CN107473927A - A kind of preparation technology of biphenyl-benzyl dichloride - Google Patents
A kind of preparation technology of biphenyl-benzyl dichloride Download PDFInfo
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- CN107473927A CN107473927A CN201710729521.4A CN201710729521A CN107473927A CN 107473927 A CN107473927 A CN 107473927A CN 201710729521 A CN201710729521 A CN 201710729521A CN 107473927 A CN107473927 A CN 107473927A
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Abstract
The present invention relates to a kind of preparation technology of biphenyl-benzyl dichloride, belongs to technical field of chemical synthesis.The present invention is used as raw material using paraformaldehyde and biphenyl, synthesized under the catalytic action of zinc chloride, acetic acid and thiacyclohexane and biphenyl-benzyl dichloride is made, the present invention continuously provides hydrogen chloride gas with concentrated hydrochloric acid reaction using chlorosulfuric acid for synthetic reaction, so that chloromethylation is smoothed out, improve the yield and product quality of biphenyl-benzyl dichloride, sewage load is few, and processing cost is low.The preparation technology of the invention biphenyl-benzyl dichloride introduces excessive water in avoiding toward reaction system, in turn results in the reduction of zinc chloride catalytic effect, and avoids the generation of strong carcinogenic intermediate product.Production technology green, environmental protection, reduce production cost, suitable for industrializing expanding production.
Description
Technical field
The present invention relates to a kind of preparation technology of biphenyl-benzyl dichloride, belongs to technical field of chemical synthesis.
Background technology
Biphenyl-benzyl dichloride, also known as 4,4 '-dichloromethyl biphenyl, molecular formula C14C12Cl2, relative molecular weight 251, fusing point
136 DEG C, 235 DEG C of boiling point, structural formula ﹕
Biphenyl-benzyl dichloride be synthesize Stilbene-based Fluorescent Brighteners (CBS-X) and plastics brightening agent CBS-127 etc. it is important in
Mesosome, and medicine intermediate 4, the raw material of 4 '-'-bis (hydroxymethyl) biphenyl, the purity of biphenyl-benzyl dichloride directly influence synthesized production
The quality of quality.
The synthesis technique of biphenyl-benzyl dichloride, currently generally use using biphenyl, paraformaldehyde as raw material, in catalyst both at home and abroad
In the presence of zinc chloride, synthesized by Blanc chloromethylations.In building-up process, it is necessary to which chlorination is continuously provided
Hydrogen, because paraformaldehyde is excessive in the synthetic reaction, in the reaction of chloromethylation, actual participation reaction is first
Aldehyde monomer and H+With reference to monomer, because catalyst zinc chloride is very sensitive to water, and chlorination zinc concentration is got in reaction system
Height is more advantageous to the generation of chloromethylation, therefore we can not possibly add substantial amounts of hydrochloric acid so that paraformaldehyde is complete in reaction
Complete sufficiently hydrolysis and and H+The paraformaldehyde of hydrolyzed amount is much not enough to reference to, the hydrochloric acid in initial reaction liquid, and with
The carry out H of reaction+As consumption concentration gradually reduces, the protonation concentration of formaldehyde for causing to participate in reacting also decreases, to mesh
Mark product synthesis it is unfavorable, therefore be continuously passed through hydrogen chloride gas smoothly efficiently carried out as the synthetic reaction it is important
Condition.Many Que Dian ﹕ such as catalyst zinc chloride in the synthesis technique of biphenyl-benzyl dichloride at present be present and sulfuric acid dosage is very big, after
There is certain potential safety hazard in phase zinc chloride, industrial application degree is low with retrieval of sulfuric acid processing；Caused intermediate product
Dichlormethyl ether is strong carcinogen, volatile pollution environment, human body is damaged after suction；Biphenyl-benzyl dichloride yield is low etc..
The content of the invention
It is an object of the invention to：There is provided that a kind of equipment investment is few, production cost is low, and product yield is high, purity is good, system
Standby technique is green；Can effectively it avoid using the strong carcinogenic intermediate product of generation during formaldehyde direct synthesis, waste gas, waste water
The preparation technology of the big biphenyl-benzyl dichloride of discharge capacity.
The technical scheme is that：
A kind of preparation technology of biphenyl-benzyl dichloride, it is characterised in that：Comprise the following steps：
1）, first respectively by concentrated hydrochloric acid, chlorosulfuric acid is placed in the hydrochloric acid head tank above synthesis reactor and chlorosulfuric acid head tank；Again by vinegar
Acid, thiacyclohexane are put into synthesis reactor, and 15 are stirred after anhydrous zinc chloride, paraformaldehyde and biphenyl are then sequentially added in synthesis reactor again
Min, the speed of agitator in synthesis reactor is 80r/min；The acetic acid that is added, thiacyclohexane, anhydrous zinc chloride, concentrated hydrochloric acid, chlorosulfuric acid,
The mass ratio of paraformaldehyde and biphenyl is the ﹕ 0.7 of 0.64 ﹕ 1.02：The ﹕ 1 of 0.29 ﹕, 0.7 ﹕ 0.39；
2）, after the completion of mixed material stirring in synthesis reactor, by hydrochloric acid head tank and chlorosulfuric acid head tank into synthesis reactor it is same
When concentrated hydrochloric acid and chlorosulfuric acid is added dropwise, a small amount of hydrogen chloride gas is recycled by device for absorbing tail gas, in synthesis reactor
Temperature control is between 25~30 DEG C, and for Stress control between 0~0.01MPa, the reaction time is 5~7h；
3）, when sampling analysis biphenyl concentration be less than 0.2% and the benzyl chloride concentration of biphenyl one be less than 2% when simultaneously stop be added dropwise concentrated hydrochloric acid and
Chlorosulfuric acid, it then will be synthesized by steam and material in synthesis reactor be subjected to insulation reaction after temperature in the kettle is warming up to 40~50 DEG C
2h, 30min is stood after the completion of insulation reaction；
4）, after the completion of standing, lower floor's inorganic phase solution is recycled by retrieval of sulfuric acid groove, then into synthesis reactor plus
Enter concentration and be 20% sodium carbonate liquor, and then the pH value of material in synthesis reactor is adjusted to pH=6-7；
5）, after the completion of the neutralization reaction in synthesis reactor, will be synthesized between temperature in the kettle is warming up to 80~90 DEG C, adopted by steam
Go out after thiacyclohexane to condense through condenser with air-distillation and reclaim；
6）, after distillation, when synthesizing temperature in the kettle and being cooled to 40 DEG C, add dichloromethane and by material stirring 30min, close
Speed of agitator into kettle is 80r/min, is evacuated to material in continuous washing kettle by compression pump after stirring；
7）, the material that is evacuated in continuous washing kettle add shower water in 1 ﹕ 2 ratio and washed, mixed material after the completion of washing
Out of, continuous washing kettle middle part overflow to layering tower, upper strata aqueous phase enters wastewater trough and carries out waste water recycling device, and lower floor is organic
Mutually enter through intermediate storage tank and carried out in distillation still air-distillation 3-4 hours, distillation temperature in the kettle is 40-50 DEG C, is distilled out
Enter flux bath after the condensed device condensation of dichloromethane and carry out recycling, remaining material is that biphenyl-benzyl dichloride is thick in distillation still
Product；
8）, will in the interlayer of crystallization kettle full of -10 DEG C concentration be 80% calcium chloride solution, open distillation still bottom valve, will
Biphenyl-benzyl dichloride crude product in above-mentioned distillation still, which is transferred in crystallization kettle, carries out crystallisation by cooling 4 hours, and crystallization temperature in the kettle is 0-
10 DEG C, crystallization time is 4 hours, and the biphenyl-benzyl dichloride crude product after crystallisation by cooling, which is transferred in centrifuge, carries out centrifugal treating, from
Scheming rotating speed is 60 r/min, isolated biphenyl-benzyl dichloride wet product, biphenyl-benzyl dichloride wet product is transferred in chuck and is filled with 90
It is 0.06MPa negative pressure dryings that vacuum is carried out in the drying machine of DEG C hot water, produces biphenyl-benzyl dichloride finished product.
Described concentrated hydrochloric acid and the rate of addition of chlorosulfuric acid are respectively 33Kg/ hours and 78Kg/ hours.
Described concentrated hydrochloric acid, chlorosulfuric acid, acetic acid, thiacyclohexane, anhydrous zinc chloride, the concentration of paraformaldehyde and biphenyl are respectively
35%、99%、99%、99%、99%、99%、99%。
By process above production biphenyl-benzyl dichloride, its yield is 92%, and its product design is 98.0%.
