CN108568128A - The recovery method of synthetic - Google Patents
The recovery method of synthetic Download PDFInfo
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- CN108568128A CN108568128A CN201710753529.4A CN201710753529A CN108568128A CN 108568128 A CN108568128 A CN 108568128A CN 201710753529 A CN201710753529 A CN 201710753529A CN 108568128 A CN108568128 A CN 108568128A
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- phthalimide
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- cyclohexyl
- water
- synthetic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Abstract
Problem of the present invention is that after in order to synthesize N (cyclohexyl thio) phthalimide in the solvent of saturated hydrocarbons, solvent is recycled, and a kind of industrially advantageously method of recycling design is provided.The solution of the present invention is a kind of recovery method of synthetic, wherein, so that cyclohexyl time sulfonic acid chloride and phthalimide is reacted in the solvent comprising saturated hydrocarbons and after synthesizing N (cyclohexyl thio) phthalimide, detaching by N (cyclohexyl thio) phthalimide partial crystallizations and by crystal, alkaline matter and water are added into partial crystallization mother liquor, distill solvent in the presence of alkaline matter and water.
Description
Technical field
The present invention relates to the useful compound Ns-of the premature vulcanization retarder in the vulcanization process as rubber (cyclohexyl thio)
The recovery method of the synthetic of phthalimide, the synthetic of N- (cyclohexyl thio) phthalimide
It is to synthesize the solvent used when N- (cyclohexyl thio) phthalimide.More specifically, provide industrially it is advantageous simultaneously
And the method that the synthetic of N- (cyclohexyl thio) phthalimide is recycled there is no the problem in safety operation.
Background technology
In general, N- (cyclohexyl thio) phthalimides under the coexisting of alkali by making cyclohexyl time sulfonic acid chloride and neighbour
Phthalimide is reacted and is manufactured.In general, in the preparation method, using chlorine, in strong acidic condition, synthesis material cyclohexyl time sulphonyl
Chlorine, next, under strongly alkaline conditions, cyclohexyl time sulfonic acid chloride is made to be condensed with phthalimide.Therefore, as to strong acid
And the solvent that highly basic is stable and the burden to environment is small, saturated hydrocarbons can be used.In plant-scale synthesis, in order to reduce
Manufacturing cost and efficent use of resources can recycle by synthetic is recycled in distillation etc..
For this method, the Physical Loss or Damage of solvent is big, moreover, in the presence of the danger that accident occurs when being distilled to recover.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-186438 bulletins
Invention content
Problems to be solved by the invention
The purpose of the present invention is to provide industrially advantageously recycle N- (cyclohexyl thio) phthalimide
The method of synthetic.
Means for solving the problems
The inventors of the present invention have made intensive studies the method for solving aforementioned problems, as a result, it has been found that, in synthesis N- (cyclohexyl
It is thio) after phthalimide, by simply handling, you can synthetic is efficiently and safely recycled, so as to complete
The present invention.
That is, the present invention provides a kind of recovery method of synthetic, wherein make cyclohexyl time sulfonic acid chloride and O-phthalic
Acid imide reacts in the solvent of saturated hydrocarbons and synthesizes N- (cyclohexyl thio) phthalimide, makes N- (cyclohexyl thio)
Phthalimide partial crystallization and after detaching crystal, alkaline matter and water is added into partial crystallization mother liquor, in alkaline matter and water
In the presence of solvent is distilled.
The effect of invention
Through the invention, by when carrying out the recycling of synthetic, alkaline matter and water being added, so as to industrially
Advantageously recycle the synthetic of N- (cyclohexyl thio) phthalimide.
In the present invention, the Physical Loss or Damage of the synthetic of N- (cyclohexyl thio) phthalimide declines.In addition, this
In invention, the danger that accident occurs when being distilled to recover is small, is remarkably contributing to plant-scale stable operation.The synthesis of the present invention
The recovery method of solvent is highly useful in the industrial production of N- (cyclohexyl thio) phthalimide.
Specific implementation mode
The present invention described further below.
