CN106928104B - The technique and device of catalysis of iodine method production dialkyl disulfides - Google Patents
The technique and device of catalysis of iodine method production dialkyl disulfides Download PDFInfo
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- CN106928104B CN106928104B CN201710233354.4A CN201710233354A CN106928104B CN 106928104 B CN106928104 B CN 106928104B CN 201710233354 A CN201710233354 A CN 201710233354A CN 106928104 B CN106928104 B CN 106928104B
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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
The invention discloses a kind of dialkyl disulfides production technologies, specifically it is passed through in the aqueous phase solution containing iodine with alkyl hydrosulfide, alkyl hydrosulfide obtains dialkyl disulfides and hydroiodic acid (under neutrality to acid condition) or dialkyl disulfides and iodide salt by iodine oxidation (under alkaline condition)；It is passed through oxygen or oxygen-enriched air in the hydroiodic acid or iodide salt solution generated again to oxidation step, iodide are oxidized to iodine；The reaction condition of entire technical process is mild, is not related to the severe poisonous chemicals such as dimethyl suflfate, is more economical and environmentally friendly worth compared with the traditional processing technology of two sulphur of dimethyl disulfide or diethyl without other by-products in addition to water.
Description
Technical field
The invention belongs to field of chemical technology, and in particular to and it is a kind of to use alkyl hydrosulfide, oxygen for raw material, it is to urge with iodine
The technique of agent production dialkyl disulfides.
Background technique
Dialkyl disulfides are a kind of sulfur-bearing Organic chemical products, most commonly seen with dimethyl disulfide and two sulphur of diethyl.Its
In, dimethyl disulfide can be used for the industries such as pesticide, dyestuff, petroleum, chemical industry, rubber, food additives；Two sulphur of diethyl frequently as
The intermediate of agriculture chemicals fungicide or raw material as organic synthesis.
Currently, domestic dimethyl disulfide mostly uses dimethyl sulfate method to produce, since dimethyl suflfate is severe toxicityization
Product, which 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 dimethyl disulfide in foreign countries, but due to methyl mercaptan and the direct gas of oxygen
It mixes and easily forms explosive mixture, cause this method there are serious security risk, reaction condition is difficult to control, the current party
The only a small amount of experiment report of method, is not implemented industrialized production.
Two sulphur of diethyl reacts to obtain frequently with chloroethanes with sodium persulfide, and the production process is simple, but by-product is more
Sulfide and sodium chloride abraum salt are more intractable, this industrial method often with chlorine industry matching running.
Summary of the invention
The present invention provides a kind of techniques of catalysis of iodine method production dialkyl disulfides, can be used for producing dimethyl disulfide, two
Two sulphur class product of two sulphur of ethyl or other alkyl.
Institute's technique of the invention comprises the following steps:
A) mercaptan oxidation: being passed through alkyl hydrosulfide into the aqueous solution of iodine, at 0 DEG C~60 DEG C of temperature, under the conditions of 0-0.1MPa,
Reaction generates dialkyl disulfides and iodide:
2RSH + I2→ RSSR+2HI (acid condition)
Or 2RSH+I2 + 2NaOH → RSSR + 2NaI +2H2O (alkaline condition)
It reacts obtained dialkyl disulfides and mutually and in water phase, by stratification, isolates two oily respectively with iodide
Two sulphur product of alkyl and iodide aqueous solution；
B) iodine regenerates: under the conditions of 30 DEG C~80 DEG C, oxygen or oxygen-enriched air, iodine are passed through into iodide aqueous solution
It is regenerated:
4HI + O2 → 2I2 + 2H2O (acid condition)
Or 4NaI+O2 + 2H2O → 4NaOH + 2I2(alkaline condition)
The aqueous phase solution for the iodine that step b regenerates, return step a are recycled and reused for mercaptan oxidation；Step a isolate two
It is dissolved with a small amount of iodine in two sulphur crude product of alkyl, passes through water extraction and separation；Extraction water return system containing iodine is reused, and iodine is contained
Solution periodically removes the extra water in part.
In the above reaction, R can be methyl, ethyl or other alkyl groups, and different dialkyl disulfides can be obtained in correspondence
Product；Reaction can carry out under acid condition or alkaline condition, and wherein mercaptan absorbs more thorough, acid condition under alkaline condition
Faster, producer can select lower iodine regeneration rate according to the actual situation.
The present invention also provides a kind of devices of catalysis of iodine method production dialkyl disulfides, and oxidizing tower top is through pipeline and liquid separation tank
Connection, liquid separation pot bottom connect with regenerator, and regenerator is connect with mother liquor holding tank, and two-way is divided through pipeline in mother liquor holding tank bottom, and one
Road is connect with oxidation tower bottom, is connect all the way with dewatering system.