The chemical equation of above-mentioned technique for example Xias ﹕
The beneficial effect Yu ﹕ of the present invention compared with prior art
In the preparation technology of the biphenyl-benzyl dichloride, chlorosulfuric acid reacts with the water in concentrated hydrochloric acid generates hydrogen chloride gas, generation
Hydrogen chloride gas cause the synthetic reaction is positive to carry out, the synthetic reaction be exothermic reaction, liberated heat promotion concentrated hydrochloric acid
Middle hydrogen chloride gas separate out from solution participates in synthetic reaction, is continuously passed through so as to reach for the synthetic reaction
The purpose of hydrogen chloride gas so that the high income of biphenyl-benzyl dichloride.Chlorosulfuric acid and an accessory substance sulfuric acid part for water reaction generation
Promote the generation of biphenyl-benzyl dichloride as the synthesis reaction catalyst, another part sulfuric acid through retrieval of sulfuric acid groove recycling,
Whole set process is economic and environment-friendly, and hydrogen chloride gas is prepared and completed in same synthesis reactor；Avoid hydrogen chloride gas in the prior art
Prepared by body need hcl reaction kettle and by-product recovery device, and low yield, the problem of easily causing environmental pollution.The biphenyl dichloro
It is whole raw that the preparation technology of benzyl only needs a set of synthesis reactor, washing kettle, layering tower, distillation still, crystallization kettle and centrifuge just to complete
Production. art, production equipment is saved, reduced production cost.
The synthesis material of the preparation technology of the biphenyl-benzyl dichloride distills crystallization after being layered by successive washing, instead of biography
System method is first added in buck using the operating method of one-pot repetition washing layering and is synthesized material and then pass through stratification
The method for reheating water stratification again afterwards is handled；The successive washing layered shaping process both saves manpower, saves again
Time, production efficiency is improved, and successive washing kettle is simple in construction, operation is easy, and sewage load is few, and processing cost is low.
The preparation technology of the biphenyl-benzyl dichloride is produced in the reaction system of hydrogen chloride gas not using chlorosulfuric acid and concentrated hydrochloric acid
Can only zinc chloride catalyst be set to be dissolved in wherein, while form mixed catalyst with catalyst acetic acid to make whole reaction in acidity
In atmosphere, paraformaldehyde can be efficiently dissociated, obtains formaldehyde and and H+With reference to, and then reaction is participated in, and add reaction
The contact probability of thing and catalyst zinc chloride, accelerate the speed of reaction.Use of the thiacyclohexane as phase transfer catalyst so that
The zinc chloride being dissolved in concentrated hydrochloric acid fully contacts with organic phase biphenyl, equally there is the effect for accelerating reaction rate.
Embodiment
With reference to specific embodiment, the invention will be further described, and the invention is not restricted to embodiment, embodiments thereof
It can be any mode described in the content of the invention.
Embodiment 1
The concentrated hydrochloric acid that concentration is 35%, 99% chlorosulfuric acid are placed on synthesis reactor by a kind of Zhi of biphenyl-benzyl dichloride respectively for Gong Yi ﹕
In the hydrochloric acid head tank and chlorosulfuric acid head tank of side；Then by concentration be 99% acetic acid, 99% thiacyclohexane be put into synthesis reactor,
Then concentration is sequentially added to stir 15 min, synthesis reactor after 99% anhydrous zinc chloride, 99% paraformaldehyde and 99% biphenyl
The speed of agitator of interior mixed material is 80r/min；The acetic acid that is added, thiacyclohexane, anhydrous zinc chloride, concentrated hydrochloric acid, chlorosulfuric acid,
The mass ratio of paraformaldehyde and biphenyl is the ﹕ 0.7 of 0.64 ﹕ 1.02：The ﹕ 1 of 0.29 ﹕, 0.7 ﹕ 0.39；.The dropwise addition of concentrated hydrochloric acid and chlorosulfuric acid
