CN108046975A - A kind of preparation method of biphenyl - Google Patents
A kind of preparation method of biphenyl Download PDFInfo
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- CN108046975A CN108046975A CN201711445924.2A CN201711445924A CN108046975A CN 108046975 A CN108046975 A CN 108046975A CN 201711445924 A CN201711445924 A CN 201711445924A CN 108046975 A CN108046975 A CN 108046975A
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- kettle
- biphenyl
- toluene
- reaction
- triphenylphosphine
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 86
- 239000004305 biphenyl Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 135
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 94
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 25
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 238000010792 warming Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009413 insulation Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012044 organic layer Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000013517 stratification Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 31
- 238000004064 recycling Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 125000006267 biphenyl group Chemical group 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000011105 stabilization Methods 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- -1 hydrogen furans Chemical class 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012065 filter cake Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 239000002932 luster Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000010009 beating Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OCAPBUJLXMYKEJ-UHFFFAOYSA-N 1-[biphenyl-4-yl(phenyl)methyl]imidazole Chemical compound C1=NC=CN1C(C=1C=CC(=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 OCAPBUJLXMYKEJ-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 229960002206 bifonazole Drugs 0.000 description 1
- QRZAKQDHEVVFRX-UHFFFAOYSA-N biphenyl-4-ylacetic acid Chemical compound C1=CC(CC(=O)O)=CC=C1C1=CC=CC=C1 QRZAKQDHEVVFRX-UHFFFAOYSA-N 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 229960000192 felbinac Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of biphenyl, include the following steps：(1) mixed liquor that chlorobenzene, toluene and tetrahydrofuran are prepared is squeezed into head tank；(2) magnesium chips is thrown to grignard reaction kettle, adds a small amount of mixed liquor, trigger grignard reaction, then residual mixed liquor is added dropwise, insulation reaction；(3) reaction solution is pressed into kettle of formatting, phosphine tri chloride, insulation reaction is added dropwise；(4) centrifuge mother liquor carries out being distilled to recover THF/ toluene, to residue plus toluene, material is transferred in layering kettle, dilute hydrochloric acid solution, stratification is added dropwise；(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent, and salvage stores adds methanol, is warming up to reflux, is cooled to room temperature, and centrifuges；Mother liquor is distilled to recover methanol and applies mechanically, and filter cake obtains biphenyl and triphenylphosphine in melting rectifying separation after heating in tank.Advantages of the present invention is：Biphenyl is prepared using by-product in triphenylphosphine preparation process, whole making time, energy and the cost of producer is greatly saved.
Description
Technical field
The present invention relates to field of compound preparation more particularly to a kind of preparation methods of biphenyl.
Background technology
Biphenyl is important medicine intermediate, be Meike, inspire confidence in fine jade, Bifonazole cream must be lied prostrate, must fluorine that azoles, hydroxyl is joined
Benzene, the primary raw material to the medicine such as bromo biphenyl, biphenyl dichloro resin, felbinac.Meanwhile biphenyl is widely used in high-tech
Field, the supplementary material produced such as electronic liquid crystal screen, lithium battery, fluorescent whitening agent.In chemical field, it is high-grade to be mainly used in production
The products such as heat carrier (conduction oil), fine-chemical intermediate, pesticide intermediate and daily use chemicals.
At present, the domestic market demand amount of biphenyl is ten thousand tons/year of 2-3, and with average annual 10% increasing rate；International market
Demand is about ten thousand tons/year of 7-10, domestic only 6000-8000 tons/year of biphenyl yield.Most of biphenyl, particularly high-end production
Product rely on import.Presently, domestic market notch is larger, good market prospect.
At present, the synthesis of biphenyl mainly uses purified petroleum benzin catalytic pyrolysis synthesis technology；The synthesis technology is specially to prepare biphenyl
Special process, the preparation of biphenyl needs regular hour, energy and cost.
Therefore, it is badly in need of a kind of by-product using in other compound preparation process at present further to prepare biphenyl
Method so that go specially to prepare biphenyl without in addition expending time, energy and cost, the entirety of producer can be greatlyd save
Making time, energy and cost.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind can greatly save whole making time,
The method for preparing biphenyl using by-product in triphenylphosphine preparation process of energy and cost.
