CN107986999A - A kind of preparation method of thio two sweet mercaptan - Google Patents
A kind of preparation method of thio two sweet mercaptan Download PDFInfo
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- CN107986999A CN107986999A CN201711224663.1A CN201711224663A CN107986999A CN 107986999 A CN107986999 A CN 107986999A CN 201711224663 A CN201711224663 A CN 201711224663A CN 107986999 A CN107986999 A CN 107986999A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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Abstract
The present invention provides a kind of preparation method of thio two sweet mercaptan, comprise the following steps：A) salt-forming reaction will be carried out after Thiodiglycol, thiocarbamide and mixed in hydrochloric acid, adds aqueous slkali and reaction is hydrolyzed, obtain reaction mixture；B) reaction mixture for obtaining step a) carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction waste；Then the thio two sweet mercaptan crude product is washed, respectively obtains thio two sweet mercaptan and washing waste water；C) the obtained reaction wastes of step b) and washing waste water are subjected to flocculation treatment respectively, obtain cycling use of water.Compared with prior art, preparation method provided by the invention has higher product quality and yield, and can realize recycling for waste water.Test result indicates that the stable content for the thio two sweet mercaptan that preparation method provided by the invention obtains, more than 99%, yield realizes the zero-emission of waste water more than 98%.
Description
Technical field
The present invention relates to technical field of organic synthesis, is to be related to a kind of preparation side of thio two sweet mercaptan more specifically
Method.
Background technology
Thio two sweet mercaptan is a kind of organic compound with special unhappy smell, its structure is referring to formula (I) Suo Shi：
It is often used as intermediate product when synthesizing other organic compounds containing sulfurs, especially suitable for sulfide synthesis, thio
Ester, sub- maple and maple etc..Thio two sweet mercaptan is industrially widely used in chemical reagent, fine chemicals, medicine intermediate, material
Intermediate etc..
The application field of thio two sweet mercaptan mainly includes：Organic compounds containing sulfur intermediate, chemical reagent, dyestuff hydrotropy
Agent dyeing, eyeglass optical resin etc..Application in terms of organic compounds containing sulfur intermediate：Thio two sweet mercaptan is synthesizing
Be often used as intermediate product during other organic compounds, its can dehydrogenation oxidation be thioether, and be further oxidized to sulfoxide, sulfone,
In addition, monothioester can also be generated with inorganic acid reaction；Application in terms of chemical reagent：Such as medicine intermediate thiocarbamic acid
Ester, it occurs oxidation carbonylation by thio two sweet mercaptan and aniline in the presence of CO and oxygen and obtains, is mainly used for
The fields such as medicine, pesticide, textile finishing and resin modified；Application in terms of dyestuff cosolvent：Thio two sweet mercaptan can be with dyestuff shape
Into hydrogen bond, dye ions surface is formed hydrated ion protective layer, prevent dye molecule cohesion and intermolecular interaction, promote
Dyestuff ionizes and dissolving, therefore can be used as the various dyes of positive ion of phthalocyanin IF3G, the cosolvent of reducing dye；Dyeing application
Aspect application：Thio two sweet mercaptan can be used as vat printing agent of sizing mixing, levelling agent, hygroscopic agent, can increase dyeing material
Vividness；Application in terms of eyeglass optical resin：Since thio two sweet mercaptan have higher refractive index, it can be with isocyanates
Synthesizing optical resin, product mainly application for lens resin synthesize, play the role of in the polymer improve refractive index, thio two
Sweet mercaptan standard items refractive index 1.5961,1.60, during its market orientation belongs to are not higher than to synthetic resin refractive index in principle
High-end refraction resin, lens resin field, the part resin accounting rank among the best at home at present, and market has certain downstream
Development prospect.
At present, the synthesis technique of Thiodiglycol sulphur is mainly using thiocarbamide, Thiodiglycol as raw material, in certain temperature and
Under reaction condition, obtained by chemical reaction.But there are product quality is high, reaction yield for the synthesis technique of the prior art
Relatively low and quantity of three wastes is big, and especially wastewater flow rate is big, it is difficult to the deficiencies of handling.
The content of the invention
In view of this, it is provided by the invention it is an object of the invention to provide a kind of preparation method of thio two sweet mercaptan
Preparation method has higher product quality and yield, and can realize recycling for waste water.
The present invention provides a kind of preparation method of thio two sweet mercaptan, comprise the following steps：
A) salt-forming reaction will be carried out after Thiodiglycol, thiocarbamide and mixed in hydrochloric acid, adds aqueous slkali and reaction is hydrolyzed,
Obtain reaction mixture；
B) reaction mixture for obtaining step a) carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction is useless
Water；Then the thio two sweet mercaptan crude product is washed, respectively obtains thio two sweet mercaptan and washing waste water；
C) the obtained reaction wastes of step b) and washing waste water are subjected to flocculation treatment respectively, obtain cycling use of water.
Preferably, the mass ratio of Thiodiglycol, thiocarbamide and hydrochloric acid described in step a) is 5：(6~8)：(6~8)；
The hydrochloric acid is the concentrated hydrochloric acid that mass concentration is 37%.
Preferably, the temperature of hydrolysis described in step a) is 60 DEG C~80 DEG C, and the time is 2h~4h.
Preferably, the temperature washed described in step b) is 65 DEG C~75 DEG C, and number is 2 times~5 times；The water washed every time
Wash water dosage is 90mL~110mL, and the time is 5min~10min.
Preferably, the step c) is specially：
C1) reaction waste that step b) is obtained is mixed with the first flocculant, first time flocculation treatment is carried out, respectively obtains
For the raw water of the preparation aqueous slkali in step a) and the washing water for water-washing process in step b)；
C2) washing waste water that step b) is obtained is mixed with the second flocculant, second of flocculation treatment is carried out, is used for
The washing water of water-washing process in step b).
Preferably, step c1) described in the first flocculant be selected from aluminum sulfate, alum, Iron trichloride hexahydrate, ferrous sulfate
In hydrate, ferric sulfate, aluminium polychloride, polyaluminium sulfate, poly-ferric chloride, bodied ferric sulfate and polymerization Polyferric Sulfate silicon flocculant
One or more.
Preferably, step c1) described in the mass ratio of reaction waste and the first flocculant be 100：(0.5~5).
Preferably, step c2) described in the second flocculant be selected from aluminum sulfate, alum, Iron trichloride hexahydrate, ferrous sulfate
One or more in hydrate and ferric sulfate.
Preferably, step c2) described in the mass ratio of washing waste water and the second flocculant be 100：(0.1~3).
Preferably, the temperature of flocculation treatment described in step c) is 10 DEG C~40 DEG C, and the time is 8min~12min.
The present invention provides a kind of preparation method of thio two sweet mercaptan, comprise the following steps：A) by Thiodiglycol, sulphur
Salt-forming reaction is carried out after urea and mixed in hydrochloric acid, aqueous slkali is added and reaction is hydrolyzed, obtain reaction mixture；B) by step a)
Obtained reaction mixture carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction waste；Then by described thio two
Sweet mercaptan crude product is washed, and respectively obtains thio two sweet mercaptan and washing waste water；C) reaction waste for obtaining step b) and
Washing waste water carries out flocculation treatment respectively, obtains cycling use of water.Compared with prior art, preparation method provided by the invention has
Higher product quality and yield, and can realize recycling for waste water.Test result indicates that preparation side provided by the invention
For the stable content for the thio two sweet mercaptan that method obtains more than 99%, yield realizes the zero-emission of waste water more than 98%.
In addition, preparation method provided by the invention does not have the three wastes substantially, pollution is small, realizes comprehensive utilization and the money of resource
Source value maximization, and energy consumption is low, clean environment firendly, and new thinking is provided for thio two sweet mercaptan productions.
Brief description of the drawings
Fig. 1 is the gas phase collection of illustrative plates for the thio two sweet mercaptan that the preparation method that the embodiment of the present invention 1 provides is prepared.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's all other embodiments obtained without making creative work, belong to this hair
The scope of bright protection.
The present invention provides a kind of preparation method of thio two sweet mercaptan, comprise the following steps：
A) salt-forming reaction will be carried out after Thiodiglycol, thiocarbamide and mixed in hydrochloric acid, adds aqueous slkali and reaction is hydrolyzed,
Obtain reaction mixture；
B) reaction mixture for obtaining step a) carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction is useless
Water；Then the thio two sweet mercaptan crude product is washed, respectively obtains thio two sweet mercaptan and washing waste water；
C) the obtained reaction wastes of step b) and washing waste water are subjected to flocculation treatment respectively, obtain cycling use of water.
The present invention will carry out salt-forming reaction after Thiodiglycol, thiocarbamide and mixed in hydrochloric acid first, add aqueous slkali progress
Hydrolysis, obtains reaction mixture.In the present invention, the hydrochloric acid is preferably the concentrated hydrochloric acid that mass concentration is 37%.At this
In invention, the aqueous slkali is preferably that mass concentration is 10% sodium hydroxide solution.The present invention is to the Thiodiglycol, sulphur
The source of urea, hydrochloric acid and aqueous slkali is not particularly limited, using commercial goods well known to those skilled in the art.The present invention
The device of the above process is not particularly limited, is filled using well known to those skilled in the art equipped with thermometer, blender, ventilation
The four-hole boiling flask put.
In the present invention, the process by Thiodiglycol, thiocarbamide and mixed in hydrochloric acid is preferably specially：
Under conditions of stirring, hydrochloric acid is added in thiocarbamide, dissolving is warming up to, adds Thiodiglycol, be warming up to back
Stream, completes mixed process.In the present invention, the mass ratio of the Thiodiglycol, thiocarbamide and hydrochloric acid is preferably 5：(6~8)：(6
~8) 25, are more preferably：(34~36)：(34~36).
In the present invention, shown in the mechanism of the salt-forming reaction such as formula (II)；
The present invention is abundant to ensure reaction, is kept the temperature after reflux, samples and tracks every 2h, if having raw material Thiodiglycol after
Continuous insulation reaction, stops reacting if without Thiodiglycol, cools down, and completes salt-forming reaction process, obtains isothiuronium salts hydrochlorate.
After obtaining the isothiuronium salts hydrochlorate, the present invention adds aqueous slkali and reaction is hydrolyzed, and obtains reaction mixture.
In the present invention, the dripping quantity of the aqueous slkali is preferably 250mL~350mL, more preferably 300mL.
In the present invention, shown in the mechanism of the hydrolysis such as formula (III)；
In the present invention, the temperature of the hydrolysis is preferably 60 DEG C~80 DEG C, more preferably 70 DEG C；The hydrolysis is anti-
The time answered is preferably 2h~4h, more preferably 3h.
After obtaining the reaction mixture, obtained reaction mixture is carried out liquid separation by the present invention, respectively obtains thio two
Sweet mercaptan crude product and reaction waste；Then the thio two sweet mercaptan crude product is washed, respectively obtains thio two sweet mercaptan
And washing waste water.The present invention is not particularly limited the device of the liquid separation, is leaked using liquid separation well known to those skilled in the art
Bucket.The present invention carries out liquid separation by the way of standing, and the time of the standing is preferably 25min~35min, more preferably
30min。
In the present invention, the temperature of the washing is preferably 65 DEG C~75 DEG C, more preferably 70 DEG C；The number of the washing
Preferably 2 times~5 times, more preferably 3 times；The washing water consumption washed every time is preferably 90mL~110mL, more preferably
100mL, the time washed every time are preferably 5min~10min, more preferably 8min.
After completing the water-washing process, the present invention is preferably layered by way of standing, then that upper water is tangent
Go out, respectively obtain thio two sweet mercaptan and washing waste water.
After obtaining the reaction waste and washing waste water, the present invention carries out obtained reaction waste and washing waste water respectively
Flocculation treatment, obtains cycling use of water.In the present invention, it is described to carry out obtained reaction waste and washing waste water at flocculation respectively
The process of reason is preferably specially：
C1) reaction waste that step b) is obtained is mixed with the first flocculant, first time flocculation treatment is carried out, respectively obtains
For the raw water of the preparation aqueous slkali in step a) and the washing water for water-washing process in step b)；
C2) washing waste water that step b) is obtained is mixed with the second flocculant, second of flocculation treatment is carried out, is used for
The washing water of water-washing process in step b).