In the present invention, in the solvent comprising saturated hydrocarbons, cyclohexyl time sulfonic acid chloride is made to be reacted with phthalimide.This
The saturated hydrocarbons that the preferred carbon atom number of saturated hydrocarbon solvent used in invention is 5~10.Pentane, ring penta can further preferably be enumerated
Alkane, n-hexane, hexamethylene, normal heptane, hexahydrotoluene, normal octane, cyclooctane etc..It is molten for the saturated hydrocarbons used in the present invention
For agent, a kind of saturated hydrocarbon solvent can be used, two or more saturated hydrocarbon solvent can also be mixed and be used.
In the present invention, for saturated hydrocarbons, saturated hydrocarbons can be used only.In addition, also can will be other than saturated hydrocarbons and saturated hydrocarbons
Solvent mixing and use.About the solvent being used in mixed way with saturated hydrocarbons, aromatic hydrocarbon, chlorohydrocarbon etc. can be enumerated.Aromatic hydrocarbon
It is preferred that the aromatic hydrocarbon that carbon atom number is 6~8, can further preferably enumerate toluene, dimethylbenzene, ethylo benzene etc..Chlorohydrocarbon is preferred
The chlorohydrocarbon that carbon atom number is 1~6, can further preferably enumerate ethylene dichloride, chlorobenzene etc..
The cyclohexyl time sulfonic acid chloride used in the recovery method of the synthetic of the present invention is usually by making dicyclohexyl two
Thioether or cyclohexanethiol are reacted with chlorine and are synthesized.Synthesis ring is being reacted with chlorine by dicyclohexyldisulfide or cyclohexanethiol
In the case of hexyl time sulfonic acid chloride, it is preferable to use the solvents comprising saturated hydrocarbons for solvent.Further preferred use and cyclohexyl time sulphur
Acyl chlorides reacts the identical solvent of used solvent with phthalimide.
For making dicyclohexyldisulfide or cyclohexanethiol be reacted with chlorine and chlorine when synthesizing cyclohexyl time sulfonic acid chloride
It it is 0.5~2 times mole, preferably 1~1.5 times mole in general, relative to material thioether or mercaptan for usage amount.For molten
It is 0.5~10 times of weight in general, relative to dicyclohexyldisulfide or cyclohexanethiol for the usage amount of agent, preferably 1
~5 times of weight.Reaction temperature is usually -30~20 DEG C, preferably -20~5 DEG C.Reaction time with chlorine is usually 0.1~
10 hours.Reaction time with chlorine is preferably 1~5 hour.For reaction pressure, usually carry out under normal pressure, but
It can carry out, can also carry out under elevated pressure under reduced pressure.For reaction method, in general, in the solvent comprising saturated hydrocarbons
Dicyclohexyldisulfide or cyclohexanethiol are dissolved, chlorine is blown into and synthesizes.
In the recovery method of the synthetic of the present invention, for cyclohexyl time sulfonic acid chloride, for example, by the hexamethylene of synthesis
Base time sulfonic acid chloride is held in low temperature and uses.Usually -30~20 DEG C of the storage temperature of cyclohexyl time sulfonic acid chloride, preferably -20
~5 DEG C.
The phthalimide used in the recovery method of the synthetic of the present invention can utilize any synthesis side
The phthalimide of method manufacture.For example, the manufacturing method reacted based on ammonia or urea etc. with phthalic anhydride can be enumerated.
In the recovery method of the synthetic of the present invention, for reacting for cyclohexyl time sulfonic acid chloride and phthalimide
For condition, cyclohexyl time sulfonic acid chloride is usually 0.5~3 times mole relative to the molar ratio of phthalimide, preferably
0.8~1.5 times mole.If cyclohexyl time sulfonic acid chloride is 0.5~3 times mole relative to the molar ratio of phthalimide,
Unreacted phthalimide is few, and unreacted cyclohexyl time sulfonic acid chloride is not easily decomposed.
In the recovery method of the synthetic of the present invention, the reaction temperature of cyclohexyl time sulfonic acid chloride and phthalimide
Usually 0~100 DEG C, preferably 10~80 DEG C.If reaction temperature is 0~100 DEG C, rapid reaction, the N- as object
(cyclohexyl thio) phthalimide, cyclohexyl time sulfonic acid chloride do not decompose.Reaction time is usually 0.1~10 hour.It is excellent
It is selected as 1~5 hour.If the reaction time is 0.1~10 hour, yield, productivity are high.Reaction pressure can under normal pressure or be subtracted
Pressure.
In the recovery method of the synthetic of the present invention, in reacting for cyclohexyl time sulfonic acid chloride and phthalimide
In, for the usage amount of solvent, in general, being 0.5~10 times of weight, preferably 1~5 weight relative to phthalimide
Amount times.If the usage amount of solvent is 0.5~10 times of weight for phthalimide, yield improves, productivity
Well.
In the recovery method of the synthetic of the present invention, for reacting for cyclohexyl time sulfonic acid chloride and phthalimide
For, in general, cyclohexyl time chloride solution can be added in the slurry or solution of phthalimide, alternatively, by adjacent
The slurry or solution of phthalimide are added in cyclohexyl time chloride solution, alternatively, adding simultaneously and making its contact.It is right
For the reacting of cyclohexyl time sulfonic acid chloride and phthalimide, preferably will be to the cyclohexyl time sulfonic acid chloride of thermally labile
While solution is kept in a low temperature of -30~20 DEG C, the molten of the phthalimide in reactor is added it to
In liquid or slurry.
In the recovery method of the synthetic of the present invention, in reacting for cyclohexyl time sulfonic acid chloride and phthalimide
In, byproduct hydrogen chloride is generated, it is therefore preferable that alkali has coexisted as agent for capturing.The alkali used can be organic base, inorganic base or
Their mixture.As organic base, preferred tertiary amine can enumerate such as Trimethylamine, triethylamine, tripropylamine, tributyl
Amine, dimethyl benzyl amine, N-methylmorpholine etc..Further preferably triethylamine, dimethyl benzyl amine.It, can as inorganic base
Enumerate metal hydroxides, metal oxide etc..As inorganic base, preferably alkali metal hydroxide, alkaline-earth metal hydroxide
Object, alkaline earth oxide.Specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide can be enumerated.Further preferably
For sodium hydroxide, potassium hydroxide, calcium hydroxide.Inorganic base can be used in the form of slurry in aqueous solution or water.
In the present invention, for the usage amount of alkali coexist in reaction, in general, relative to cyclohexyl time sulfonic acid chloride,
For 0.7 times mole~3 times moles of range.For the usage amount of alkali, preferably 0.9 times mole~2 times moles.Further
Preferably 1.0 times moles~1.5 times moles.For alkali, whole amount is usually added before starting the reaction.Cyclohexyl is secondary
It, also can be with the addition of cyclohexyl time chloride solution in the case that chloride solution is added in the slurry of phthalimide
Together, it simultaneously continuously supplies.In addition, using inorganic base, it can not also be used alone, make adjacent benzene two in advance
Carboximide is reacted with the inorganic base used, adjacent benzene two as synthesis potassium phthalimide, phthalimide sodium
Carboximide salt makes it be reacted with cyclohexyl time sulfonic acid chloride.
In the present invention, N- (cyclohexyl thio) phthalimide of synthesis is subjected to partial crystallization, obtains N- (cyclohexyl sulphur
Generation) phthalimide.Obtained N- (cyclohexyl thio) phthalimide is preferably crystalline solid.
In the recovery method of the synthetic of the present invention, in general, for salt, alkali, the raw material that will be generated as by-product
Deng removing, reaction mixture is mixed with water, neutralized with acid, then carry out liquid separation, obtained comprising the adjacent benzene of N- (cyclohexyl thio)
The oil reservoir of dicarboximide.Preferably will include N- for N- (cyclohexyl thio) phthalimide in the present invention
The oil reservoir of (cyclohexyl thio) phthalimide is cooling and carries out partial crystallization.For the crystal that partial crystallization goes out, can by into
Row is filtered and is detached with mother liquor, is dried to remove solvent.It may further be preferable that in the present invention, including saturation
It carries out cooling in the solvent of hydrocarbon and carries out partial crystallization.It should be noted that for the solvent removed when dry, in order to carry out
It recycles, condenser etc. can also be used and cooled down, it is made to condense and be recycled.