The present invention is achieved by the following technical solutions：A kind of preparation method of biphenyl, includes the following steps：
(1) chlorobenzene, toluene and tetrahydrofuran THF for squeezing into certain proportional quantity with pump in the mixing kettle of workshop prepare total amount
For the mixed liquor of 4000-5000kg, beat Xun Huan with pump and be uniformly mixed, mixed liquor is squeezed into head tank；
(2) 100-200kg magnesium chips is put by feeder for solid materials into 4500-5500L grignard reaction kettles, opens nitrogen and protect
Then shield adds the mixed liquor that 350-450kg steps (1) obtain by head tank；50-60 DEG C of initiation grignard reaction of heating, then
100-110 DEG C is warming up to again, and residual mixed liquor, completion of dropwise addition are slowly added dropwise in 4.5-5.5h by head tank at this temperature
Afterwards in 100-110 DEG C of insulation reaction 4.5-5.5h；To the end of grignard reaction, sampling detection and analysis grignard content；
(3) after sampling detection is qualified, reaction solution press-in 4500-5500L in grignard reaction kettle is formatted kettle using nitrogen
It is interior, less than 80 DEG C are cooled to, 240-280kg phosphine tri chlorides are slowly added dropwise in 2.5-3.5h by head tank into Grignard solution,
Temperature is controlled after completion of dropwise addition at 40-50 DEG C, insulation reaction 4.5-5.5h；It treats after reaction, ON cycle water makes reaction solution
Room temperature is cooled to, is centrifuged；
(4) centrifuge mother liquor is pumped to 2500-3500L concentration kettles and carries out being distilled to recover THF/ toluene, and recycling design is applied mechanically, to
Toluene dissolving is added in residue, material is transferred to the 2.5-3.5% dilute hydrochloric acid water that 350-450kg is slowly added dropwise in layering kettle
Solution, stratification；
(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent to doing, recycling toluene is applied mechanically, remaining in kettle
Material adds 1000-2000kg methanol, is warming up to 105-115 DEG C of reflux, is cooled to room temperature, and centrifugation, mother liquor is distilled to recover methanol set
With filter cake is the crude product containing triphenylphosphine and diphenyl mixture；By the crude product containing triphenylphosphine and diphenyl mixture in melting tank
It is transferred to after interior heating in rectifying still and carries out rectifying separation, obtain biphenyl and triphenylphosphine.
One of preferred embodiment as the present invention, the mass ratio of chlorobenzene, toluene and tetrahydrofuran is 1 in the step (1)：
(2-2.5)：(3.1-3.2).
One of preferred embodiment as the present invention, the mass ratio of chlorobenzene, toluene and tetrahydrofuran is specific in the step (1)
For 1：2.28：3.14.
One of preferred embodiment as the present invention, the step (2) is middle to detect grignard content using analysis by titration.
One of preferred embodiment as the present invention, the qualified standard of the middle sampling detection of the step (3) are big for grignard content
In 20%.
One of preferred embodiment as the present invention, the step (4) is middle to be distilled to recover THF/ in centrifuge mother liquor and cleaning solution
The specific method of toluene is：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105-115 DEG C, begins to boil off,
It is received back after being condensed again by condenser and receives THF/ toluene.
One of preferred embodiment as the present invention, the middle specific method for being distilled to recover toluene in organic layer of the step (5)
For：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105-115 DEG C, begins to boil off, then is condensed by condenser
After be received back receipts toluene.
One of preferred embodiment as the present invention, the middle specific side for being distilled to recover methanol in centrifuge mother liquor of the step (5)
Method is：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105-115 DEG C, begins to boil off, then cold by condenser
Receipts methanol is received back after solidifying.
One of preferred embodiment as the present invention, by the crude product containing triphenylphosphine and diphenyl mixture in the step (5)
The progress separated specific method of rectifying in rectifying still is transferred to after being heated in melting tank is：Triphenylphosphine and diphenyl mixture will be contained
Crude product input melt tank in, be warming up to 80-100 DEG C, after material melting, open stirring, while decompression steam it is therein low
It boil-off dose, can not treat liquid, stop stirring, be transferred to rectifying still；Vacuum pump set is opened, after vacuum stabilization, heat up rectifying, according to
Secondary collection biphenyl, mixed fraction and triphenylphosphine.
