08 | 山东豪迈化工技术有限公司 | Reaction unit, purposes and synthetic method in synthesis of methyl mercaptan sodium |
| CN112516753A (en) * | 2020-11-13 | 2021-03-19 | 鸣洋(武汉)化工工程有限公司 | Continuous production process and device for methylamine aqueous solution |
| CN112778174A (en) * | 2021-04-12 | 2021-05-11 | 蓝星安迪苏南京有限公司 | Device and method for preparing high-concentration sodium methyl mercaptide solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6235941B1 (en) * | 1998-02-13 | 2001-05-22 | Albemarle Corporation | Process for production of organic disulfides |
| CN201268672Y (en) * | 2008-07-31 | 2009-07-08 | 郑凌峰 | Sodium methyl mercaptide producing system |
| CN105330577A (en) * | 2015-11-30 | 2016-02-17 | 白国强 | Production technology of high-purity sodium methyl mercaptide |
| CN105646302A (en) * | 2016-02-05 | 2016-06-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Production method of methyl mercaptan salt |
| CN105693573A (en) * | 2016-03-11 | 2016-06-22 | 湖北兴发化工集团股份有限公司 | Method and device for producing sodium thiomethoxide from by-product obtained through synthesis of dimethyl sulfide |
| CN208200790U (en) * | 2018-03-01 | 2018-12-07 | 湖北兴发化工集团股份有限公司 | A kind of sodium methyl mercaptide process units |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101048593B1 (en) * | 2009-02-27 | 2011-07-12 | 씨제이제일제당 (주) | How to increase methionine production using a mixture of methylmercaptan and dimethylsulfide |
-
2018
- 2018-03-01 CN CN201810171741.4A patent/CN108250114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6235941B1 (en) * | 1998-02-13 | 2001-05-22 | Albemarle Corporation | Process for production of organic disulfides |
| CN201268672Y (en) * | 2008-07-31 | 2009-07-08 | 郑凌峰 | Sodium methyl mercaptide producing system |
| CN105330577A (en) * | 2015-11-30 | 2016-02-17 | 白国强 | Production technology of high-purity sodium methyl mercaptide |
| CN105646302A (en) * | 2016-02-05 | 2016-06-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Production method of methyl mercaptan salt |
| CN105693573A (en) * | 2016-03-11 | 2016-06-22 | 湖北兴发化工集团股份有限公司 | Method and device for producing sodium thiomethoxide from by-product obtained through synthesis of dimethyl sulfide |
| CN208200790U (en) * | 2018-03-01 | 2018-12-07 | 湖北兴发化工集团股份有限公司 | A kind of sodium methyl mercaptide process units |
Non-Patent Citations (2)
| Title |
|---|
| 3-甲硫基-1-丙醇的合成研究;刘玉平，等;《香料香精化妆品》;1-2 * |
| Michael addition of amines and thiols to dehydroalanine amides: a remarkable rate acceleration in water;B. Narasimhulu Naidu，等;《Journal of Organic Chemistry》;10098-10102 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250114A (en) | 2018-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250114B (en) | Sodium methyl mercaptide production process and device | |
| CN109205573B (en) | Efficient separation and utilization process for tail gas of acyl chlorination reaction | |
| CN105439095A (en) | Method and device for preparing sodium chlorite through comprehensive method chlorine dioxide process | |
| CN106145059A (en) | A kind of thionyl chloride reclaims, in producing, the method that sulfur dioxide recycles | |
| CN103819375A (en) | Synthetic method of high-purity solid sodium dimethyl dithiocarbamate | |
| CN105085338B (en) | The production method and device of DMDS | |
| CN102351153B (en) | Method for producing sodium bisulfide products by viscose fiber industrial waste gas | |
| CN104258704B (en) | Waste gas treatment and methyl mercaptan recycling process in cimetidine and ranitidine production | |
| CN206660898U (en) | One kind improves hydrogen chloride as by product of chlorinated paraffin production absorptivity and purifier | |
| CN219050812U (en) | Tail gas treatment system | |
| CN218665415U (en) | Equipment for preparing hydrobromic acid by distillation with finished liquid as raw material | |
| CN1062854A (en) | Hydrogen sulfide and ammonia process for recovering mixing gas | |
| CN208200790U (en) | A kind of sodium methyl mercaptide process units | |
| CN104592062B (en) | A kind of beta-naphthalenesulfonic-acid neutralizes and waste gas recovery method of comprehensive utilization and device thereof continuously | |
| CN213356975U (en) | Ammonia recovery system in methyl sulfonamide production | |
| CN104370783A (en) | Hydrogen sulfide recycling method and hydrogen sulfide recycling system for continuously producing mercaptoacetic acid by adopting sodium hydrosulfide method | |
| CN107930366A (en) | The technique that thionyl chloride integrates treating tail gas | |
| CN102952115B (en) | Sulfurized isobutylene closed path preparation industrialization method | |
| CN101306980A (en) | Method for preparing perchloro cyclopentadiene | |
| CN209721594U (en) | A kind of cryogenic separation system of nitric-sulfuric acid | |
| CN104710301B (en) | The technique of sodium formiate is reclaimed in a kind of vat powder raffinate | |
| CN112778174A (en) | Device and method for preparing high-concentration sodium methyl mercaptide solution | |
| CN203990257U (en) | Between/paraphthaloyl chloride produce in emission-control equipment | |
| CN101440106B (en) | Novel process for recovering waste acid from glyphosate production | |
| CN202555174U (en) | Tail gas cyclic utilization device for chlorination reaction of sulfonyl chloride during synthesis of 4-chloro-2-methoxy carbonyl methoxy imino-3-oxobutyric acid (CMOBA) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231130 Address after: 550500 Machangping Office, Fuquan City, Qiannan Buyi and Miao Autonomous Prefecture, Guizhou Province Applicant after: GUIZHOU XINGFA CHEMICAL Co.,Ltd. Address before: 443711 Hunan Road, Gufu Town, Xingshan County, Yichang City, Hubei Province Applicant before: HUBEI XINGFA CHEMICALS GROUP Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |