CN108147431B - A kind of aryl phosphonium chloride production Solid state fermentation technique - Google Patents
A kind of aryl phosphonium chloride production Solid state fermentation technique Download PDFInfo
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- CN108147431B CN108147431B CN201710598681.XA CN201710598681A CN108147431B CN 108147431 B CN108147431 B CN 108147431B CN 201710598681 A CN201710598681 A CN 201710598681A CN 108147431 B CN108147431 B CN 108147431B
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- chloride
- butanol
- hydrochloric acid
- acid solution
- waste residue
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- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 aryl phosphonium chloride Chemical compound 0.000 title claims abstract description 11
- 238000010563 solid-state fermentation Methods 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 38
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000008139 complexing agent Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 3
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 3
- PHLJWFAYUAZPJR-UHFFFAOYSA-M P.[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P.[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 PHLJWFAYUAZPJR-UHFFFAOYSA-M 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005120 petroleum cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 229940062527 alendronate Drugs 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Solid state fermentation technique, especially diphenyl phosphine chloride, which are produced, the invention discloses aryl phosphonium chloride produces Solid state fermentation technique；Aluminium chloride in the technology utilization waste residue separates the two with different solubility of the potassium chloride in n-butanol, the potassium chloride of recycling can be reused directly as de-complexing agent, the crystal aluminum chloride obtained after hydrolysis can also be taken out directly as product, a small amount of outer processing of organic matter bottoms committee.
Description
Technical field
The present invention relates to a kind for the treatment of process of aryl phosphonium chloride production waste residue, specifically diphenyl phosphine chloride produces waste residue
Treatment process.
Technical background
Diphenyl phosphine chloride is the important intermediate for preparing photoinitiator TPO again, and demand will increasingly increase, due to two
The special physical characteristic of tetraphenylphosphonium chloride phosphine, preparation process are comparatively laborious, it is difficult to realize large-scale industrial production, great Liang Xu
Import is relied on, there is Qingdao Fu Silin Chemical Industry Science Co., Ltd in the producer of the main production diphenyl phosphine chloride in the whole nation at present；Mountain
Dong Hong sunlight Chemical Co., Ltd. etc., prepares diphenyl phosphine chloride and is mainly the following preparation method:
1) conventional production process: with benzene, phosphine tri chloride, anhydrous aluminum chloride is Material synthesis dichlorophenyl phosphine, using height
Temperature obtains tetraphenylphosphonium chloride phosphine after resetting, and acquired dichlorophenyl phosphine exists in the form of the complex compound with aluminium chloride, needs to use again
Alkali metal chloride destroys complex, is evaporated under reduced pressure after solvent extraction, obtains about 60% chloride 2-phenyl-phosphine of yield.
2) grignard reagent method: by grignard reagent PH-Mg-Br and N, N- dimethyl phosphine amino dichloride (6.64mL,
36mmol) mix, it is to be mixed completely after, by reaction be warming up to room temperature and under stiring overnight, then again add hexamethylene (200mL)
Reaction solution is diluted, dry HCl gas sparging is finally filtered acquired solution by solution 0.5h, is removed solvent and is both obtained two
The mixture of tetraphenylphosphonium chloride phosphine and bromide, product yield is 40%.
3) petroleum cracking method: Shandong Hong Yu Chemical Co., Ltd. produces diphenyl phosphine chloride using the method, and detailed process is such as
Under: it uses Petroleum Aromatics, anhydrous sodium metasilicate, trimerization Alendronate and phosphine tri chloride for base-material, is added in right amount by mixing, filtering
Aluminum chloride catalyst so that it is further reflected cracking, using filtering be fractionated, finally decompose produce fuel detergent (hexichol
Base phosphonium chloride) and aluminium polychloride.
4) ionic liquid-catalyzed method: Qingdao Fu Silin Chemical Industry Science Co., Ltd and University Of Science and Technology Of Shandong combine the section undertaken
Skill brainstorm project " exploitation of ionic liquid-catalyzed method synthesis diphenyl phosphine chloride technology " using phosphine tri chloride and excessive benzene as raw material,
It is reacted under Lewis acidic ionic liquid catalytic action, after reaction reaction solution point two layers, one layer is ionic liquid layer, one layer
To mix liquid layer.Through direct liquid separation, ionic liquid layer through extracting, extract liquor and mixed liquor it is laminated simultaneously, respectively through air-distillation, subtract
Pressure distills to obtain object diphenyl phosphine chloride and by-product phenylphosphonic dichloride.
