CN102924517B - Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides - Google Patents
Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides Download PDFInfo
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- CN102924517B CN102924517B CN201210395802.8A CN201210395802A CN102924517B CN 102924517 B CN102924517 B CN 102924517B CN 201210395802 A CN201210395802 A CN 201210395802A CN 102924517 B CN102924517 B CN 102924517B
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- Prior art keywords
- gas
- formaldehyde
- thpc
- phosphine
- chloride
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 46
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 title claims abstract 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 150000003003 phosphines Chemical class 0.000 title abstract 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 58
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000012159 carrier gas Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229960003280 cupric chloride Drugs 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 10
- AIRPJJGSWHWBKS-UHFFFAOYSA-N hydroxymethylphosphanium;chloride Chemical compound [Cl-].OC[PH3+] AIRPJJGSWHWBKS-UHFFFAOYSA-N 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a process for preparing a fire retardant which is tetramethylolphosphonium chloride (THPC) by catalyzing and oxidizing high-concentration phosphine gas with copper chlorides. The process comprises the following steps of: effectively preparing the fire retardant THPC by using the copper chlorides as unsupported catalysts, and catalyzing the high-concentration phosphine gas with formaldehyde and hydrochloric acid with the copper chlorides under protection of nitrogen and by action of carrier gas. Due to high-efficiency catalysis properties of the process, the conversion ratio of phosphines is up to 99 %, and the THPC can be effectively separated from the catalysts. Compared with the conventional industrial production of THPC, the phosphines can be fully absorbed by primary catalytic oxidation so as to reduce the yield of the waste phosphine gas; and a primary absorber just is arranged so as to increase convenience in technological operations and reduce investment cost.
Description
Technical field
The invention belongs to the field that fire retardant Tetrakis hydroxymethyl phosphonium chloride (THPC) is produced, particularly relate to the novel process that cupric chloride high performance liquid phase catalyzed oxidation phosphuret-(t)ed hydrogen prepares fire retardant THPC.
Background technology
Current THPC preparation technology reacts with hydrochloric acid and formaldehyde essentially by phosphuret-(t)ed hydrogen under the condition mixed, and then concentrating under reduced pressure obtains product THPC.Phosphuret-(t)ed hydrogen is added gas-liquid cycle mixed reactor by Patents CN 102167709 A report, carry out the synthesis of THPC, in absorption tower, carry out hydrochloric acid in patent CN 101224378A and patent CN101134763A report sodium hypophosphite production course middle and high concentration waste gas treatment process, formaldehyde contacts with the liquid phase of phosphuret-(t)ed hydrogen and synthesizes THPC.Adopt catalyzer owing to not reporting in these 2 sections of patents, in reaction process, the transformation efficiency of phosphuret-(t)ed hydrogen is not high, and the productive rate of THPC is lower.Need to add conversion unit, carrying out multistage absorption could remove completely by phosphuret-(t)ed hydrogen.Patent CN 88101082A reports by adopting zinc, aluminium, tin ion carry out catalysis phosphuret-(t)ed hydrogen and prepare THPC, though this technique adopts catalyzer to carry out catalyzed reaction, exist product and zinc, aluminium, tin ion be separated a difficult problem.
Consider the catalysis characteristics of catalyzer and the separating difficulty of product THPC and catalyzer, current THPC industrial production does not adopt catalyzer, the transformation efficiency of phosphuret-(t)ed hydrogen is 60% ~ 70%, therefore need in reaction find efficient and be easy to the catalyzer with product separation, to improve the separation degree of phosphuret-(t)ed hydrogen transformation efficiency and catalyzer and product.The present invention adopts cupric chloride as catalyzer, catalyzed oxidation phosphuret-(t)ed hydrogen, prepares fire retardant THPC, and phosphuret-(t)ed hydrogen transformation efficiency is up to 99%, and due to catalyzer be solid phase, product be easy to be separated.Not only can process high density phosphine waste gas, more can realize effectively being separated of product fire retardant THPC and catalyzer, this will improve the comprehensive utilization ratio of phosphor resource effectively.
Summary of the invention
In order to reduce the transformation efficiency of equipment cost and raising phosphuret-(t)ed hydrogen, the invention provides a kind of technique of cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, the method utilizes cupric chloride to prepare fire retardant THPC as catalyzer high performance liquid phase catalyzed oxidation phosphuret-(t)ed hydrogen, realize the efficiently catalyzing and oxidizing of phosphine gas, and product and catalyzer are easy to effectively be separated, one time catalyzed oxidation almost can absorb phosphuret-(t)ed hydrogen completely, do not need to arrange multistage absorption tower, greatly reduce the feasibility of process costs and raising technique.
