CN206872711U

CN206872711U - The equipment of one-step method continuous production DMDS

Info

Publication number: CN206872711U
Application number: CN201720434049.7U
Authority: CN
Inventors: 王杰; 田云清; 敖含
Original assignee: Hubei Xingfa Chemicals Group Co Ltd
Current assignee: Hubei Xingfa Chemicals Group Co Ltd
Priority date: 2017-04-24
Filing date: 2017-04-24
Publication date: 2018-01-12
Anticipated expiration: 2027-04-24

Abstract

The utility model discloses the equipment of one-step method continuous production DMDS, reactor head charging aperture is connected with feed preheater by material pipeline, and reactor bottom syngas outlet at the top of sulphur trap with being connected；It is connected in the middle part of sulphur trap with synthesis gas condenser overhead import；Synthesis gas condenser bottom is connected through pipeline with condensate tank import and synthesis gas condenser overhead import respectively；Synthesis gas condenser bottom is connected with condenser inlet；Condenser outlet at bottom in the middle part of liquid separation tank with being connected；Liquid separation pot bottom exports to be connected with thick methyl disulfide rectifying charging pump inlet；Rectifying charging pump discharge is connected with rectifying column；Rectifying column is configured with reboiler, rectifying column condenser and circulating pump；Backflow pump discharge is connected with rectifier backflow material inlet and feed preheater import.The equipment synthesis tail gas fixed gas is used as hydrogen sulfide, can directly reclaim and be reused as raw material, to the utilization rate of raw material close to 100%.

Description

The equipment of one-step method continuous production DMDS

Technical field

The utility model belongs to field of chemical technology, and in particular to and one kind uses methanol, hydrogen sulfide and sulphur as raw material, Single step reaction produces the technique and its corollary apparatus of 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, it 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, it can be used as solvent, regenerative agent, soft Agent and plasticizer etc.；In addition, DMDS also acts as inhibitor of fuel, lubricating additive and some organic chemical reactionses etc.. The use of industry is mainly the industries such as agricultural chemicals, dyestuff, oil, chemical industry, rubber, 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 this method by-product are difficult to handle.

There are the report using methyl mercaptan direct oxidation method production DMDS in foreign countries, but due to methyl mercaptan and the direct gas of oxygen Mix and easily form explosive mixture, cause this method serious security risk to be present, reaction condition is difficult to control, the current party The only a small amount of experiment report of method, is not implemented industrialized production.

The content of the invention

The utility model provides a kind of production technology and equipments of one-step method continuous production DMDS.

Technical scheme is used by the utility model：Using methanol, hydrogen sulfide, sulphur simple substance as raw material, 400 DEG C of temperature~ 500 DEG C, under the conditions of pressure 50kPa~200kPa, reacted under the effect of catalyst in reactor bed catalyst, generate dimethyl two Sulphur and water：

2CH₃OH + H₂S + S → CH₃SSCH₃ + 2H₂O

With hydrogen sulfide side reaction generation methyl mercaptan occurs for part methanol：

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 methanol：Hydrogen sulfide：Sulphur=2:1:1, it is actual raw Molar ratio methanol is controlled during production：Hydrogen sulfide：Sulphur=(2.0~2.4)：(1.0~1.2)：1, preferably methanol：Hydrogen sulfide：Sulphur Mol ratio 2.1: 1.2:1, hydrogen sulfide is controlled relative to the methanol amount of skipping over to ensure that methanol reaction is complete；Control methanol and vulcanization Hydrogen relative to the sulphur amount of skipping over prevent dimethyl polysulfide generate, while avoid elemental sulfur enter follow-up workshop section may caused by Equipment pipe blocks.

Production technology described in the utility model, realized by following device：

The present apparatus include feed preheater, reactor, sulphur trap, synthesis gas condenser, condensate tank, liquid separation tank, Rectifying column, rectifying column reboiler and condenser, and supporting circulating pump, material pipeline etc..

Be provided with the top of reactor b methanol 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 Sulphur feed distributor connects, for mixed material sulphur and methanol, hydrogen sulfide；Feed distributor bottom, and two layers of 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 mouth is connected with feed preheater by material pipeline, bottom syngas outlet 3. with sulphur Connected at the top of trap c；It is connected in the middle part of sulphur trap c with synthesis gas condenser d top inlets；Condenser d bottoms and condensate liquid Storage tank f imports and the connection of condenser e top inlets；Condenser e bottoms are connected with condenser g imports；Condenser fg outlet at bottoms With being connected in the middle part of liquid separation tank h；Liquid separation tank h outlet at bottoms are 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 connection.