In the present invention, after making N- (cyclohexyl thio) phthalimide partial crystallizations and detaching crystal, in order to carry out
It recycles, and the solvent in partial crystallization mother liquor is distilled to recover.At this point, alkaline matter and water are added into partial crystallization mother liquor,
Solvent distillation is important in the presence of alkaline matter and water.
The alkaline matter added in the process of the distillation recovery of progress solvent in the present invention can be organic base, inorganic base
Or their mixture.As organic base, preferably amine, such as monoethanolamine, diethanol amine, triethanolamine, diformazan can be enumerated
Base benzyl amine, N-methylmorpholine etc..Further preferably triethanolamine, dimethyl benzyl amine.As inorganic base, metal can be enumerated
Hydroxide, metal oxide etc..As inorganic base, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide can be preferably enumerated.
Further preferably sodium hydroxide.
In the present invention, for the amount of the alkaline matter added in the process for carrying out the distillation recovery of solvent, relatively
It is 0.1 weight of weight %~10 % in remaining N- (cyclohexyl thio) phthalimide in partial crystallization mother liquor.Preferably
0.5 weight of weight %~5 %.If additive amount is the 0.1 weight % of weight %~10, big, the discarded residue of effect of the invention
Amount is reduced.
In the present invention, remaining residue is preferably alkalinity after solvent distillation.Residue is alkalinity, i.e. hydrogen ion exponent pH is 7
When above, the fulminant decomposition of residue can inhibit.
Carry out in the present invention addition alkaline matter in the process of the distillation recovery of solvent opportunity can be distillation before,
It can be distillation midway.With the progress of the concentration of partial crystallization mother liquor, the effect of alkaline matter increases, it is therefore preferable that in solvent
The amount that amount essentially becomes half by weight is added before.Further preferably alkaline matter is added before distillation starts.
The water added in the process of distillation recovery about the progress solvent in the present invention, can enumerate pure water, distilled water, from
Sub- exchanged water, tap water, seawater etc..It can be by water together with the inorganic base added in distillation recovery, to be starched in aqueous solution or water
The form of material is added.In addition it is also possible to be blown into water as water vapor.Think that water residual solvents is being discharged and by basic species
There is effect in terms of matter dispersion.
In the present invention, for the water added in the process for carrying out the distillation recovery of solvent, relative in partial crystallization
Remaining N- (cyclohexyl thio) phthalimide, preferably 0.1 weight of weight %~1000 % in mother liquor.It is further excellent
It is selected as 0.5 weight of weight %~100 %.If additive amount is the 0.1 weight % of weight %~1000, the effect of the present invention is big, water
Distillate few, efficiency is good.
In the present invention, added in the distillation recovery of solvent water opportunity can be distillation before, can also be midway.So
And since water is distillated with the progress of the concentration of partial crystallization mother liquor, it is therefore preferable that being added in partial crystallization mother liquor in distillation.Into
One step preferably adds addition for several times in distillation in midway.Intermittently or continuously add.
In the present invention, in the process for carrying out the distillation recovery of solvent, the alkaline matter of addition is more preferably dissolved in water
In and be added in form of an aqueous solutions.It is added further preferably in the form of sodium hydrate aqueous solution.Sodium hydroxide is water-soluble
The concentration of liquid is preferably 1~50%, and more preferably 20~49%.
In the recovery method of N- (cyclohexyl thio) phthalimide synthetic of the present invention, solvent is carried out
The interior temperature being distilled to recover is usually 0~100 DEG C, preferably 40~70 DEG C.
The synthetic being distilled to recover from partial crystallization mother liquor in the manner described above does not have special problem in quality, can be
It is recycled in the reacting of cyclohexyl time sulfonic acid chloride and phthalimide.
Embodiment
Hereinafter, enumerate embodiment illustrates the present invention in further detail.