Under the present invention be carrier gas and protection gas, cupric chloride is catalysts conditions at nitrogen, phosphine gas and formaldehyde and hydrochloric acid reaction, obtains liquid product Tetrakis hydroxymethyl phosphonium chloride after product suction filtration is separated.
The inventive method concrete operations are as follows: pass into air 20-30min in nitrogen purging reaction system, air is discharged; Pass in reaction system by nitrogen and phosphuret-(t)ed hydrogen gas mixture, in gas mixture, phosphine gas concentration is 50,000-300,000ppm, phosphine gas through copper chloride catalyst act in synthesis reactor with formaldehyde, hydrochloric acid reaction, temperature of reaction is 45-65 DEG C, and air speed is 100-200h
-1, the rear gas of reaction enters absorption bottle and discharges after the vitriol oil absorbs further, and then catalyst solid is carried out suction filtration with product THPC and be separated, obtain liquid product and be Tetrakis hydroxymethyl phosphonium chloride, wherein catalyzer cupric chloride addition is 0.05 ~ 0.25g CuCl
2/ g formaldehyde, the mol ratio of formaldehyde and hydrochloric acid is 4-4.5:1.
In the present invention, building-up reactions chemical equation is: 4HCHO+HCl+PH
3 (HOCH
2)
4pCl
Utilize N
2pressure phosphine gas and hydrochloric acid and formaldehyde solution reacted generate fire retardant THPC.
In the present invention, the mass percent concentration of formaldehyde is 30-38%, and the mass percent concentration of hydrochloric acid is 31-38%.
Advantage of the present invention is as follows:
Copper chloride catalyst has the characteristic of efficient catalytic in THPC preparation process, phosphine gas transformation efficiency is up to 99%, and due to cupric chloride be solid phase, generation THPC is liquid phase, after suction filtration, these two kinds of liquid-solid two-phases of product THPC and catalyzer can effectively be separated.This, compared with current THPC industrial production, not only reduces the generation of phosphine waste gas, and product is easy to be separated; And only need arrange first absorber, can greatly reduce cost of investment and improve technological operation accessibility, the method is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the THPC preparation flow schematic diagram of this patent.
In figure: 1 is under meter I; 2 is T-valve; 3 is under meter II; 4 is absorption reactor thermallies; 5 is waste gas absorption bottles.
Embodiment
Below by drawings and Examples, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, particular content is as follows:
First nitrogen purging reaction system 30min is passed into, then the gas and vapor permeation of nitrogen and phosphuret-(t)ed hydrogen is passed in reaction system after under meter I 1 and under meter II 3 measures, in mixed gas, phosphine gas concentration is 500, 000ppm, 38% formaldehyde and 38% hydrochloric acid are added Homogeneous phase mixing in absorption reactor thermally 4 respectively, the mol ratio of formaldehyde and hydrochloric acid is 4:1, wherein catalyzer cupric chloride addition is 0.05g/g formaldehyde, phosphine gas through copper chloride catalyst act in absorption reactor thermally with formaldehyde, hydrochloric acid reaction, gas outer row after the vitriol oil in waste gas absorption bottle 5 absorbs further after reaction.At 45 DEG C, air speed is 200h
-1under condition, phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction terminates, products therefrom leaves standstill, and be then separated through suction filtration with product THPC by solid catalyst, obtain liquid product and be Tetrakis hydroxymethyl phosphonium chloride, product purity is 98%.
Embodiment 2: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, particular content is as follows:
Pass into nitrogen purging reaction system 25min, to pass in reaction system after nitrogen and phosphine gas mixing, in mixed gas, phosphine gas concentration is 150,000ppm, 36% formaldehyde and 37% hydrochloric acid are added Homogeneous phase mixing in absorption reactor thermally respectively, the mol ratio of formaldehyde and hydrochloric acid is 4.25:1, wherein catalyzer cupric chloride addition is 0.1g/g formaldehyde, phosphine gas through copper chloride catalyst act in absorption reactor thermally with formaldehyde, hydrochloric acid reaction, gas outer row after the vitriol oil in waste gas absorption bottle absorbs further after reaction.At 50 DEG C, air speed is 150h
-1under condition, phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction terminates, products therefrom leaves standstill, and then solid catalyst is carried out suction filtration with product THPC and be separated, obtain liquid product and be Tetrakis hydroxymethyl phosphonium chloride, product purity is 98%.
