CN106928105A - One-step method continuously produces the Processes and apparatus of DMDS - Google Patents
One-step method continuously produces the Processes and apparatus of DMDS Download PDFInfo
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- CN106928105A CN106928105A CN201710271987.4A CN201710271987A CN106928105A CN 106928105 A CN106928105 A CN 106928105A CN 201710271987 A CN201710271987 A CN 201710271987A CN 106928105 A CN106928105 A CN 106928105A
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- sulphur
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- hydrogen sulfide
- dmds
- methyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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Abstract
Continuously produce the Processes and apparatus of DMDS the invention discloses one-step method, after the mixing in the preheater of material benzenemethanol, hydrogen sulfide is preheated to 200 DEG C~400 DEG C, reactor is passed through from reactor head with gaseous state；Raw material sulphur enters reactor with gaseous state after being heated to 445 DEG C~450 DEG C from reactor top sulphur charging aperture；Material benzenemethanol, hydrogen sulfide and sulphur are heated to 400 DEG C~500 DEG C of reaction temperature in reactor by heat exchange coil, and under the conditions of pressure 50kPa~200kPa, raw material is from top to bottom by catalyst in reactor bed, single step reaction generation DMDS and water.Synthesis tail gas fixed gas is hydrogen sulfide, can directly reclaim and be reused as raw material；Tai gas of rectifying fixed gas amount is minimum, without other three waste discharges during normal production, a small amount of waste water can be only produced when overhaul of the equipments is cleaned.Therefore technique of the present invention is to the utilization rate of raw material close to 100%.
Description
Technical field
The invention belongs to field of chemical technology, and in particular to it is raw material, a step that one kind uses methyl alcohol, hydrogen sulfide and sulphur
The technique and its corollary apparatus of reaction production DMDS.
Background technology
DMDS（DMDS）It is a kind of important chemical products, there is extensive use.In pesticide industry, for making
Take the intermediate of insecticide；In the oil industry, can be used as anti-corrosion, the antiscorching agent of ethane cracking furnace, oil hydrogenation refining catalytic
The vulcanizing agent of agent, the inhibitor of hydrogenation cracking in benzene nucleus decarboxylation reaction；In rubber industry, can be used as solvent, regenerative agent, soft
Agent and plasticizer etc.；Additionally, DMDS also acts as inhibitor of fuel, lubricating additive and some organic chemical reactionses etc..
Main is the industries such as agricultural chemicals, dyestuff, oil, chemical industry, rubber using industry, is in the market fine chemical product in great demand.
Currently, domestic DMDS is mostly produced using dimethyl sulfate ester process, because dimethyl suflfate is severe toxicityization
Product, the technique is faced with serious environmental protection, security risk, while a large amount of metabisulfite solutions of the method by-product are difficult to process.
There are the report that DMDS is produced using methyl mercaptan direct oxidation method in foreign countries, but due to methyl mercaptan and the direct gas of oxygen
Mix and easily form explosive mixture, cause the method to there is serious security risk, reaction condition is difficult to control to, the current party
Method only has a small amount of experiment report, and industrialized production is not implemented.
The content of the invention
The invention provides the production technology and equipments that a kind of one-step method continuously produces DMDS.
The technical solution adopted in the present invention is：With methyl alcohol, hydrogen sulfide, sulphur simple substance as raw material, in temperature 400 DEG C~500
DEG C, under the conditions of pressure 50kPa~200kPa, reacted under the effect of catalyst in reactor bed catalyst, generate DMDS
And water：
2CH3OH + H2S + S → CH3SSCH3 + 2H2O
There is side reaction generation methyl mercaptan with hydrogen sulfide in part methyl alcohol：
CH3OH + H2S → CH3SH + H2O
Methyl mercaptan can continue reaction generation DMDS with sulphur：
2CH3SH + S → CH3SSCH3 +H2S
In the technique, the theoretical molar ratio for generating DMDS is methyl alcohol：Hydrogen sulfide：Sulphur=2:1:1, during actual production
Control molar ratio methyl alcohol：Hydrogen sulfide：Sulphur=(2.0~2.4)：(1.0~1.2)：1, preferably methyl alcohol：Hydrogen sulfide：Sulphur mole
Than 2.1: 1.2:1, control hydrogen sulfide is complete to ensure methyl alcohol reaction relative to the methyl alcohol amount of skipping over；Control methyl alcohol and hydrogen sulfide phase
For the sulphur amount of skipping over to prevent dimethyl polysulfide from generating, while avoiding the equipment that elemental sulfur is likely to result in into follow-up workshop section
Line clogging.