Method 1) 1 ton of diphenyl phosphine chloride of every production can generate 1.5 tons of waste residue, and post-processing is difficult, and environmental protection pressure is suitable
Greatly.
Method 2) grignard reagent preparation requirement height, product yield is low, and expensive starting materials are not suitable for industrialized production.
Method 3) petroleum cracking method reaction condition requirement high temperature and pressure, equipment requirement is high, and main product yield is subsequent less than 10%
Separation process is more.
Method 4) ionic liquid synthesis cost is high and to extraneous condition responsive, it is easy to and failure cannot not only be reused simultaneously
And a large amount of waste residue is generated, and post-process friendship method 1) it is more difficult.
In conclusion method 1) synthesis diphenyl phosphine chloride it is at low cost, equipment is simple, and yield is reliable, but Solid state fermentation is
The problem of production is restricted, the present invention provides the treatment process of the waste residue.
Summary of the invention
A kind for the treatment of process of aryl phosphonium chloride production waste residue, especially diphenyl phosphine chloride produce Solid state fermentation technique；
Technique main purpose is that aluminium chloride, the potassium chloride in waste residue are separated with a small amount of organic matter.
A kind for the treatment of process of aryl phosphonium chloride production waste residue, which is characterized in that complete according to the following steps:
Aryl phosphonium chloride production waste residue is crushed, granularity is made to reach 50 mesh or less；
Under collet circulating water, filters pressing is obtained the waste residue crushed is put into n-butanol stirring at normal temperature reaction 2h in batches after
To filter residue and filtrate；N-butanol used and slag quality ratio are 2:1-5:1；
Filter residue main component is potassium chloride, is reused after roasting, and maturing temperature is 200-250 DEG C；
Filtrate slowly instills in hydrochloric acid solution and is hydrolyzed, and organic phase and water phase are obtained after liquid separation, and hydrochloric acid solution used is dense
Degree is 10-30%, and hydrochloric acid solution and filtrate volume ratio are 2:1-5:1, and hydrolysis temperature is 20-80 DEG C；
Gained water phase distillation and concentration obtains byproduct crystal aluminum chloride, and concentration gained hydrochloric acid solution is back to use step 4)；
N-butanol is distilled to recover after the organic phase dehydration of gained, the n-butanol of recycling is back to use step 2), a small amount of vinasse
The outer processing of committee.
The present invention has the effect of positive: the method that the present invention handles waste residue, environmental protection and public nuisance free, operating procedure is simple, at
This is low, and the potassium chloride, the n-butanol that recycle can add recycling again, and the crystal aluminum chloride of recycling can be used as outside commodity
It sells, it is good in economic efficiency, it is suitable for popularity and uses.
Specific embodiment
The present invention will be described in detail for the following example, but following example is not limited only to the present invention again.
Embodiment 1:
(1) 100kg aryl phosphonium chloride production waste residue is crushed, granularity is made to reach 50 mesh or less；
(2) under collet circulating water, the waste residue crushed is put into stirring at normal temperature in the n-butanol of 200kg in batches and is reacted
2h, filters pressing obtain 53.0kg filter residue and 250L n-butanol filtrate；
(3) filter residue is sent into roaster, and maturing temperature is 200 DEG C, obtains potassium chloride 49.7kg；
(4) 250L n-butanol filtrate slowly instills in 10% hydrochloric acid solution of 500L and is hydrolyzed, and control hydrolysis temperature does not surpass
50 DEG C are crossed, hydrolysis obtains organic phase and water phase after finishing standing liquid separation；
(5) gained water phase distillation and concentration obtains product crystal aluminum chloride 47kg, and concentration gained hydrochloric acid solution is back to use step
4)；
(6) it is distilled to recover n-butanol 232L after the organic phase dehydration of gained, the n-butanol of recycling is back to use step 2), distills residual
The outer processing of liquid committee.