The present invention compared with prior art the advantages of be：
(1) for exclusively for the technical process for preparing biphenyl and setting, the present invention utilizes triphenylphosphine preparation process
By-product in the process prepares biphenyl, goes specially to prepare biphenyl without in addition expending time, energy and cost, can save significantly
Save whole making time, energy and the cost of producer；
(2) present invention be prepared biphenyl high income, purity is good, color and luster is good；
(3) utilization rate of raw material of the present invention to being used in technical process is high, and the toluene to being introduced in technical process, first
Alcohol etc. is handled using rational recovery process, and green, environmental protection influence minimum caused by environment.
Description of the drawings
Fig. 1 is the integrated artistic flow chart of the preparation method of the biphenyl and triphenylphosphine in embodiment 1-3.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of biphenyl of the present embodiment is straight as source using the by-product in triphenylphosphine preparation process
It obtains.Wherein, as shown in Figure 1, triphenylphosphine preparation process comprises the following specific steps that：
(1) mass ratio is squeezed into as 1 with pump in the mixing kettle of workshop：2：3.1 chlorobenzene, toluene and tetrahydrofuran THF is prepared
Total amount is the mixed liquor of 4000kg, and beating Xun Huan with pump is uniformly mixed, and mixed liquor is squeezed into head tank；
(2) 100kg magnesium chips is put by feeder for solid materials into 4500L grignard reaction kettles, opens nitrogen protection, Ran Houtong
Cross the mixed liquor that head tank adds 350kg steps (1) to obtain；50 DEG C of initiation grignard reactions of heating, reaction equation are as follows：
Then, then 100 DEG C are warming up to, residual mixed liquor is slowly added dropwise in 4.5h by head tank at this temperature, dripped
In 100 DEG C of insulation reaction 4.5h after adding；
To the end of grignard reaction, sampled using analysis by titration and detect and analyze its grignard content；
(3) when the testing result of sample shows as grignard content more than 20%, confirm that it is qualified；It then, will using nitrogen
Reaction solution press-in 4500L formats in kettle in grignard reaction kettle, less than 80 DEG C is cooled to, into Grignard solution by head tank in 2.5h
240kg phosphine tri chlorides are inside slowly added dropwise, temperature is controlled after completion of dropwise addition, and reaction equation is as follows at 40 DEG C, insulation reaction 4.5h：
It treats after reaction, ON cycle water makes reaction solution be cooled to 24 DEG C of room temperature, centrifugation；
(4) centrifuge mother liquor is pumped to 2500L concentration kettles and carries out being distilled to recover THF/ toluene that (recycling kettle chuck leads to steam heating
Heating, treats that temperature in the kettle rises to 105 DEG C, begins to boil off, then is received back after being condensed by condenser and receives THF/ toluene), recycling is molten
Agent is applied mechanically, and toluene dissolving is added in into residue, and material is transferred to the 2.5% dilute hydrochloric acid water that 350kg is slowly added dropwise in layering kettle
Solution, stratification；
(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent and (recycles kettle chuck to dry and lead to steam heating liter
Temperature is treated that temperature in the kettle rises to 105 DEG C, is begun to boil off, then is received back after being condensed by condenser and receives toluene), recycling toluene is applied mechanically,
Salvage stores adds 1000kg methanol in kettle, is warming up to 105 DEG C of reflux, is cooled to room temperature, and centrifugation, mother liquor is distilled to recover methanol and applies mechanically
(recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105 DEG C, begins to boil off, then is received after being condensed by condenser
Recycle methanol), filter cake is the crude product containing triphenylphosphine and diphenyl mixture；
It is melted being put into containing the crude product of triphenylphosphine and diphenyl mixture in tank, is warming up to 80 DEG C, after material melting, opens
Stirring is opened, while decompression steams low boiling solvent therein, can not treat liquid, stops stirring, is transferred to rectifying still；Open vacuum machine
Group, after vacuum stabilization, heat up rectifying, collects by-product biphenyl, mixed fraction and index parameter target as shown in Table 1 successively
Product triphenylphosphine.
The triphenylphosphine index parameter of 1 embodiment 1 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White powder or flaky crystal |
| 2 | Purity | ＞ 99.5% |
| 3 | Loss on drying | ≤ 98% |
Above-mentioned triphenylphosphine preparation process uses improved grignard reaction technique, and process, stabilization are easy to operate,
The target product triphenylphosphine that high income, purity are good, color and luster is good can not only be quickly obtained, moreover it is possible to obtain biphenyl this by-product；
In addition, in entire technical process, it is not only high to the utilization rate of raw material, and toluene, tetrahydrofuran, first to being introduced in technical process
Alcohol etc. applies mechanically processing, green, environmental protection using distillation recovery.