Production technology of the present invention, is realized by following device：
The present apparatus includes feed preheater, reactor, sulphur trap, synthesis gas condenser, condensate tank, point flow container, rectifying
Tower, rectifying column reboiler and condenser, and supporting circulating pump, material pipeline etc..
Reactor b top be provided with methyl alcohol and hydrogen sulfide charging aperture 1., sulphur charging aperture 2., syngas outlet 3., heat exchange jacket
Charging aperture 4., outlet 5., heat exchange coil 6., heat exchange jacket 7., beds 8..Wherein, sulphur charging aperture 2. with reactor in
Sulphur feed distributor is connected, for mixed material sulphur and methyl alcohol, hydrogen sulfide；Feed distributor bottom, and two-layer beds
Heat exchange coil is provided between screen, for providing reaction institute's calorific requirement and maintenance reaction equalized temperature.
1. reactor b its top feeds mouthful are connected with feed preheater by material pipeline, bottom syngas outlet 3. with sulphur
The connection of trap c tops；Sulphur trap c middle parts are connected with synthesis gas condenser d top inlets；Condenser d bottoms and condensate liquid
Storage tank f imports and condenser e top inlets are connected；Condenser e bottoms are connected with condenser g imports；Condenser fg outlet at bottoms
It is connected with a point flow container h middle parts；Flow container h outlet at bottoms are divided to be connected with thick methyl disulfide rectifying feed pump m imports；Rectifying feed pump m
Outlet is connected with rectifying column i；Rectifying column i is configured with reboiler j, condenser k and circulating pump n；Reflux pump n is exported and rectifying column i
Upper return material inlet and feed preheater a imports are connected.
By technique of the present invention and device, the continuous prodution of DMDS is capable of achieving, its technological process is simple,
Byproduct of reaction is less, and the water of by-product can be recycled as technique soft water；The many sulphur of a small amount of dimethyl of by-product can be with methyl mercaptan
Continue reaction and be converted into DMDS, or directly as vulcanizing agent sale；Synthesis tail gas fixed gas is hydrogen sulfide, can directly be returned
It is incorporated as being reused for raw material；Tai gas of rectifying fixed gas amount is minimum, without other three waste discharges during normal production, only in overhaul of the equipments
A small amount of waste water can be produced during cleaning.Therefore, to the utilization rate of raw material close to 100%, three waste discharge is few, is one for technique of the present invention
Plant ideal DMDS production technology.
Brief description of the drawings
Fig. 1 is one-step method DMDS continuous production processes structure drawing of device of the present invention.Device name： a：Raw material is pre-
Hot device； b：Synthesis reactor； c：Sulphur trap； d、e：Synthesis gas condenser；f、g：Condensate tank；h：Divide flow container； i：
DMDS rectifying column； j：Rectifying column reboiler；k：Rectifying column condenser； m：Thick DMDS feed pump； n：Backflow
Circulating pump.
Fig. 2 is synthesis reactor sketch of the present invention.In figure, 1. methyl alcohol hydrogen sulfide charging aperture；2. sulphur charging
Mouthful；3. syngas outlet；4. 5. heat exchange jacket feed inlet and outlet；6. heat exchange coil；7. heat exchange jacket；8. beds.
Specific embodiment
It is expanded on further Processes and apparatus of the present invention below in conjunction with the accompanying drawings.