By technique described in the utility model and device, the continuous production of DMDS, its technological process can be achieved Simply, byproduct of reaction is less, and the water of by-product can be used as technique soft water to recycle；The more sulphur of a small amount of dimethyl of by-product can be with first Mercaptan continues reaction and is converted into DMDS, or is sold directly as vulcanizing agent；Synthesis tail gas fixed gas is hydrogen sulfide, can be straight Take back and be incorporated as reusing for raw material；Tai gas of rectifying fixed gas amount is minimum, normally without other three waste discharges during production, only in equipment A small amount of waste water can be produced during maintenance cleaning.Therefore technique described in the utility model to the utilization rate of raw material close to 100%, arrange by the three wastes Put less, be a kind of ideal DMDS production technology.

Brief description of the drawings

Fig. 1 is the utility model one-step method DMDS continuous production processes structure drawing of device.Device name： a：It is former Expect preheater； b：Synthesis reactor； c：Sulphur trap； d、e：Synthesize gas condenser；f、g：Condensate tank；h：Liquid separation tank； i：DMDS rectifying column； j：Rectifying column reboiler；k：Rectifying column condenser； m：Thick DMDS feed pump； n：Return Flow circulating pump.

Fig. 2 is synthesis reactor sketch used by the utility model.In figure, 1. methanol hydrogen sulfide charging aperture；2. sulphur Charging aperture；3. syngas outlet；5. 4. heat exchange jacket feed inlet and outlet；6. heat exchange coil；7. heat exchange jacket；8. catalyst bed Layer.

Embodiment

It is expanded on further Processes and apparatus described in the utility model below in conjunction with the accompanying drawings.

Technique described in the utility model, including feed preheater, reactor, sulphur trap, synthesis gas condenser, condensation Liquid storage tank, liquid separation tank, rectifying column, rectifying column reboiler and condenser, and the device of the equipment such as supporting circulating pump, material pipeline Middle realization.Wherein, be provided with the top of reactor b methanol and hydrogen sulfide charging aperture 1., sulphur charging aperture 2., syngas outlet 3., heat exchange Chuck charging aperture 4., outlet 5., heat exchange coil 6., heat exchange jacket 7., beds 8..Wherein, sulphur charging aperture 2. with reaction Sulphur feed distributor connects in device, for mixed material sulphur and methanol, hydrogen sulfide；Feed distributor bottom, and two layers of catalyst Heat exchange coil is provided between bed screen, for providing reaction institute's calorific requirement and maintenance reaction equalized temperature.

Embodiment 1

When producing DMDS using device described in the utility model, using methanol, hydrogen sulfide, elemental sulfur as raw material, Single step reaction generates DMDS in synthesis reactor.Wherein, methanol and the preheated device a of hydrogen sulfide are mixed, are preheated to 300 DEG C Afterwards, 1. entered by reactor b its top feeds mouth；After elemental sulfur is heated to 450 DEG C, reacted device b tops are entered in a gaseous form 2. material mouth enters reactor；Control molar ratio methanol：Hydrogen sulfide：Sulphur 2.1: 1.2: 1.Elemental sulfur passes through feed distributor Mixed with methanol hydrogen sulfide in reactor, 450 DEG C are heated to by heat exchange coil, from top to bottom by beds, urged The lower reaction generation DMDS of agent effect, while a small amount of methyl mercaptan of by-product.Reaction by self-heat generation and heat exchange coil 6., Reactor jacket 7. maintenance reaction temperature；3. synthesis gas is drawn by reactor bottom outlet, unreacted is removed using sulphur trap c Elemental sulfur；Condensed device d, e again, condensation recovery DMDS, water, methyl mercaptan, unreacted methanol etc.；Fixed gas is main Composition is hydrogen sulfide and micro methyl mercaptan, is back to raw material hydrogen sulfide after compression and is recycled and reused for synthesizing；The dimethyl two of condensation Sulphur, water, methyl mercaptan, methanol enter liquid separation tank h after being collected using condensate tank f, g, form aqueous phase and organic phase layering；Upper strata After methanol is reclaimed in rectifying, remaining water reuses aqueous phase as technique soft water；Lower floor's organic phase mainly containing DMDS, Methanol, methyl mercaptan and the more sulphur of a small amount of dimethyl, rectifying column i is squeezed into by rectifying feed pump m；In distillation system, light component first sulphur After alcohol and the condensed recovery of a small amount of methanol, feed preheater a is returned by reflux pump n；Heavy constituent is mainly DMDS, by essence After evaporating tower bottom extraction, into product purification process.