Based on above-mentioned triphenylphosphine preparation process, the direct barrelling bag of by-product biphenyl that the present embodiment obtains step (5)
Dress, it is final to obtain index parameter biphenyl finished product as shown in Table 2.Wherein, the acquisition reaction equation of by-product biphenyl is as follows：
The biphenyl index parameter of 2 embodiment 1 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White or yellowish flake-like crystal |
| 2 | Purity | ＞ 99% |
The present embodiment prepares biphenyl using the by-product in triphenylphosphine preparation process, compared with exclusively for preparation
Biphenyl and for the technical process that sets, go specially to prepare biphenyl without in addition expending time, energy and cost, can greatly save
Whole making time, energy and the cost of producer；In addition, the high income of the biphenyl finally obtained, purity are good, color and luster is good.
Embodiment 2
A kind of preparation method of biphenyl of the present embodiment is straight as source using the by-product in triphenylphosphine preparation process
It obtains.Wherein, as shown in Figure 1, triphenylphosphine preparation process comprises the following specific steps that：
(1) mass ratio is squeezed into as 1 with pump in the mixing kettle of workshop：2.5：3.2 chlorobenzene, toluene and tetrahydrofuran THF is matched somebody with somebody
Total amount processed is the mixed liquor of 5000kg, and beating Xun Huan with pump is uniformly mixed, and mixed liquor is squeezed into head tank；
(2) 200kg magnesium chips is put by feeder for solid materials into 5500L grignard reaction kettles, opens nitrogen protection, Ran Houtong
Cross the mixed liquor that head tank adds 450kg steps (1) to obtain；60 DEG C of initiation grignard reactions of heating, reaction equation are as follows：
Then, then 110 DEG C are warming up to, residual mixed liquor is slowly added dropwise in 5.5h by head tank at this temperature, dripped
In 110 DEG C of insulation reaction 5.5h after adding；
To the end of grignard reaction, sampled using analysis by titration and detect and analyze its grignard content；
(3) when the testing result of sample shows as grignard content more than 20%, confirm that it is qualified；It then, will using nitrogen
Reaction solution press-in 5500L formats in kettle in grignard reaction kettle, less than 80 DEG C is cooled to, into Grignard solution by head tank in 3.5h
280kg phosphine tri chlorides are inside slowly added dropwise, temperature is controlled after completion of dropwise addition, and reaction equation is as follows at 50 DEG C, insulation reaction 5.5h：
It treats after reaction, ON cycle water makes reaction solution be cooled to 26 DEG C of room temperature, centrifugation；
(4) centrifuge mother liquor is pumped to 3500L concentration kettles and carries out being distilled to recover THF/ toluene that (recycling kettle chuck leads to steam heating
Heating, treats that temperature in the kettle rises to 115 DEG C, begins to boil off, then is received back after being condensed by condenser and receives THF/ toluene), recycling is molten
Agent is applied mechanically, and toluene dissolving is added in into residue, and material is transferred to the 3.5% dilute hydrochloric acid water that 450kg is slowly added dropwise in layering kettle
Solution, stratification；
(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent and (recycles kettle chuck to dry and lead to steam heating liter
Temperature is treated that temperature in the kettle rises to 115 DEG C, is begun to boil off, then is received back after being condensed by condenser and receives toluene), recycling toluene is applied mechanically,
Salvage stores adds 2000kg methanol in kettle, is warming up to 115 DEG C of reflux, is cooled to room temperature, and centrifugation, mother liquor is distilled to recover methanol and applies mechanically
(recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 115 DEG C, begins to boil off, then is received after being condensed by condenser
Recycle methanol), filter cake is the crude product containing triphenylphosphine and diphenyl mixture；
It is melted being put into containing the crude product of triphenylphosphine and diphenyl mixture in tank, is warming up to 100 DEG C, after material melting,
Stirring is opened, while decompression steams low boiling solvent therein, can not treat liquid, stops stirring, is transferred to rectifying still；Open vacuum
Unit, after vacuum stabilization, heat up rectifying, collects by-product biphenyl, mixed fraction and index parameter mesh as shown in table 3 successively
Mark product triphenylphosphine.