The present invention mixes obtained reaction waste with the first flocculant, carries out first time flocculation treatment, respectively obtains use
The washing water of water-washing process in the middle raw waters for preparing the aqueous slkali of step a) and for step b).In the present invention, institute
State the first flocculant and be preferably selected from aluminum sulfate (Al2(SO4)3·18H2O), alum (Al2(SO4)3·K2SO4·24H2O), trichlorine
Change molten iron compound (FeCl3·6H2O), ferrous sulfate hydrate (FeSO4·7H2O), ferric sulfate (Fe2(SO4)3), polyaluminium
In aluminium (PAC), polyaluminium sulfate (PAS), poly-ferric chloride (PFC), bodied ferric sulfate (PFS) and polymerization Polyferric Sulfate silicon flocculant
One or more, more preferably alum (Al2(SO4)3·K2SO4·24H2O), polyaluminium sulfate (PAS), bodied ferric sulfate
(PFS) or polymerization Polyferric Sulfate silicon flocculant.The present invention is not particularly limited the source of first flocculant, using this area skill
Above-mentioned aluminum sulfate (Al known to art personnel2(SO4)3·18H2O), alum (Al2(SO4)3·K2SO4·24H2O), ferric trichloride
Hydrate (FeCl3·6H2O), ferrous sulfate hydrate (FeSO4·7H2O), ferric sulfate (Fe2(SO4)3), aluminium polychloride
(PAC), polyaluminium sulfate (PAS), poly-ferric chloride (PFC), bodied ferric sulfate (PFS) and polymerization Polyferric Sulfate silicon flocculant is commercially available
Commodity.
In the present invention, the mass ratio of the reaction waste and the first flocculant is preferably 100：(0.5~5), more preferably
For 100：(0.8~2).
In the present invention, the temperature of the first time flocculation treatment is preferably 10 DEG C~40 DEG C；At the first time flocculation
The time of reason is preferably 8min~12min, more preferably 10min.
The present invention mixes obtained washing waste water with the second flocculant, carries out second of flocculation treatment, obtains being used to walk
It is rapid b) in water-washing process washing water.In the present invention, second flocculant is preferably selected from aluminum sulfate (Al2(SO4)3·
18H2O), alum (Al2(SO4)3·K2SO4·24H2O), Iron trichloride hexahydrate (FeCl3·6H2O), ferrous sulfate hydrate
(FeSO4·7H2) and ferric sulfate (Fe O2(SO4)3) in one or more, more preferably aluminum sulfate (Al2(SO4)3·18H2O)、
Alum (Al2(SO4)3·K2SO4·24H2) or ferrous sulfate hydrate (FeSO O4·7H2O).The present invention is flocculated to described second
The source of agent is not particularly limited, using above-mentioned aluminum sulfate (Al well known to those skilled in the art2(SO4)3·18H2O), alum
(Al2(SO4)3·K2SO4·24H2O), Iron trichloride hexahydrate (FeCl3·6H2O), ferrous sulfate hydrate (FeSO4·
7H2) and ferric sulfate (Fe O2(SO4)3) commercial goods.
In the present invention, the mass ratio of the washing waste water and the second flocculant is preferably 100：(0.1~3), more preferably
For 100：1.
In the present invention, the temperature of second of flocculation treatment is preferably 10 DEG C~40 DEG C, more preferably 10 DEG C；It is described
The time of second of flocculation treatment is preferably 8min~12min, more preferably 10min.
Obtained cycling use of water is respectively used to prepare the raw water and step b) of the aqueous slkali in step a) by the present invention
The washing water of middle water-washing process, realizes the zero-emission of waste water.