Speed is controlled as 33Kg/ hours, 78Kg/ hours.After the completion of mixed material stirring in synthesis reactor, pass through hydrochloric acid head tank
The concentrated hydrochloric acid and 99% chlorosulfuric acid that concentration is 35% is added dropwise simultaneously into synthesis reactor with chlorosulfuric acid head tank, by a small amount of hydrogen chloride
Gas is recycled by device for absorbing tail gas, and temperature control is 25 DEG C in synthesis reactor, when Stress control is 0Pa, reaction
Time is 5h.Stopping dropwise addition concentration simultaneously when sampling analysis biphenyl concentration is less than 0.2% and the benzyl chloride concentration of biphenyl one is less than 2% is
35% concentrated hydrochloric acid and 99% chlorosulfuric acid, then it will be synthesized material in synthesis reactor after temperature in the kettle is warming up to 40 DEG C by steam
Insulation reaction 2h is carried out, 30min is stood after the completion of insulation reaction.After 30min is stood, lower floor's inorganic phase solution is returned by sulfuric acid
Receive groove to be recycled, the sodium carbonate liquor that concentration is 20% is then added into synthesis reactor, and then by material pH in synthesis reactor
Value is adjusted to pH=6-7.After pH=6-7 in synthesis reactor, 80 DEG C are warming up to by temperature in the kettle is synthesized by steam, is steamed using normal pressure
Reclaimed after distillating thiacyclohexane through condenser condensation.After distillation, when synthesis temperature in the kettle is cooled to 40 DEG C, dichloromethane is added
Alkane and by material stirring 30min, the speed of agitator of synthesis reactor is 80r/min, is evacuated to material by compression pump after stirring
In continuous washing kettle.The material being evacuated in continuous washing kettle adds shower water in 1 ﹕ 2 ratio and washed, and is mixed after the completion of washing
Out of, continuous washing kettle middle part overflow to layering tower, upper strata aqueous phase enters wastewater trough and carries out waste water recycling device compound material, under
Layer organic phase enters through intermediate storage tank carries out air-distillation 3 hours in distillation still, distillation temperature in the kettle is 40 DEG C, is distilled out
Enter flux bath after the condensed device condensation of dichloromethane and carry out recycling, remaining material is that biphenyl-benzyl dichloride is thick in distillation still
Product.- 10 DEG C of 80% calcium chloride solution will be full of in the interlayer of crystallization kettle, distillation still bottom valve be opened, by above-mentioned distillation still
Biphenyl-benzyl dichloride crude product be transferred in crystallization kettle and carry out crystallisation by cooling 4 hours, crystallization temperature in the kettle is 0-10 DEG C, crystallization time
For 4 hours, the biphenyl-benzyl dichloride crude product after crystallisation by cooling, which is transferred in centrifuge, carried out centrifugal treating, centrifuge speed 60
R/min, separate, biphenyl-benzyl dichloride wet product, biphenyl-benzyl dichloride wet product is transferred to the drying machine that 90 DEG C of hot water are filled with chuck
Interior progress vacuum is 0.06MPa negative pressure dryings, is obtained, biphenyl-benzyl dichloride finished product.The reaction equation Wei ﹕ of reaction above
。
Embodiment 2
The concentrated hydrochloric acid that concentration is 35%, 99% chlorosulfuric acid are placed on synthesis reactor by a kind of Zhi of biphenyl-benzyl dichloride respectively for Gong Yi ﹕
In the hydrochloric acid head tank and chlorosulfuric acid head tank of side；Then by concentration be 99% acetic acid, 99% thiacyclohexane be put into synthesis reactor,
Then 15 min are stirred after sequentially adding anhydrous zinc chloride, 99% paraformaldehyde and 99% biphenyl that concentration is 99%, are synthesized
The speed of agitator of mixed material in kettle is 80r/min；Acetic acid, thiacyclohexane, anhydrous zinc chloride, concentrated hydrochloric acid, the sulfonyl added
The mass ratio of chlorine, paraformaldehyde and biphenyl is the ﹕ 0.7 of 0.64 ﹕ 1.02：The ﹕ 1 of 0.29 ﹕, 0.7 ﹕ 0.39；The drop of concentrated hydrochloric acid and chlorosulfuric acid