The triphenylphosphine index parameter of 3 embodiment 2 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White powder or flaky crystal |
| 2 | Purity | ＞ 99.5% |
| 3 | Loss on drying | ≤ 98% |
Above-mentioned triphenylphosphine preparation process uses improved grignard reaction technique, and process, stabilization are easy to operate,
The target product triphenylphosphine that high income, purity are good, color and luster is good can not only be quickly obtained, moreover it is possible to obtain biphenyl this by-product；
In addition, in entire technical process, it is not only high to the utilization rate of raw material, and toluene, tetrahydrofuran, first to being introduced in technical process
Alcohol etc. applies mechanically processing, green, environmental protection using distillation recovery.
Based on above-mentioned triphenylphosphine preparation process, the direct barrelling bag of by-product biphenyl that the present embodiment obtains step (5)
Dress, it is final to obtain index parameter biphenyl finished product as shown in table 4.Wherein, the acquisition reaction equation of by-product biphenyl is as follows：
The biphenyl index parameter of 4 embodiment 2 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White or yellowish flake-like crystal |
| 2 | Purity | ＞ 99% |
The present embodiment prepares biphenyl using the by-product in triphenylphosphine preparation process, compared with exclusively for preparation
Biphenyl and for the technical process that sets, go specially to prepare biphenyl without in addition expending time, energy and cost, can greatly save
Whole making time, energy and the cost of producer；In addition, the high income of the biphenyl finally obtained, purity are good, color and luster is good.
Embodiment 3
A kind of preparation method of biphenyl of the present embodiment is straight as source using the by-product in triphenylphosphine preparation process
It obtains.Wherein, as shown in Figure 1, triphenylphosphine preparation process comprises the following specific steps that：
(1) mass ratio is squeezed into as 1 with pump in the mixing kettle of workshop：2.28：3.14 chlorobenzene, toluene and tetrahydrofuran THF
The mixed liquor that total amount is 4500kg is prepared, beating Xun Huan with pump is uniformly mixed, and mixed liquor is squeezed into head tank；
(2) 150kg magnesium chips is put by feeder for solid materials into 5000L grignard reaction kettles, opens nitrogen protection, Ran Houtong
Cross the mixed liquor that head tank adds 400kg steps (1) to obtain；55 DEG C of initiation grignard reactions of heating, reaction equation are as follows：
Then, then 105 DEG C are warming up to, residual mixed liquor is slowly added dropwise in 5.0h by head tank at this temperature, dripped
In 105 DEG C of insulation reaction 5.0h after adding；
To the end of grignard reaction, sampled using analysis by titration and detect and analyze its grignard content；
(3) when the testing result of sample shows as grignard content more than 20%, confirm that it is qualified；It then, will using nitrogen
Reaction solution press-in 5000L formats in kettle in grignard reaction kettle, less than 80 DEG C is cooled to, into Grignard solution by head tank in 3.0h
260kg phosphine tri chlorides are inside slowly added dropwise, temperature is controlled after completion of dropwise addition, and reaction equation is as follows at 45 DEG C, insulation reaction 5.0h：
It treats after reaction, ON cycle water makes reaction solution be cooled to 25 DEG C of room temperature, centrifugation；
(4) centrifuge mother liquor is pumped to 3000L concentration kettles and carries out being distilled to recover THF/ toluene that (recycling kettle chuck leads to steam heating
Heating, treats that temperature in the kettle rises to 110 DEG C, begins to boil off, then is received back after being condensed by condenser and receives THF/ toluene), recycling is molten
Agent is applied mechanically, and toluene dissolving is added in into residue, and material is transferred to the 3.0% dilute hydrochloric acid water that 400kg is slowly added dropwise in layering kettle
Solution, stratification；
(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent and (recycles kettle chuck to dry and lead to steam heating liter
Temperature is treated that temperature in the kettle rises to 110 DEG C, is begun to boil off, then is received back after being condensed by condenser and receives toluene), recycling toluene is applied mechanically,
Salvage stores adds 1500kg methanol in kettle, is warming up to 110 DEG C of reflux, is cooled to room temperature, and centrifugation, mother liquor is distilled to recover methanol and applies mechanically
(recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 110 DEG C, begins to boil off, then is received after being condensed by condenser
Recycle methanol), filter cake is the crude product containing triphenylphosphine and diphenyl mixture；
It is melted being put into containing the crude product of triphenylphosphine and diphenyl mixture in tank, is warming up to 90 DEG C, after material melting, opens