Reference example 1
In stirring groove profile enamel (glass lining) 3m processed3In reactor, it is packed into dicyclohexyldisulfide 910Kg and (divides
Son amount 230.4, purity 94%, 3.71Kg moles) and toluene (111 DEG C of boiling point)/hexamethylene (81 DEG C of boiling point) mixed solvent
1250Kg (14 weight % of toluene, density 0.781Kg/L, 1600L), -20 DEG C are cooled to refrigerant.Exist -20 while stirring
Through being blown within 2.0 hours chlorine 303Kg (molecular weight 70.9,4.27Kg moles) thereto under~-10 DEG C of liquid temperature, by dicyclohexyl two
Thioether chlorination, obtain cyclohexyl time sulfonic acid chloride solution 2460Kg (molecular weight 150.7, cyclohexyl time sulphonyl chlorinity 1120Kg,
7.43Kg mole).
Reference example 2
In addition to using the mixed solvent 1340Kg of ethlyene dichloride (83 DEG C of boiling point)/hexamethylene (20 weight % of ethlyene dichloride, close
Spend 0.838Kg/L, 1600L) it is used as except cyclohexyl time sulfonic acid chloride synthetic, it is operated in the same manner as reference example 1, obtains hexamethylene
The solution 2550Kg (7.43Kg moles) of base time sulfonic acid chloride.
Embodiment 1
To the stirring slot type enamel 6m for having the Stirring device that there is stirring blade in bottom3It is packed into reactor adjacent
Phthalimide 1050Kg (molecular weight 147.1,7.14Kg moles), (molecular weight 101.2,9.65Kg's triethylamine 977Kg rub
You) and first benzene/cyclohexane mixed solvent 1090Kg (14 weight % of toluene, density 0.781Kg/L, 1400L), heated with warm water
To 60 DEG C.With while stirring (mean speed 100rpm) 63~67 DEG C reaction temperature, supplied thereto through 22.0 hours
The cyclohexyl time chloride solution 2460Kg prepared in the reference example 1 that cold insulation is -10 DEG C, then continues at the same temperature
It stirs within 0.5 hour, obtains comprising N- (cyclohexyl thio) phthalimide, unreacted phthalimide, chlorination three
The reaction mixture of ethyl ammonium etc..
Be stirred on one side in 60~65 DEG C of temperature, add 1000Kg warm water into the reaction mixture on one side and by ammonium
The dissolvings such as salt, then, by filterings such as unreacted phthalimides.The temperature in 60~65 DEG C is stirred on one side, and one
While adding sulfuric acid in order to remove the superfluous triethylamine etc. in filtrate into water layer and neutralizing.Next, on one side in
60~65 DEG C of temperature is stirred, on one side in order to by the oil reservoir isolated remaining phthalimide remove and add
The sodium hydroxide for adding 48 weight %, water layer is detached.
On one side in post-processing remaining oil reservoir be stirred, be cooled to 10 DEG C on one side, by N- (cyclohexyl thio) neighbour
Phthalimide partial crystallization.By being filtered, drying by the crystal (when dry, with condenser recycling design), product is obtained
1680g (rub by molecular weight 261.3, purity 99.0%, N- (cyclohexyl thio) phthalimide content 1660g, 6.35Kg
You) and partial crystallization mother liquor 2600Kg (N- (cyclohexyl thio) phthalimides content 70Kg, 0.27Kg mole).Relative to neighbour
The total recovery of phthalimide is 93% (1730Kg, 6.64Kg mole), N- (cyclohexyl thio) phthalyl in product
The partial crystallization rate of imines is 97%.
Next, adding 48% sodium hydrate aqueous solution 2.0Kg (sodium hydrate contents into partial crystallization mother liquor 2600Kg
0.96Kg, water content 1.04Kg), it is decompressed to 50mmHg (6.7kPa) from 300mmHg (40kPa) on one side, on one side with 82 DEG C of warm water
It is heated from outside, until interior temperature rises to 52 DEG C, is concentrated under reduced pressure, when distillating about 1000Kg solvents, additional addition
Water 1.0Kg, solvent is distilled to recover.After the water distillated is detached, recovered solvent is 2240Kg (toluene while being dried
14 weight %).The loss amount started from charging is 100Kg, loss late 4.3%.In addition, residue obtained from being concentrated under reduced pressure
360Kg is filled into 2 metal buckets (200L), is discarded.The part (0.1g) for acquiring residue, is added to ion exchange water
It in (10mL) and is mixed, as a result pH is 10, in alkalinity.