Acceleration is controlled as 33Kg/ hours, 78Kg/ hours.It is high-order by hydrochloric acid after the completion of mixed material stirring in synthesis reactor
The concentrated hydrochloric acid and 99% chlorosulfuric acid that concentration is 35% are added dropwise into synthesis reactor with chlorosulfuric acid head tank simultaneously for groove, by a small amount of chlorination
Hydrogen is recycled by device for absorbing tail gas, and temperature control is at 30 DEG C in synthesis reactor, and Stress control is in 0.005MPa
Between, reaction time 6h；Stop simultaneously when sampling analysis biphenyl concentration is less than 0.2% and the benzyl chloride concentration of biphenyl one is less than 2%
The concentrated hydrochloric acid and 99% chlorosulfuric acid that concentration is 35% is added dropwise, then will be synthesized after temperature in the kettle is warming up to 45 DEG C by steam to close
Material carries out insulation reaction 2h in into kettle, and 30min is stood after the completion of insulation reaction.After 30min is stood, lower floor's inorganic phase solution
Recycled by retrieval of sulfuric acid groove, the sodium carbonate liquor that concentration is 20% is then added into synthesis reactor, and then will synthesis
Material pH value is adjusted to pH=6-7 in kettle；As pH=6-7 in synthesis reactor, 85 DEG C are warming up to by temperature in the kettle is synthesized by steam,
Go out after thiacyclohexane to condense through condenser using air-distillation and reclaim.After distillation, when synthesis temperature in the kettle is cooled to 40 DEG C,
Add dichloromethane and by material stirring 30min, the speed of agitator of synthesis reactor is 80r/min, passes through material after stirring
Compression pump is evacuated in continuous washing kettle.The material being evacuated in continuous washing kettle adds shower water in 1 ﹕ 2 ratio and washed, water
Out of, continuous washing kettle middle part overflow to layering tower, upper strata aqueous phase enters wastewater trough and carries out waste water time mixed material after the completion of washing
Receipts processing, lower floor's organic phase enters through intermediate storage tank carries out air-distillation 4 hours in distillation still, distillation temperature in the kettle is 45
DEG C, enter flux bath after the condensed device condensation of dichloromethane distilled out and carry out recycling, remaining material is in distillation still
Biphenyl-benzyl dichloride crude product；Be 80% calcium chloride solution by -10 DEG C of concentration is full of in the interlayer of crystallization kettle, opening distillation still bottom
Valve, the biphenyl-benzyl dichloride crude product in above-mentioned distillation still is transferred in crystallization kettle and carries out crystallisation by cooling 4 hours, it is warm in crystallization kettle
Spend for 0-10 DEG C, crystallization time is 4 hours, and the biphenyl-benzyl dichloride crude product after crystallisation by cooling, which is transferred in centrifuge, to be carried out at centrifugation
Reason, centrifuge speed is 60 r/min, separates, biphenyl-benzyl dichloride wet product, biphenyl-benzyl dichloride wet product is transferred in chuck and filled
It is 0.06MPa negative pressure dryings to enter to carry out vacuum in the drying machine of 90 DEG C of hot water, is obtained, biphenyl-benzyl dichloride finished product.React above
Reaction equation is the same as embodiment 1.
Embodiment 3
The concentrated hydrochloric acid that concentration is 35%, 99% chlorosulfuric acid are placed on synthesis reactor by a kind of Zhi of biphenyl-benzyl dichloride respectively for Gong Yi ﹕
In the hydrochloric acid head tank and chlorosulfuric acid head tank of side；Then by concentration be 99% acetic acid, 99% thiacyclohexane be put into synthesis reactor,
Then 15 min are stirred after sequentially adding anhydrous zinc chloride, 99% paraformaldehyde and 99% biphenyl that concentration is 99%, are synthesized
The speed of agitator of mixed material in kettle is 80r/min；Acetic acid, thiacyclohexane, anhydrous zinc chloride, concentrated hydrochloric acid, the sulfonyl added
The mass ratio of chlorine, paraformaldehyde and biphenyl is the ﹕ 0.7 of 0.64 ﹕ 1.02：The ﹕ 1 of 0.29 ﹕, 0.7 ﹕ 0.39；The drop of concentrated hydrochloric acid and chlorosulfuric acid