Stirring is opened, while decompression steams low boiling solvent therein, can not treat liquid, stops stirring, is transferred to rectifying still；Open vacuum machine
Group, after vacuum stabilization, heat up rectifying, and it is as shown in table 5 to collect another by-product biphenyl, mixed fraction and index parameter successively
Target product triphenylphosphine；Wherein, the direct loading barrel packaging of biphenyl, triphenylphosphine are transferred to finished product kettle tabletting packaging, and mixed fraction turns
Enter lower batch of rectifying；Wherein, the acquisition reaction equation of by-product biphenyl is as follows：
The triphenylphosphine technical indicator of 5 embodiment 3 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White powder or flaky crystal |
| 2 | Purity | ＞ 99.5% |
| 3 | Loss on drying | ≤ 98% |
Above-mentioned triphenylphosphine preparation process uses improved grignard reaction technique, and process, stabilization are easy to operate,
The target product triphenylphosphine that high income, purity are good, color and luster is good can not only be quickly obtained, moreover it is possible to obtain biphenyl this by-product；
In addition, in entire technical process, it is not only high to the utilization rate of raw material, and toluene, tetrahydrofuran, first to being introduced in technical process
Alcohol etc. applies mechanically processing, green, environmental protection using distillation recovery.
Based on above-mentioned triphenylphosphine preparation process, the direct barrelling bag of by-product biphenyl that the present embodiment obtains step (5)
Dress, it is final to obtain index parameter biphenyl finished product as shown in table 6.Wherein, the acquisition reaction equation of by-product biphenyl is as follows：
The biphenyl index parameter of 6 embodiment 3 of table
| Sequence number | Index | Numerical value |
| 1 | Appearance | White or yellowish flake-like crystal |
| 2 | Purity | ＞ 99% |
The present embodiment prepares biphenyl using the by-product in triphenylphosphine preparation process, compared with exclusively for system
For the technical process set for biphenyl, go specially to prepare biphenyl without in addition expending time, energy and cost, can save significantly
Save whole making time, energy and the cost of producer；In addition, the high income of the biphenyl finally obtained, purity are good, color and luster
It is good.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of biphenyl, which is characterized in that include the following steps：
(1) in the mixing kettle of workshop with pump squeeze into certain proportional quantity chlorobenzene, toluene and tetrahydrofuran THF prepare total amount be
The mixed liquor of 4000-5000kg is beaten Xun Huan with pump and is uniformly mixed, mixed liquor is squeezed into head tank；
(2) 100-200kg magnesium chips is put by feeder for solid materials into 4500-5500L grignard reaction kettles, opens nitrogen protection,
Then the mixed liquor that 350-450kg steps (1) obtain is added by head tank；50-60 DEG C of initiation grignard reaction of heating, then rises again
Residual mixed liquor is slowly added dropwise by head tank at this temperature to 100-110 DEG C in temperature in 4.5-5.5h, after completion of dropwise addition
100-110 DEG C of insulation reaction 4.5-5.5h；To the end of grignard reaction, sampling detection and analysis grignard content；
(3) after sampling detection is qualified, reaction solution press-in 4500-5500L in grignard reaction kettle is formatted in kettle using nitrogen, is cooled down
To less than 80 DEG C, 240-280kg phosphine tri chlorides, completion of dropwise addition is slowly added dropwise in 2.5-3.5h by head tank into Grignard solution
Temperature is controlled afterwards at 40-50 DEG C, insulation reaction 4.5-5.5h；It treats after reaction, ON cycle water makes reaction solution be cooled to room
Temperature, centrifugation；
(4) centrifuge mother liquor is pumped to 2500-3500L concentration kettles and carries out being distilled to recover THF/ toluene, and recycling design is applied mechanically, to residual
Toluene dissolving is added in object, material is transferred to the 2.5-3.5% diluted hydrochloric acid aqueous solutions that 350-450kg is slowly added dropwise in layering kettle,
Stratification；
(5) organic layer is transferred to crystallization kettle after water washing, is distilled to recover solvent to doing, recycling toluene is applied mechanically, salvage stores in kettle
Add 1000-2000kg methanol, be warming up to 105-115 DEG C of reflux, be cooled to room temperature, centrifuge, mother liquor is distilled to recover methanol and applies mechanically, and filters
Cake is the crude product containing triphenylphosphine and diphenyl mixture；Crude product containing triphenylphosphine and diphenyl mixture is heated in melting tank
After be transferred in rectifying still and carry out rectifying separation, obtain biphenyl and triphenylphosphine.