It is residual obtained from being concentrated under reduced pressure for carrying out similarly after reaction, post-processing, partial crystallization, distillation recovery
For slag fills the operation into metal bucket, carry out 4~5 times within one day, whole year is repeated.The metal bucket that will be filled with residue is stored in
Open air, no exceptions in bucket.
It should be noted that the analysis and utilization gas chromatography of product and mother liquor carries out.Analysis condition is as described below.
GC devices：Shimadzu GC-17A
Column：NB-1, length 60m × internal diameter0.40 μm of film thickness
Column temperature：70 → 270 DEG C, 5 DEG C/min
Carrier gas He gas：180kPa(70℃)
Inlet fid detector：270℃.
Embodiment 2
Using ethlyene dichloride/hexamethylene mixed solvent 1170Kg (20 weight % of ethlyene dichloride, density 0.838kg/L,
1400L) the synthetic as N- (cyclohexyl thio) phthalimide uses the cyclohexyl prepared in reference example 2
In addition to this chloride solution 2550Kg is reacted, is post-processed similarly to Example 1.
On one side in post-processing remaining oil reservoir be stirred, be cooled to 10 DEG C on one side, by N- (cyclohexyl thio) neighbour
Phthalimide partial crystallization.It washs, be dried by the way that the crystal to be filtered, with a small amount of solvent, to obtain product
1710Kg (purity 99.1%, N- (cyclohexyl thio) phthalimides content 1700Kg, 6.50Kg mole) and partial crystallization are female
Liquid 2700Kg (N- (cyclohexyl thio) phthalimides content 72Kg, 0.28Kg mole).Relative to phthalyl Asia
The total recovery of amine is 95% (1770kg, 6.77Kg mole), the partial crystallization of N- (cyclohexyl thio) phthalimide in product
Rate is 96%.
Next, adding 48% sodium hydrate aqueous solution 1.0Kg (sodium hydrate contents into partial crystallization mother liquor 2700Kg
0.48Kg, water content 0.52Kg), it is concentrated under reduced pressure similarly to Example 1, when distillating about 1000Kg solvents, addition adds
Add 48% sodium hydrate aqueous solution 1.0Kg and water 1.0kg, solvent is distilled to recover.After the water distillated is detached, it is dried
Recovered solvent is 2440Kg (20 weight % of ethlyene dichloride) simultaneously.The loss amount started from charging is 70Kg, and loss late is
2.8%.In addition, filling residue 260Kg obtained from reduced pressure into 2 metal buckets (200L), discarded.It acquires residual
A part (0.1g) for slag, is added in ion exchange water (10mL) and is mixed, and as a result pH is 11, in alkalinity.
It is residual obtained from being concentrated under reduced pressure for carrying out similarly after reaction, post-processing, partial crystallization, distillation recovery
For slag fills the operation into metal bucket, carry out 4~5 times within one day, whole year is repeated.The metal bucket that will be filled with residue is stored in
Open air, no exceptions in bucket.
Embodiment 3
Other than adding sodium hydroxide 1.0Kg into partial crystallization mother liquor, reacted, post-processed similarly to Example 1,
Partial crystallization, then, for partial crystallization mother liquor 2600Kg (N- (cyclohexyl thio) phthalimides content 70Kg), with embodiment 1
Similarly it is distilled to recover solvent.Recovered solvent is 2200Kg (14 weight % of toluene) while being dried.It is started from charging
Loss amount be 140Kg, loss late 6.0%.The part (0.1g) for acquiring residue, is added in ion exchange water (10mL)
And mixed, as a result pH is 9, in alkalinity.