Acceleration is controlled as 33Kg/ hours, 78Kg/ hours.It is high-order by hydrochloric acid after the completion of mixed material stirring in synthesis reactor
The concentrated hydrochloric acid and 99% chlorosulfuric acid that concentration is 35% are added dropwise into synthesis reactor with chlorosulfuric acid head tank simultaneously for groove, by a small amount of chlorination
Hydrogen is recycled by device for absorbing tail gas, in synthesis reactor temperature control at 30 DEG C, Stress control in 0.01MPa,
Reaction time is 7h.When sampling analysis biphenyl concentration is less than 0.2% and the benzyl chloride concentration of biphenyl one is less than 2% simultaneously stop being added dropwise it is dense
The concentrated hydrochloric acid and 99% chlorosulfuric acid for 35% are spent, then will be synthesized in synthesis reactor after temperature in the kettle is warming up to 50 DEG C by steam
Material carries out insulation reaction 2h, and 30min is stood after the completion of insulation reaction.After the completion of standing, lower floor's inorganic phase solution passes through sulphur
Acid recovery groove is recycled, and the sodium carbonate liquor that concentration is 20% is then added into synthesis reactor, and then by thing in synthesis reactor
Matter pH value is adjusted to pH=6-7；As pH=6-7 in synthesis reactor, by steam will synthesize temperature in the kettle be warming up to 90 DEG C when, use
Air-distillation goes out after thiacyclohexane condenses recovery through condenser.After distillation, when synthesis temperature in the kettle is cooled to 40 DEG C, add
Dichloromethane and by material stirring 30min, the speed of agitator of synthesis reactor is 80r/min, and material is passed through into pressure after stirring
In pumping to continuous washing kettle.The material being evacuated in continuous washing kettle adds shower water in 1 ﹕ 2 ratio and washed, and has washed
Into rear mixed material out of, continuous washing kettle middle part overflow to layering tower, upper strata aqueous phase enters wastewater trough and carried out at Sewage treatment
Reason, lower floor's organic phase enters through intermediate storage tank carries out air-distillation 4 hours in distillation still, distillation temperature in the kettle is 50 DEG C, is steamed
Enter flux bath after the condensed device condensation of dichloromethane distillated and carry out recycling, remaining material is biphenyl two in distillation still
Benzyl chloride crude product.Be 80% calcium chloride solution by -10 DEG C of concentration is full of in the interlayer of crystallization kettle, open distillation still bottom valve, general
Biphenyl-benzyl dichloride crude product in above-mentioned distillation still, which is transferred in crystallization kettle, carries out crystallisation by cooling 4 hours, and crystallization temperature in the kettle is 0-
10 DEG C, crystallization time is 4 hours, and the biphenyl-benzyl dichloride crude product after crystallisation by cooling, which is transferred in centrifuge, carries out centrifugal treating, from
Scheming rotating speed is 60 r/min, separates, biphenyl-benzyl dichloride wet product, biphenyl-benzyl dichloride wet product is transferred in chuck and is filled with 90 DEG C
It is 0.06MPa negative pressure dryings that vacuum is carried out in the drying machine of hot water, is obtained, biphenyl-benzyl dichloride finished product.The reaction side of reaction above
Formula is the same as embodiment 1.
Simply presently preferred embodiments of the present invention described above, the example above illustrate not make the substantive content of the present invention
Any formal limitation, technology of the person of an ordinary skill in the technical field after this specification has been read according to the present invention
Any simple modification or deformation that essence is made to above embodiment, and the technology contents possibly also with the disclosure above
The equivalent embodiment of equivalent variations is changed or is modified to, in the range of still falling within technical solution of the present invention, without departing from
The spirit and scope of the invention.