Technique of the present invention, comprising feed preheater, reactor, sulphur trap, synthesis gas condenser, condensate liquid storage
It is real in tank, point flow container, rectifying column, rectifying column reboiler and condenser, and the device of equipment such as supporting circulating pump, material pipeline
It is existing.Wherein, reactor b top be provided with methyl alcohol and hydrogen sulfide charging aperture 1., sulphur charging aperture 2., syngas outlet 3., heat exchange jacket
Charging aperture 4., outlet 5., heat exchange coil 6., heat exchange jacket 7., beds 8..Wherein, sulphur charging aperture 2. with reactor in
Sulphur feed distributor is connected, for mixed material sulphur and methyl alcohol, hydrogen sulfide；Feed distributor bottom, and two-layer beds
Heat exchange coil is provided between screen, for providing reaction institute's calorific requirement and maintenance reaction equalized temperature.
1. reactor b its top feeds mouthful are connected with feed preheater by material pipeline, bottom syngas outlet 3. with sulphur
The connection of trap c tops；Sulphur trap c middle parts are connected with synthesis gas condenser d top inlets；Condenser d bottoms and condensate liquid
Storage tank f imports and condenser e top inlets are connected；Condenser e bottoms are connected with condenser g imports；Condenser fg outlet at bottoms
It is connected with a point flow container h middle parts；Flow container h outlet at bottoms are divided to be connected with thick methyl disulfide rectifying feed pump m imports；Rectifying feed pump m
Outlet is connected with rectifying column i；Rectifying column i is configured with reboiler j, condenser k and circulating pump n；Reflux pump n is exported and rectifying column i
Upper return material inlet and feed preheater a imports are connected.
Embodiment 1
When producing DMDS using device of the present invention, with methyl alcohol, hydrogen sulfide, elemental sulfur as raw material, in synthetic reaction
Single step reaction generation DMDS in device.Wherein, methyl alcohol and hydrogen sulfide preheated device a mixing, be preheated to 300 DEG C after, by anti-
Device b its top feeds mouthful are answered 1. to enter；After elemental sulfur is heated to 450 DEG C, 2. reacted device b upper feed inlets enter in a gaseous form
Enter reactor；Control molar ratio methyl alcohol：Hydrogen sulfide：Sulphur 2.1: 1.2: 1.Elemental sulfur is by feed distributor and methyl alcohol sulphur
Change hydrogen to mix in reactor, 450 DEG C are heated to by heat exchange coil, from top to bottom by beds, in catalyst action
Lower reaction generation DMDS, while a small amount of methyl mercaptan of by-product.Reaction by self-heat generation and heat exchange coil 6., reactor presss from both sides
Cover 7. maintenance reaction temperature；3. synthesis gas is drawn by reactor bottom outlet, and unreacted simple substance is removed using sulphur trap c
Sulphur；Condensed device d, e, condense and reclaim DMDS, water, methyl mercaptan, unreacted methyl alcohol etc. again；Fixed gas main component is
Hydrogen sulfide and micro methyl mercaptan, are back to raw material hydrogen sulfide and are recycled and reused for synthesis after compression；The DMDS of condensation, water,
Methyl mercaptan, methyl alcohol enter a point flow container h after being collected using condensate tank f, g, form water phase and organic phase layering；Upper strata aqueous phase is passed through
After methyl alcohol is reclaimed in rectifying, remaining water is reused as technique soft water；Lower floor's organic phase mainly containing DMDS, methyl alcohol,
Methyl mercaptan and many sulphur of a small amount of dimethyl, rectifying column i is squeezed into by rectifying feed pump m；In distillation system, light component methyl mercaptan and few
After the amount condensed recovery of methyl alcohol, feed preheater a is returned by reflux pump n；Heavy constituent is mainly DMDS, by rectifying column bottom
After portion's extraction, into product purification operation.