Liquid separation tank top is connect through pipeline with water extraction tower, and water extraction top of tower is connect through pipeline with dewatering system, dewatering system
Bottom is through pipeline and mother liquor holding tank.Iodine remover is provided at the top of regenerator.Dewatering system is connect through pipeline with water extraction tower.
When producing dialkyl disulfides using the technique, need that a certain amount of iodine or iodide are added into system before driving
(iodine solution containing sodium iodide can be used to increase meltage of the iodine in water phase), total iodo quantity no consumption in production process are practical
Raw materials for production are alkyl hydrosulfide and oxygen, and iodine can be considered that catalyst, product are dialkyl disulfides and water, and no other by-products generate.
The reaction condition of entire technical process is mild, aoxidizes 10 DEG C of optimum operating temperature or so, there is no the height that direct oxidation method is related to
Warm high pressure and the risk for forming explosive mixture；It is not related to the severe poisonous chemicals such as dimethyl suflfate；With dimethyl sulfate method technique
It compares, this technique not by-product sodium sulphate, thioether etc., and feed stock conversion is increased to about 95% from 87% or so；With chlorine alkane-over cure
Change sodium method to compare, this technique not byproduct sodium chloride abraum salt, polysulphide content is also down to 0.2% from 3%~10% or so in crude product
Hereinafter, being more economical and environmentally friendly worth.
Detailed description of the invention
Fig. 1 is the device that a kind of catalysis of iodine method produces dialkyl disulfides, wherein 1. oxidizing towers, 2. liquid separation tanks, 3. mother liquors are slow
Tank is rushed, 4. water extract tower, 5. dewatering systems, 6. regenerators, 7. iodine remover, 8. mother liquor storage tanks.
Specific embodiment
A kind of device of catalysis of iodine method production dialkyl disulfides, 1 top of oxidizing tower are connect through pipeline with liquid separation tank 2, liquid separation
2 bottom of tank is connect with regenerator 6, and regenerator 6 is connect with mother liquor holding tank 8, and two-way is divided through pipeline in 8 bottom of mother liquor holding tank, all the way with
The connection of 1 bottom of oxidizing tower, connect with dewatering system 5 all the way.
2 top of liquid separation tank is connect through pipeline with water extraction tower 4, and 4 top of water extraction tower is connect through pipeline with dewatering system 5, is dehydrated
5 bottom of system is connect through pipeline with mother liquor holding tank 8.
Iodine remover 7 is provided at the top of regenerator 6, dewatering system 5 is connect through pipeline with water extraction tower 4.
Oxidative system: alkyl hydrosulfide is entered by 1 lower part of oxidizing tower, is connect with the fair current containing iodine aqueous solution from mother liquor holding tank 8
It touches, 10 DEG C of temperature of charge of control, under the conditions of 0~0.1MPa of pressure (gauge pressure), mercaptan generates dialkyl disulfides, iodine quilt by iodine oxidation
It is reduced to I-Ion；Reaction product enters liquid separation tank 2, two sulphur and aqueous solution stratification by tower top overflow；Upper organic phase
For the dialkyl disulfides dissolved with a small amount of iodine, extract tower 4 into water；Lower layer is aqueous solution, 3. into mother liquor surge tank；
Water extracts system: the upper organic phase from liquid separation tank 2 enters water extraction 4 top of tower, uses come from normal temperatures and pressures
The soft water extraction that dewatering system 5 produces is produced after removing iodine as crude product by 4 bottom of tower, into refining step；It is extracted
Dewatering system 5 is returned containing iodine aqueous solution；
Regenerative system: the aqueous solution from mother liquor surge tank 3 is exchanged heat to 50 DEG C, squeezes into 6 top of regenerator with pump, with
The oxygen or oxygen-enriched air that 6 lower part of tower is passed through inversely contact mixing, under 50 DEG C, condition of normal pressure, I-Ion is reoxidized into
Elemental iodine；Solution after oxidation is produced by 6 bottom of tower, into mother liquor holding tank 8；Regenerator tail gas is oxygen or richness containing a small amount of iodine
Oxygen air removes elemental iodine after-purification recycling through iodine remover 7；The iodine trapped in remover periodically recycles；In mother liquor holding tank 8
Solution is got with pump, be divided to two strands, one return oxidizing tower 1 re-starts oxidation reaction, and another stock is into 5 elimination reaction of dewatering system
The superfluous water of generation.
In the technical process, mercaptan oxidation process reaction rate is slightly faster than iodine regeneration rate, and enterprise can be according to reality when producing
Border situation selects double regenerators, or the mode that a small amount of hydrogen peroxide improves regeneration rate is added into regenerative system, make iodine oxidation with
Regeneration rate matches.