The present invention provides a kind of preparation method of thio two sweet mercaptan, comprise the following steps：A) by Thiodiglycol, sulphur
Salt-forming reaction is carried out after urea and mixed in hydrochloric acid, aqueous slkali is added and reaction is hydrolyzed, obtain reaction mixture；B) by step a)
Obtained reaction mixture carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction waste；Then by described thio two
Sweet mercaptan crude product is washed, and respectively obtains thio two sweet mercaptan and washing waste water；C) reaction waste for obtaining step b) and
Washing waste water carries out flocculation treatment respectively, obtains cycling use of water.Compared with prior art, preparation method provided by the invention has
Higher product quality and yield, and can realize recycling for waste water.Test result indicates that preparation side provided by the invention
For the stable content for the thio two sweet mercaptan that method obtains more than 99%, yield realizes the zero-emission of waste water more than 98%.
In addition, preparation method provided by the invention does not have the three wastes substantially, pollution is small, realizes comprehensive utilization and the money of resource
Source value maximization, and energy consumption is low, clean environment firendly, and new thinking is provided for thio two sweet mercaptan productions.
In order to further illustrate the present invention, it is described in detail below by following embodiments.
Embodiment 1
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 34g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 34g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 70 DEG C, keeps the temperature 3h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 510g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：70 DEG C of washing waters of 100mL are added in beaker, stir 8min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 300g.
(4) the 510g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 5g bodied ferric sulfates (PFS), stir 10min, 411g first circulation water is then obtained by filtration, collect stand-by；Wherein, take
The above-mentioned first circulation water of 300g is used in step (2) prepare the raw water that the mass concentration is 10% sodium hydroxide solution,
Remaining first circulation water is stand-by.
(5) the 300g washing waste waters that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 3g alum (Al2(SO4)3·K2SO4·24H2O), 10min is stirred, 222g second circulation water is then obtained by filtration, with step
(4) after remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the gas phase collection of illustrative plates such as Fig. 1 institutes for the thio two sweet mercaptan that the preparation method that the embodiment of the present invention 1 provides obtains
Show；The content of thio two sweet mercaptan is 99.52% obtained by product, and yield realizes the zero-emission of waste water more than 98%.
Embodiment 2
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 35g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 35g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 70 DEG C, keeps the temperature 3h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：70 DEG C of washing waters of 100mL are added in beaker, stir 8min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 40 DEG C, added into flask
Enter 7.5g polymerization Polyferric Sulfate silicon flocculants, stir 10min, 370g first circulation water is then obtained by filtration, collect stand-by；Wherein,
The above-mentioned first circulation water of 250g is taken to be used in step (2) prepare the raw material that the mass concentration is 10% sodium hydroxide solution
Water, remaining first circulation water are stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 40 DEG C, into flask
Add 2.5g aluminum sulfate (Al2(SO4)3·18H2O), 10min is stirred, 205g second circulation water is then obtained by filtration, with step
(4) after remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 2 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 99%.
Embodiment 3
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 36g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 36g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 75 DEG C, keeps the temperature 2h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：70 DEG C of washing waters of 100mL are added in beaker, stir 8min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 10g alum (Al2(SO4)3·K2SO4·24H2O), 10min is stirred, 350g first circulation water is then obtained by filtration, is collected
It is stand-by；Wherein, it is that 10% sodium hydroxide is molten to take the above-mentioned first circulation water of 250g to be used to prepare the mass concentration in step (2)
The raw water of liquid, remaining first circulation water are stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 15 DEG C, into flask
Add 2.5g aluminum sulfate (Al2(SO4)3·18H2O), 10min is stirred, 210g second circulation water is then obtained by filtration, with step
(4) after remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 3 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 99%.
Embodiment 4
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 34g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 34g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 65 DEG C, keeps the temperature 4h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：70 DEG C of washing waters of 100mL are added in beaker, stir 8min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 10g polyaluminium sulfates (PAS), stir 10min, 360g first circulation water is then obtained by filtration, collect stand-by；Wherein, take
The above-mentioned first circulation water of 255g is used in step (2) prepare the raw water that the mass concentration is 10% sodium hydroxide solution,
Remaining first circulation water is stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 10 DEG C, into flask
Add 2.5g ferrous sulfate hydrates (FeSO4·7H2O), 10min is stirred, 208g second circulation water is then obtained by filtration, with
After step (4) remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 4 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 98%.