Embodiment 2:
(1) 100kg aryl phosphonium chloride production waste residue is crushed, granularity is made to reach 50 mesh or less；
(2) under collet circulating water, the waste residue crushed is put into stirring at normal temperature in the n-butanol of 300kg in batches and is reacted
2h, filters pressing obtain 50.8kg filter residue and 400L n-butanol filtrate；
(3) filter residue is sent into roaster, and maturing temperature is 200 DEG C, obtains potassium chloride 48.9kg；
(4) n-butanol filtrate slowly instills in 10% hydrochloric acid solution of 800L and is hydrolyzed, and control hydrolysis temperature is no more than 80
DEG C, hydrolysis obtains organic phase and water phase after finishing standing liquid separation；
(5) gained water phase distillation and concentration obtains product crystal aluminum chloride 48.2kg, and concentration gained hydrochloric acid solution is back to use step
It is rapid 4)；
(6) it is distilled to recover n-butanol 374L after the organic phase dehydration of gained, the n-butanol of recycling is back to use step 2), distills residual
The outer processing of liquid committee.
Claims (1)
1. a kind for the treatment of process of aryl phosphonium chloride production waste residue, especially diphenyl phosphine chloride produce Solid state fermentation technique,
It is characterized in that, completes according to the following steps:
1) aryl phosphonium chloride production waste residue is crushed, granularity is made to reach 50 mesh or less；
2) under collet circulating water, the waste residue crushed is put into stirring at normal temperature in n-butanol in batches and reacts 2h, filters pressing obtains
Filter residue and filtrate, n-butanol used and slag quality ratio are 2:1-5:1；
3) filter residue main component is potassium chloride, is reused after roasting, and maturing temperature is 200-250 DEG C；
4) filtrate slowly instills in hydrochloric acid solution and is hydrolyzed, and organic phase and water phase, concentration of hydrochloric acid solution used are obtained after liquid separation
For 10-30%, hydrochloric acid solution and filtrate volume ratio are 2:1-5:1, and hydrolysis temperature is 20-80 DEG C；
5) gained water phase distillation and concentration obtains byproduct crystal aluminum chloride, and concentration gained hydrochloric acid solution is back to use step 4)；
6) n-butanol is distilled to recover after the organic phase dehydration of gained, the n-butanol of recycling is back to use step 2), a small amount of vinasse committee
Outer processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710598681.XA CN108147431B (en) | 2017-07-21 | 2017-07-21 | A kind of aryl phosphonium chloride production Solid state fermentation technique |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710598681.XA CN108147431B (en) | 2017-07-21 | 2017-07-21 | A kind of aryl phosphonium chloride production Solid state fermentation technique |
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| Publication Number | Publication Date |
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| CN108147431A CN108147431A (en) | 2018-06-12 |
| CN108147431B true CN108147431B (en) | 2019-09-03 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615812A (en) * | 2019-09-30 | 2019-12-27 | 江苏多森化工有限公司 | Preparation method of diphenyl phosphine chloride |
| CN110684047B (en) * | 2019-11-18 | 2022-07-29 | 怀化泰通新材料科技有限公司 | Joint production method of phenyl phosphine dichloride and diphenyl phosphine chloride |
| CN114620745B (en) * | 2020-12-10 | 2024-04-05 | 洪湖市一泰科技有限公司 | Comprehensive recycling method for alkyl dichlorophosphine production byproducts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803873A (en) * | 2015-03-26 | 2015-07-29 | 洪湖市一泰科技有限公司 | Method for recycling Al resources in Friedel-Crafts reaction |
| CN104961767A (en) * | 2015-06-25 | 2015-10-07 | 北京理工大学 | Recycling method of aluminum chlorate ionic liquid catalyst composition |
-
2017
- 2017-07-21 CN CN201710598681.XA patent/CN108147431B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803873A (en) * | 2015-03-26 | 2015-07-29 | 洪湖市一泰科技有限公司 | Method for recycling Al resources in Friedel-Crafts reaction |
| CN104961767A (en) * | 2015-06-25 | 2015-10-07 | 北京理工大学 | Recycling method of aluminum chlorate ionic liquid catalyst composition |
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