2. the preparation method of biphenyl according to claim 1, which is characterized in that chlorobenzene, toluene and four in the step (1)
The mass ratio of hydrogen furans is 1：(2-2.5)：(3.1-3.2).
3. the preparation method of biphenyl according to claim 2, which is characterized in that chlorobenzene, toluene and four in the step (1)
The mass ratio of hydrogen furans is specially 1：2.28：3.14.
4. the preparation method of biphenyl according to claim 1, which is characterized in that titrimetry is used in the step (2)
Method detects grignard content.
5. the preparation method of biphenyl according to claim 1, which is characterized in that sampling detection is qualified in the step (3)
Standard for grignard content be more than 20%.
6. the preparation method of biphenyl according to claim 1, which is characterized in that centrifugation is distilled to recover in the step (4)
The specific method of THF/ toluene is in mother liquor and cleaning solution：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to
It 105-115 DEG C, begins to boil off, then is received back after being condensed by condenser and receives THF/ toluene.
7. the preparation method of biphenyl according to claim 1, which is characterized in that be distilled to recover in the step (5) organic
The specific method of toluene is in layer：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105-115 DEG C, starts vapour
Change, then receipts toluene is received back after being condensed by condenser.
8. the preparation method of biphenyl according to claim 1, which is characterized in that centrifugation is distilled to recover in the step (5)
The specific method of methanol is in mother liquor：Recycling kettle chuck leads to steam heat temperature raising, treats that temperature in the kettle rises to 105-115 DEG C, starts
Vaporization, then receipts methanol is received back after being condensed by condenser.
9. the preparation method of biphenyl according to claim 1, which is characterized in that triphenylphosphine will be contained in the step (5)
The progress separated specific method of rectifying in rectifying still is transferred to after being heated in melting tank with the crude product of diphenyl mixture is：Three will be contained
The crude product of Phenylphosphine and diphenyl mixture input is melted in tank, is warming up to 80-100 DEG C, after material melting, opens stirring, together
When decompression steam low boiling solvent therein, can not treat liquid, stop stirring, be transferred to rectifying still；Vacuum pump set is opened, treats vacuum
After stabilization, heat up rectifying, collects biphenyl, mixed fraction and triphenylphosphine successively.
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| CN111548244A (en) * | 2020-05-11 | 2020-08-18 | 江苏中能化学科技股份有限公司 | Method for recovering benzene and high-purity hydrogen in high yield from tail gas of biphenyl preparation process |
| CN111848453A (en) * | 2020-07-22 | 2020-10-30 | 浙江金立源药业有限公司 | Production process and production line of 4-methyl-2' -cyanobiphenyl |
| CN112341304A (en) * | 2020-12-24 | 2021-02-09 | 江苏新瑞药业有限公司 | Method for recovering solvent in valsartan preparation process mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111548244A (en) * | 2020-05-11 | 2020-08-18 | 江苏中能化学科技股份有限公司 | Method for recovering benzene and high-purity hydrogen in high yield from tail gas of biphenyl preparation process |
| CN111848453A (en) * | 2020-07-22 | 2020-10-30 | 浙江金立源药业有限公司 | Production process and production line of 4-methyl-2' -cyanobiphenyl |
| CN111848453B (en) * | 2020-07-22 | 2022-09-02 | 浙江金立源药业有限公司 | Production process and production line of 4-methyl-2' -cyanobiphenyl |
| CN112341304A (en) * | 2020-12-24 | 2021-02-09 | 江苏新瑞药业有限公司 | Method for recovering solvent in valsartan preparation process mother liquor |
| CN112341304B (en) * | 2020-12-24 | 2024-05-24 | 江苏新瑞药业有限公司 | Recovery method of solvent in valsartan preparation process mother liquor |
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