Embodiment 3: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, particular content is as follows:
Pass into nitrogen purging reaction system 20min, air is discharged, and will pass in reaction system after nitrogen and phosphine gas mixing, in mixed gas, phosphine gas concentration is 300,000ppm, 30% formaldehyde and 31% hydrochloric acid are added Homogeneous phase mixing in absorption reactor thermally respectively, the mol ratio of formaldehyde and hydrochloric acid is 4.5:1, wherein catalyzer cupric chloride addition is 0.25g/g formaldehyde, phosphine gas through copper chloride catalyst act in absorption reactor thermally with formaldehyde, hydrochloric acid reaction, gas outer row after the vitriol oil in waste gas absorption bottle absorbs further after reaction.At 65 DEG C, air speed is 100h
-1under condition, phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction terminates, products therefrom leaves standstill, and then solid catalyst is carried out suction filtration with product THPC and be separated, obtain liquid product and be Tetrakis hydroxymethyl phosphonium chloride, product purity is 98%.
Claims (2)
1. the technique of a cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, it is characterized in that: under be carrier gas and protection gas, cupric chloride being catalysts conditions at nitrogen, make phosphuret-(t)ed hydrogen and formaldehyde and hydrochloric acid reaction, product is obtained liquid product Tetrakis hydroxymethyl phosphonium chloride after suction filtration is separated;
Aforesaid method concrete operations are as follows: pass into the air 20-30min in nitrogen purging pipeline, the gas of nitrogen and phosphine containing is passed in reaction system, in mixed gas, phosphine gas concentration is 50,000-300,000ppm, phosphine gas through copper chloride catalyst act in synthesis reactor with formaldehyde, hydrochloric acid reaction, temperature of reaction is 45-65 DEG C, and air speed is 100-200h
-1, the rear gas of reaction enters absorption bottle and discharges after the vitriol oil absorbs further, and then catalyst solid is carried out suction filtration with product THPC and be separated, obtain liquid product and be Tetrakis hydroxymethyl phosphonium chloride, wherein catalyzer cupric chloride addition is 0.05-0.25g CuCl
2/ g formaldehyde, the mol ratio of formaldehyde and hydrochloric acid is 4-4.5:1.
2. the technique of cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine according to claim 1, it is characterized in that: the mass percent concentration of formaldehyde is 30-38%, the mass percent concentration of hydrochloric acid is 31-38%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210395802.8A CN102924517B (en) | 2012-10-18 | 2012-10-18 | Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210395802.8A CN102924517B (en) | 2012-10-18 | 2012-10-18 | Process for preparing tetramethylolphosphonium chloride by catalyzing phosphines with copper chlorides |
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| Publication Number | Publication Date |
|---|---|
| CN102924517A CN102924517A (en) | 2013-02-13 |
| CN102924517B true CN102924517B (en) | 2015-06-03 |
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666817A (en) * | 1970-07-13 | 1972-05-30 | Hooker Chemical Corp | Tetrakis (hydroxymethyl) phosphonium chloride from phosphine and formaldehyde |
| CN88101082A (en) * | 1988-02-27 | 1988-12-21 | 王行泳 | New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method |
| CN101143878A (en) * | 2007-10-08 | 2008-03-19 | 江苏康祥集团公司 | Method for preparing tetrakis(hydroxymethyl)phosphonium chloride from phosphine generated in sodium hypophosphite production |
| CN102167709A (en) * | 2011-03-10 | 2011-08-31 | 常熟新特化工有限公司 | Method for preparing Tetrakis (hydroxymethyl) phosphonium chloride |
-
2012
- 2012-10-18 CN CN201210395802.8A patent/CN102924517B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666817A (en) * | 1970-07-13 | 1972-05-30 | Hooker Chemical Corp | Tetrakis (hydroxymethyl) phosphonium chloride from phosphine and formaldehyde |
| CN88101082A (en) * | 1988-02-27 | 1988-12-21 | 王行泳 | New preparation process of fire retardant tetrakis-hydroxymethyl-phosphonium chloride (thpc) with catalytic method |
| CN101143878A (en) * | 2007-10-08 | 2008-03-19 | 江苏康祥集团公司 | Method for preparing tetrakis(hydroxymethyl)phosphonium chloride from phosphine generated in sodium hypophosphite production |
| CN102167709A (en) * | 2011-03-10 | 2011-08-31 | 常熟新特化工有限公司 | Method for preparing Tetrakis (hydroxymethyl) phosphonium chloride |
Non-Patent Citations (1)
| Title |
|---|
| PdCl2-CuCl2液相催化氧化净化黄磷尾气中PH3;宁平等;《中南大学学报(自然科学版)》;20090426;第40卷(第2期);第341页右栏2节，第344页左栏3节 * |
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