In actual production process, molar ratio methyl alcohol is controlled：Hydrogen sulfide：Sulphur 2.1: 1.2:1, that is, keep hydrogen sulfide to omit
It is excessive ensureing that methyl alcohol fully reacts；Methyl alcohol elemental sulfur excess relative with hydrogen sulfide is kept, to ensure simple substance reaction of Salmon-Saxl completely, together
When can avoid the generation of many sulphur of diformazan.450 DEG C of controlling reaction temperature, pressure 50kPa.To prevent the improper, reaction of Salmon-Saxl of control that feeds intake
Elemental sulfur occluding device pipeline when not exclusively, reactor exit is provided with sulphur trap.After synthesis gas is through sulphur trap desulfurization, take
Sample carries out chromatography, detects that its component is methyl alcohol 3.83%, hydrogen sulfide 7.52%, water 16.58%, methyl mercaptan 2.21%, dimethyl
The many sulphur 2.32% of two sulphur 67.54%, dimethyl.After continuous dosing reacts about 12 hours, check that sulphur trap bottom has a small amount of deep yellow
Color thick liquid, is DMDS, sulphur, many sulphur mixtures of dimethyl through analysis.After continuous dosing about 86 hours, this is mixed
Compound accumulation is now returned synthesis reactor sulphur charging aperture and is reused as raw material to about 30% liquid level.
It is computed, two sulphur in product：Many sulphur mol ratios about 39:1, polysulfide about 3% in crude product, less than dimethyl sulfate
The average level of polysulfide 5%~10% in ester-sodium persulfide technique.By this technique and device, the complete raw material of unreacted is obtained
To recycling completely, it is to avoid pollutant emission and waste.
Reference examples 2
Using the technique and device of same above example 1, molar ratio methyl alcohol is controlled：Hydrogen sulfide：Sulphur 2.0: 1.0:1, i.e.,
Fed intake according to reaction theory mol ratio, keep other reaction conditions constant.Reacted through 450 DEG C, 50kPa, after trap desulfurization, inspection
Measuring synthesis gas componentses is：Methyl alcohol 2.10%, hydrogen sulfide 1.12%, water 19.71%, methyl mercaptan 0.53%, DMDS 66.89%,
The many sulphur 9.66% of dimethyl.Compareed with upper example, the amount of polysulfide substantially increases, two sulphur：Many sulphur mol ratios reach about 9.3:1, connect
The level of nearly dimethyl suflfate-sodium persulfide technique, illustrates that molar ratio control influences larger to product.Due to this batch
The polysulfide of secondary experiment by-product is more, and sulphur, the polysulfide mixture of trapping are no longer directly returned again in sulphur trap
Feed intake, but after mixture is separated, sulphur recovery to sulfur melting groove makes after polysulfide double purification as byproduct vulcanizing agent
With.
Claims (6)
1. the technique that one-step method continuously produces DMDS, it is characterised in that material benzenemethanol, hydrogen sulfide mix in preheater
After being preheated to 200 DEG C~400 DEG C, reactor is passed through from reactor head with gaseous state；Raw material sulphur is being heated to 445 DEG C~450 DEG C
Afterwards, reactor is entered from reactor top sulphur charging aperture with gaseous state；Material benzenemethanol, hydrogen sulfide and sulphur are in reactor by heat exchange disk
Pipe is heated to 400 DEG C~500 DEG C of reaction temperature, and under the conditions of pressure 50kPa~200kPa, raw material from top to bottom passes through reactor
Internal catalyst bed layer, single step reaction generation DMDS and water.
2. technique as claimed in claim 1, it is characterised in that raw material molar ratio is methyl alcohol：Hydrogen sulfide：Sulphur=(2.0~
2.4)：(1.0~1.2)：1, preferably methyl alcohol：Hydrogen sulfide：Sulphur mol ratio 2.1: 1.2:1, that is, hydrogen sulfide is controlled relative to methyl alcohol
The amount of skipping over；Methyl alcohol and hydrogen sulfide are relative to the sulphur amount of skipping over.