Embodiment 5
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 34g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 34g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 70 DEG C, keeps the temperature 3h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：65 DEG C of washing waters of 100mL are added in beaker, stir 10min, then are layered after standing 30min, then by upper strata
Water is mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 10g polymerization Polyferric Sulfate silicon flocculants, stir 10min, 350g first circulation water is then obtained by filtration, collect stand-by；Wherein, take
The above-mentioned first circulation water of 255g is used in step (2) prepare the raw water that the mass concentration is 10% sodium hydroxide solution,
Remaining first circulation water is stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 15 DEG C, into flask
Add 2.5g aluminum sulfate (Al2(SO4)3·18H2O), 10min is stirred, 208g second circulation water is then obtained by filtration, with step
(4) after remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 5 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 99%.
Embodiment 6
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 34g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 34g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 70 DEG C, keeps the temperature 3h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：75 DEG C of washing waters of 100mL are added in beaker, stir 5min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 5g polymerization Polyferric Sulfate silicon flocculants, stir 10min, 380g first circulation water is then obtained by filtration, collect stand-by；Wherein, take
The above-mentioned first circulation water of 280g is used in step (2) prepare the raw water that the mass concentration is 10% sodium hydroxide solution,
Remaining first circulation water is stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 10 DEG C, into flask
Add 2.5g aluminum sulfate (Al2(SO4)3·18H2O), 10min is stirred, 211g second circulation water is then obtained by filtration, with step
(4) after remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 6 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 99%.
Embodiment 7
(1) preparation of isothiuronium salts hydrochlorate：To equipped with thermometer, blender, air-breather 250mL four-hole boiling flasks in plus
Enter 34g thiocarbamides, open stirring, then add the concentrated hydrochloric acid that 34g mass concentrations are 37%, be warming up to dissolving, then be directly added into 25g
Thiodiglycol, is warming up to reflux after addition；Kept the temperature after reflux, sample and track every 2h, if there is raw material Thiodiglycol
Then continue insulation reaction, stop reacting if without Thiodiglycol, cool down；
(2) isothiuronium salts hydrochlorate hydrolyzes：Less than 60 DEG C are cooled to, it is 10% hydrogen that 300mL mass concentrations are added dropwise into flask
Sodium hydroxide solution, then heats to 70 DEG C, keeps the temperature 3h, and reaction terminates, and obtains reaction mixture.
(3) reaction mixture that step (2) obtains is poured into and 30min is stood in separatory funnel, carried out liquid separation, respectively obtain
Thio two sweet mercaptan crude product of oil phase and 500g reaction wastes；Thio two sweet mercaptan crude products are poured into beaker and are washed, specifically
Process is：70 DEG C of washing waters of 100mL are added in beaker, stir 8min, then are layered after standing 30min, then by upper water
Mutually cut out；So washing three times, obtains thio two sweet mercaptan products, supervenes the washing waste water of 250g.
(4) the 500g reaction wastes that step (3) obtains are poured into 1L four-hole boiling flasks, at 10 DEG C, added into flask
Enter 5g bodied ferric sulfates (PFS), stir 10min, 390.5g first circulation water is then obtained by filtration, collect stand-by；Wherein, take
The above-mentioned first circulation water of 280g is used in step (2) prepare the raw water that the mass concentration is 10% sodium hydroxide solution,
Remaining first circulation water is stand-by.
(5) the 250g washing waste waters that step (3) obtains are poured into 500mL four-hole boiling flasks, at 10 DEG C, into flask
Add 2.5g alum (Al2(SO4)3·K2SO4·24H2O), 10min is stirred, 211g second circulation water is then obtained by filtration, with
After step (4) remaining first circulation is mixed with water, as the washing water for water-washing process in step (3).
After testing, the content of thio two sweet mercaptan exists obtained by the product that the preparation method that the embodiment of the present invention 7 provides obtains
More than 99%, yield realizes the zero-emission of waste water more than 98%.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or use the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Most wide scope.