Comparative example 1
Other than adding alkaline matter not into partial crystallization mother liquor, is reacted, post-processed similarly to Example 1, is brilliant
Analysis, it is then, same with embodiment 1 for partial crystallization mother liquor 2600kg (N- (cyclohexyl thio) phthalimides content 70Kg)
It is distilled to recover solvent to sample.Recovered solvent is 2100Kg (14 weight % of toluene) while being dried.It is started from charging
Loss amount is 240Kg, loss late 10%.The part (0.1g) for acquiring residue, is added in ion exchange water (10mL) simultaneously
It is mixed, as a result, pH 4, in acidity, and non-alkaline.
Comparative example 2
Other than adding alkaline matter not into partial crystallization mother liquor, is reacted, post-processed similarly to Example 1, is brilliant
Analysis, it is then, same with embodiment 1 for partial crystallization mother liquor 2700kg (N- (cyclohexyl thio) phthalimides content 72Kg)
It is distilled to recover solvent to sample.Recovered solvent is 2230Kg (20 weight % of ethlyene dichloride) while being dried.From charging
The loss amount of calculation is 280Kg, loss late 11%.In addition, filling residue 470Kg obtained from reduced pressure to 2 metal buckets
In (200L), discarded.The part (0.1g) for acquiring residue, is added in ion exchange water (10mL) and is mixed
It closes, as a result pH is 3, in acidity, and non-alkaline.
For similarly react, post-processing, after partial crystallization, residue obtained from being concentrated under reduced pressure is filled to iron
It for operation in bucket, carries out 4~5 times within one day, will be filled with the metal bucket storage of residue outdoors.It carries out depressurizing on day 3 dense
When contracting, there is the phenomenon that interior temperature is higher than warm water, implys that the residue in concentration has decomposition, exothermic possibility.Later, outdoors
6 internal pressures in metal bucket in preservation rise, and expansion, the part in outer surface observes corrosion, specifies residue
It decomposes.There is a problem of in terms of safety operation serious.
Claims (5)
1. a kind of recovery method of synthetic, wherein make cyclohexyl time sulfonic acid chloride with phthalimide comprising full
N- (cyclohexyl thio) phthalimide is synthesized with being reacted in the solvent of hydrocarbon, by N- (cyclohexyl thio) phthalyl
Imines partial crystallization and after detaching crystal, alkaline matter and water are added into partial crystallization mother liquor, will in the presence of alkaline matter and water
Solvent distills.
2. the recovery method of synthetic as described in claim 1, wherein alkaline matter is sodium hydroxide.
3. the recovery method of synthetic as claimed in claim 2, wherein it is water-soluble to add sodium hydroxide into partial crystallization mother liquor
Liquid.
4. the recovery method of synthetic according to any one of claims 1 to 3, wherein in distillation to partial crystallization mother liquor
Middle addition water.
5. the recovery method of synthetic as described in any one of claims 1 to 4, wherein remaining residual after solvent distillation
Slag is alkalinity.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-048398 | 2017-03-14 | ||
| JP2017048398A JP6787199B2 (en) | 2017-03-14 | 2017-03-14 | Method of recovering synthetic solvent |
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| Publication Number | Publication Date |
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| CN108568128A true CN108568128A (en) | 2018-09-25 |
| CN108568128B CN108568128B (en) | 2021-09-24 |
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| CN201710753529.4A Active CN108568128B (en) | 2017-03-14 | 2017-08-29 | Method for recovering synthetic solvent |
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| JP (1) | JP6787199B2 (en) |
| CN (1) | CN108568128B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988096A (en) * | 2019-05-13 | 2019-07-09 | 汤阴永新化学有限责任公司 | The recovery method of CTP in solvent after synthesizing CTP use |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988096A (en) * | 2019-05-13 | 2019-07-09 | 汤阴永新化学有限责任公司 | The recovery method of CTP in solvent after synthesizing CTP use |
| CN109988096B (en) * | 2019-05-13 | 2022-05-10 | 汤阴永新化学有限责任公司 | Method for recovering CTP in solvent after CTP synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108568128B (en) | 2021-09-24 |
| JP6787199B2 (en) | 2020-11-18 |
| JP2018150279A (en) | 2018-09-27 |
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