When producing dialkyl disulfides using the technique, under feed stock conversion about 95%(neutrality to acid condition) to 98%(alkali
Under the conditions of property), higher than the conversion ratio of conventional method 87%~90%；In oxidation and regenerative process, material maximum temperature is no more than 80
DEG C, about 10 DEG C of oxidation reaction Optimum Operation temperature, the reaction temperature far below 200 DEG C of mercaptan direct oxidation method or more, and react
It is carried out in aqueous phase solution, security risk is far below direct oxidation method；In obtained dialkyl disulfides crude product, polysulfide
(this technological reaction process itself does not have polysulfide and generates (such as dimethyltrisulfide) total content, thick to produce down to 0.2% or less
Having micro polysulfide in product is due to containing trace hydrogen sulfide in raw material alkyl hydrosulfide, and hydrogen sulfide generates simple substance after being oxidized
Sulphur, elemental sulfur and alkyl hydrosulfide produce polysulfide), far below polysulfide 3%~10% in crude product obtained by conventional method
Content so that product purification be easier, yield is higher.
In the art production process, in addition to water without other by-products and three waste discharge, reaction condition is mild, and production process is clear
Clean environmental protection is ideal dialkyl disulfides production technology.
Claims (6)
1. a kind of device of catalysis of iodine method production dialkyl disulfides, which is characterized in that through pipeline and liquid separation tank at the top of oxidizing tower (1)
(2) it connects, liquid separation tank (2) bottom is connect with regenerator (6), and regenerator (6) is connect with mother liquor holding tank (8), mother liquor holding tank (8) bottom
Portion divides two-way through pipeline, connect with oxidizing tower (1) bottom, connect all the way with dewatering system (5) all the way, the liquid separation tank (2)
Top is connect through pipeline with water extraction tower (4), is connect through pipeline with dewatering system (5) at the top of water extraction tower (4), dewatering system (5) bottom
Portion is connect through pipeline with mother liquor holding tank (8), and dewatering system (5) is connect through pipeline with water extraction tower (4).
2. the device of catalysis of iodine method production dialkyl disulfides according to claim 1, which is characterized in that regenerator (6) top
Portion is provided with iodine remover (7).
3. the device of catalysis of iodine method production dialkyl disulfides according to claim 1, which is characterized in that use catalysis of iodine method
The technique for producing the device progress of dialkyl disulfides includes at least following steps:
(a) mercaptan oxidation: alkyl hydrosulfide is passed through in the aqueous phase solution containing iodine, is 0 in neutrality to acid and reaction pressure
~0.1MPa, under the conditions of 0~60 DEG C of temperature, alkyl hydrosulfide obtains dialkyl disulfides and hydroiodic acid by iodine oxidation, after stratification
Hydroiodic acid solution is isolated, needs that a certain amount of iodine or iodide are added into system in the step, before driving, can be used containing iodine
Change the iodine solution of sodium to increase meltage of the iodine in water phase；
(b) iodine regenerates: being passed through oxygen or oxygen-enriched air in the hydroiodic acid solution generated to oxidation step, iodide are oxidized to simple substance
Iodine in the step, selects double regenerators, or the mode that a small amount of hydrogen peroxide improves regeneration rate is added into regenerative system, makes iodine
Oxidation matches with regeneration rate.
4. the device of catalysis of iodine method production dialkyl disulfides according to claim 1, which is characterized in that use catalysis of iodine method
The technique for producing the device progress of dialkyl disulfides includes at least following steps:
(a) mercaptan oxidation: alkyl hydrosulfide is passed through in the aqueous phase solution containing iodine, alkalinity and reaction pressure be 0~
0.1MPa, under the conditions of 0~60 DEG C of temperature, alkyl hydrosulfide obtains dialkyl disulfides and iodide salt by iodine oxidation, in the step, opens
Chinese herbaceous peony needs that a certain amount of iodine or iodide are added into system, and the iodine solution containing sodium iodide can be used to increase iodine in water phase
Meltage；
(b) iodine regenerates: being passed through oxygen or oxygen-enriched air in the iodide salt solution generated to oxidation step, iodide are oxidized to list
Matter iodine selects double regenerators in the step, or the mode that a small amount of hydrogen peroxide improves regeneration rate is added into regenerative system, makes iodine
Oxidation matches with regeneration rate.
5. the device of catalysis of iodine method production dialkyl disulfides according to claim 3 or 4, which is characterized in that sulphur in step a
Alcohol oxidation reaction condition be 0~0.1MPa of pressure, 10 DEG C of temperature；The regenerated reaction condition of step b iodine is temperature 40 DEG C~60
℃。
6. the device of catalysis of iodine method production dialkyl disulfides according to claim 3 or 4, which is characterized in that the dioxane
Alkyl in two sulphur of base is methyl, ethyl or other alkyl groups, and the alkyl group in the group and raw material alkyl hydrosulfide is pair
It answers.
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