Claims (10)
1. a kind of preparation method of thio two sweet mercaptan, comprises the following steps：
A) salt-forming reaction will be carried out after Thiodiglycol, thiocarbamide and mixed in hydrochloric acid, adds aqueous slkali and reaction is hydrolyzed, obtain
Reaction mixture；
B) reaction mixture for obtaining step a) carries out liquid separation, respectively obtains thio two sweet mercaptan crude products and reaction waste；So
The thio two sweet mercaptan crude product is washed afterwards, respectively obtains thio two sweet mercaptan and washing waste water；
C) the obtained reaction wastes of step b) and washing waste water are subjected to flocculation treatment respectively, obtain cycling use of water.
2. preparation method according to claim 1, it is characterised in that Thiodiglycol, thiocarbamide and salt described in step a)
The mass ratio of acid is 5：(6~8)：(6~8)；
The hydrochloric acid is the concentrated hydrochloric acid that mass concentration is 37%.
3. preparation method according to claim 1, it is characterised in that the temperature of hydrolysis described in step a) is 60 DEG C
~80 DEG C, the time is 2h~4h.
4. preparation method according to claim 1, it is characterised in that the temperature washed described in step b) is 65 DEG C~75
DEG C, number is 2 times~5 times；The washing water consumption washed every time is 90mL~110mL, and the time is 5min~10min.
5. preparation method according to claim 1, it is characterised in that the step c) is specially：
C1) reaction waste that step b) is obtained is mixed with the first flocculant, first time flocculation treatment is carried out, respectively obtains and be used for
The raw water of the aqueous slkali and the washing water for water-washing process in step b) are prepared in step a)；
C2) washing waste water that step b) is obtained is mixed with the second flocculant, second of flocculation treatment is carried out, obtains being used for step
B) washing water of water-washing process in.
6. preparation method according to claim 5, it is characterised in that step c1) described in the first flocculant be selected from sulfuric acid
Aluminium, alum, Iron trichloride hexahydrate, ferrous sulfate hydrate, ferric sulfate, aluminium polychloride, polyaluminium sulfate, polyaluminium
One or more in iron, bodied ferric sulfate and polymerization Polyferric Sulfate silicon flocculant.
7. preparation method according to claim 5, it is characterised in that step c1) described in reaction waste and first flocculation
The mass ratio of agent is 100：(0.5~5).
8. preparation method according to claim 5, it is characterised in that step c2) described in the second flocculant be selected from sulfuric acid
One or more in aluminium, alum, Iron trichloride hexahydrate, ferrous sulfate hydrate and ferric sulfate.
9. preparation method according to claim 5, it is characterised in that step c2) described in washing waste water and second flocculation
The mass ratio of agent is 100：(0.1~3).
10. preparation method according to claim 1, it is characterised in that the temperature of flocculation treatment described in step c) is 10
DEG C~40 DEG C, the time is 8min~12min.
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| CN109651214A (en) * | 2018-12-17 | 2019-04-19 | 锦西化工研究院有限公司 | Floccule in a kind of two mercapto ethyl thioethers of removal improves product purity, the method for yield |
| CN110655481A (en) * | 2019-10-31 | 2020-01-07 | 山东益丰生化环保股份有限公司 | Preparation method of thiodiglycol |
| CN112409229A (en) * | 2020-11-30 | 2021-02-26 | 山东益丰生化环保股份有限公司 | Preparation method of thiodiglycol |
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| CN1803769A (en) * | 2006-01-19 | 2006-07-19 | 中蓝晨光化工研究院 | Method for preparing 2-sulfhydyl alkyl sulfide and 2- sulfhydyl alkyl ether compound |
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| CN110655481A (en) * | 2019-10-31 | 2020-01-07 | 山东益丰生化环保股份有限公司 | Preparation method of thiodiglycol |
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Effective date of registration: 20180810 Address after: 256500 Jingbo Industrial Park, Boxing Economic Development Zone, Binzhou, Shandong, China Applicant after: Shandong Efirm Biochemistry and Environmental Protection Co., Ltd. Address before: 256500 Binzhou Boxing Economic Development Zone Jingbo Industrial Park Yellow River Delta Jingbo Chemical Research Institute Co., Ltd. Applicant before: Yellow River Delta Jingbo Chemical Research Institute Co., Ltd. |
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