Claims (3)
1. a kind of preparation technology , of biphenyl-benzyl dichloride Qi Te signs Yu ﹕ Bao include Bu Zhou ﹕ under Yi
1）, first respectively by concentrated hydrochloric acid, chlorosulfuric acid is placed in the hydrochloric acid head tank above synthesis reactor and chlorosulfuric acid head tank；Again by vinegar
Acid, thiacyclohexane are put into synthesis reactor, and 15 are stirred after anhydrous zinc chloride, paraformaldehyde and biphenyl are then sequentially added in synthesis reactor again
Min, the speed of agitator in synthesis reactor is 80r/min；The acetic acid that is added, thiacyclohexane, anhydrous zinc chloride, concentrated hydrochloric acid, chlorosulfuric acid,
The mass ratio of paraformaldehyde and biphenyl is the ﹕ 0.7 of 0.64 ﹕ 1.02：The ﹕ 1 of 0.29 ﹕, 0.7 ﹕ 0.39；
2）, after the completion of mixed material stirring in synthesis reactor, by hydrochloric acid head tank and chlorosulfuric acid head tank into synthesis reactor it is same
When concentrated hydrochloric acid and chlorosulfuric acid is added dropwise, a small amount of hydrogen chloride gas is recycled by device for absorbing tail gas, in synthesis reactor
Temperature control is between 25~30 DEG C, and for Stress control between 0~0.01MPa, the reaction time is 5~7h；
3）, when sampling analysis biphenyl concentration be less than 0.2% and the benzyl chloride concentration of biphenyl one be less than 2% when simultaneously stop be added dropwise concentrated hydrochloric acid and
Chlorosulfuric acid, it then will be synthesized by steam and material in synthesis reactor be subjected to insulation reaction after temperature in the kettle is warming up to 40~50 DEG C
2h, 30min is stood after the completion of insulation reaction；
4）, after the completion of standing, lower floor's inorganic phase solution is recycled by retrieval of sulfuric acid groove, then into synthesis reactor plus
Enter concentration and be 20% sodium carbonate liquor, and then the pH value of material in synthesis reactor is adjusted to pH=6-7；
5）, after the completion of the neutralization reaction in synthesis reactor, will be synthesized between temperature in the kettle is warming up to 80~90 DEG C, adopted by steam
Go out after thiacyclohexane to condense through condenser with air-distillation and reclaim；
6）, after distillation, when synthesizing temperature in the kettle and being cooled to 40 DEG C, add dichloromethane and by material stirring 30min, close
Speed of agitator into kettle is 80r/min, is evacuated to material in continuous washing kettle by compression pump after stirring；
7）, the material that is evacuated in continuous washing kettle add shower water in 1 ﹕ 2 ratio and washed, mixed material after the completion of washing
Out of, continuous washing kettle middle part overflow to layering tower, upper strata aqueous phase enters wastewater trough and carries out waste water recycling device, and lower floor is organic
Mutually enter through intermediate storage tank and carried out in distillation still air-distillation 3-4 hours, distillation temperature in the kettle is 40-50 DEG C, is distilled out
Enter flux bath after the condensed device condensation of dichloromethane and carry out recycling, remaining material is that biphenyl-benzyl dichloride is thick in distillation still
Product；
8）, will in the interlayer of crystallization kettle full of -10 DEG C concentration be 80% calcium chloride solution, open distillation still bottom valve, will
Biphenyl-benzyl dichloride crude product in above-mentioned distillation still, which is transferred in crystallization kettle, carries out crystallisation by cooling 4 hours, and crystallization temperature in the kettle is 0-
10 DEG C, crystallization time is 4 hours, and the biphenyl-benzyl dichloride crude product after crystallisation by cooling, which is transferred in centrifuge, carries out centrifugal treating, from
Scheming rotating speed is 60 r/min, isolated biphenyl-benzyl dichloride wet product, biphenyl-benzyl dichloride wet product is transferred in chuck and is filled with 90
It is 0.06MPa negative pressure dryings that vacuum is carried out in the drying machine of DEG C hot water, produces biphenyl-benzyl dichloride finished product.
2. concentrated hydrochloric acid and sulphur described in a kind of preparation technology , of biphenyl-benzyl dichloride according to claim 1 Qi Te sign Yu ﹕
The rate of addition of acyl chlorides is respectively 33Kg/ hours and 78Kg/ hours.
3. concentrated hydrochloric acid, sulphur described in a kind of preparation technology , of biphenyl-benzyl dichloride according to claim 1 Qi Te sign Yu ﹕
Acyl chlorides, acetic acid, thiacyclohexane, anhydrous zinc chloride, the concentration of paraformaldehyde and biphenyl are respectively 35%, 99%, 99%, 99%, 99%,
99%、99%。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
| CN112979591A (en) * | 2021-03-01 | 2021-06-18 | 安徽金轩科技有限公司 | Oxidation extraction process for recycling dichloromethane in preparation of furan ammonium salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
| CN112573993B (en) * | 2020-11-20 | 2023-03-14 | 河北星宇化工有限公司 | Production process of 4,4' -dichloromethyl biphenyl |
| CN112979591A (en) * | 2021-03-01 | 2021-06-18 | 安徽金轩科技有限公司 | Oxidation extraction process for recycling dichloromethane in preparation of furan ammonium salt |
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| CN107473927B (en) | 2020-06-02 |
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