In actual production process, molar ratio methanol is controlled：Hydrogen sulfide：Sulphur 2.1: 1.2:1, that is, keep hydrogen sulfide to omit It is excessive to ensure that methanol fully reacts；Keep methanol elemental sulfur relative with hydrogen sulfide excessive, to ensure that simple substance reaction of Salmon-Saxl is complete, together When can avoid the generations of the more sulphur of diformazan.450 DEG C of controlling reaction temperature, pressure 50kPa.Improper, reaction of Salmon-Saxl is controlled to prevent from feeding intake Elemental sulfur occluding device pipeline when not exclusively, reactor exit are provided with sulphur trap.Synthesis gas takes after sulphur trap desulfurization Sample carries out chromatography, detects its component as methanol 3.83%, hydrogen sulfide 7.52%, water 16.58%, methyl mercaptan 2.21%, dimethyl The more sulphur 2.32% of two sulphur 67.54%, dimethyl.After continuous dosing reacts about 12 hours, it is a small amount of deep yellow to check that sulphur trap bottom has Color thick liquid, it is DMDS, sulphur, the more sulphur mixtures of dimethyl through analysis.After continuous dosing about 86 hours, this is mixed About 30% liquid level is arrived in compound accumulation, is now returned synthesis reactor sulphur charging aperture and is reused as raw material.

It is computed, two sulphur in product：More 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 obtains Complete recycling has been arrived, has avoided pollutant emission and waste.

Reference examples 2

Using the technique and device of same above example 1, molar ratio methanol 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, trap desulfurization Afterwards, detect that synthesis gas componentses are：Methanol 2.10%, hydrogen sulfide 1.12%, water 19.71%, methyl mercaptan 0.53%, DMDS 66.89%, the more sulphur 9.66% of dimethyl.Compareed with upper example, the amount of polysulfide substantially increases, two sulphur：More sulphur mol ratios reach about 9.3:1, close to the level of dimethyl suflfate-sodium persulfide technique, illustrate that molar ratio control has a great influence to reaction product. Because the polysulfide of this batch experiment by-product is more, the sulphur of trapping, polysulfide mixture are no longer direct in sulphur trap Return feeds intake again, but after mixture is separated, sulphur recovery to sulfur melting groove, is used as byproduct after polysulfide double purification Vulcanizing agent uses.

Claims

1. the device of one-step method continuous production DMDS, it is characterised in that DMDS production technology by filling as follows Put realization：

The present apparatus includes feed preheater（a）, synthesis reactor（b）, sulphur trap（c）, synthesis gas condenser（d）, synthesis gas Condenser（e）, condensate tank（f）, condensate tank（g）；

Reactor（b）Its top feed mouth（①）With feed preheater（a）Connected by material pipeline, reactor（b）Bottom synthesizes Gas exports（③）With sulphur trap（c）Top connects；Sulphur trap（c）Middle part and synthesis gas condenser（d）Top inlet connects； Synthesize gas condenser（d）Bottom is respectively through pipeline and condensate tank（f）Import and synthesis gas condenser（e）Top inlet connects Connect；Synthesize gas condenser（e）Bottom and condenser（f）Import connects；Condenser（f）Outlet at bottom and liquid separation tank（h）Middle part connects Connect；Liquid separation tank（h）Outlet at bottom and thick methyl disulfide rectifying feed pump（m）Import connects；Rectifying feed pump（m）Outlet and rectifying Tower（i）Connection；Rectifying column（i）It is configured with reboiler（j）, rectifying column condenser（k）And circulating pump（n）；Reflux pump（n）Outlet with Rectifying column（i）Upper return material inlet and feed preheater（a）Import connects.

2. the device of the continuous production DMDS described in claim 1, it is characterised in that synthesis reactor（b）Top is set There are methanol and hydrogen sulfide charging aperture（①）, sulphur charging aperture（②）, syngas outlet（③）, heat exchange jacket charging aperture（④）, discharging Mouthful（⑤）, heat exchange coil（⑥）, heat exchange jacket（⑦）, beds（⑧）, wherein, sulphur charging aperture（②）With sulphur in reactor Feed distributor connects, for mixed material sulphur and methanol, hydrogen sulfide.

3. the device of the continuous production DMDS described in claim 1, 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.