3. technique as claimed in claim 1, it is characterised in that the complete material benzenemethanol of unreacted, and accessory substance methyl mercaptan, warp
Returning reactor is reused after condensation, rectifying, light component are reclaimed；The complete hydrogen sulfide of unreacted, by condensation tail gas fixed gas
Returning reactor recycling after outlet pressure recovery.
4. one-step method continuously produces the device of DMDS, it is characterised in that DMDS production technology is by following dress
Put realization：
The present apparatus comprising feed preheater a, synthesis reactor b, sulphur trap c, synthesis gas condenser d, synthesis gas condenser e,
Condensate tank f, condensate tank g；
1. reactor b its top feeds mouthful are connected with feed preheater a by material pipeline, and reactor b bottoms syngas outlet is 3.
It is connected with sulphur trap c tops；Sulphur trap c middle parts are connected with synthesis gas condenser d top inlets；Synthesis gas condenser d bottoms
Portion is connected through pipeline with condensate tank f imports and synthesis gas condenser e top inlets respectively；Synthesis gas condenser e bottoms with
Condenser f imports are connected；Condenser f outlet at bottoms are connected with a point flow container h middle parts；Divide flow container h outlet at bottoms and thick methyl disulfide
Rectifying feed pump m imports are connected；Rectifying feed pump m outlets are connected with rectifying column i；Rectifying column i is configured with reboiler j, rectifying column
Condenser k and circulating pump n；Reflux pump n outlets are connected with rectifying column i upper returns material inlet and feed preheater a imports.
5. the device of the continuous production DMDS described in claim 4, it is characterised in that synthesis reactor b tops are provided with
Methyl alcohol and hydrogen sulfide charging aperture 1., sulphur charging aperture 2., syngas outlet 3., heat exchange jacket charging aperture 4., discharging opening 5., heat exchange disk
Pipe 6., heat exchange jacket 7., beds 8., wherein, 2. sulphur charging aperture is connected with sulphur feed distributor in reactor, for mixing
Close raw material sulphur and methyl alcohol, hydrogen sulfide.
6. the device of the continuous production DMDS described in claim 4, it is characterised in that feed distributor bottom, and two
Heat exchange coil is provided between layer beds screen, for providing reaction institute's calorific requirement and maintenance reaction equalized temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710271987.4A CN106928105B (en) | 2017-04-24 | 2017-04-24 | The Processes and apparatus of one-step method continuous production dimethyl disulfide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710271987.4A CN106928105B (en) | 2017-04-24 | 2017-04-24 | The Processes and apparatus of one-step method continuous production dimethyl disulfide |
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| CN106928105A true CN106928105A (en) | 2017-07-07 |
| CN106928105B CN106928105B (en) | 2019-06-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117109996A (en) * | 2023-10-25 | 2023-11-24 | 成都蓝湖科技有限公司 | Analysis sampling system of sulfur analysis ratio instrument |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0171092A2 (en) * | 1985-04-26 | 1986-02-12 | Pennwalt Corporation | Preparation of dialkyl disulfides |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
| CN204918438U (en) * | 2015-08-25 | 2015-12-30 | 成都德美工程技术有限公司 | Dimethyl disulfide apparatus for producing |
-
2017
- 2017-04-24 CN CN201710271987.4A patent/CN106928105B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0171092A2 (en) * | 1985-04-26 | 1986-02-12 | Pennwalt Corporation | Preparation of dialkyl disulfides |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
| CN204918438U (en) * | 2015-08-25 | 2015-12-30 | 成都德美工程技术有限公司 | Dimethyl disulfide apparatus for producing |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117109996A (en) * | 2023-10-25 | 2023-11-24 | 成都蓝湖科技有限公司 | Analysis sampling system of sulfur analysis ratio instrument |
| CN117109996B (en) * | 2023-10-25 | 2024-01-02 | 成都蓝湖科技有限公司 | Analysis sampling system of sulfur analysis ratio instrument |
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| CN106928105B (en) | 2019-06-04 |
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