CN102924517A - 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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- CN102924517A CN102924517A CN2012103958028A CN201210395802A CN102924517A CN 102924517 A CN102924517 A CN 102924517A CN 2012103958028 A CN2012103958028 A CN 2012103958028A CN 201210395802 A CN201210395802 A CN 201210395802A CN 102924517 A CN102924517 A CN 102924517A
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- Prior art keywords
- gas
- formaldehyde
- chloride
- thpc
- phosphine
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 48
- 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 49
- 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 30
- 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
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 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 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229960003280 cupric chloride Drugs 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000012263 liquid product Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000003786 synthesis reaction Methods 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
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 10
- 230000009466 transformation Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000007791 liquid phase Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 239000012467 final product Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012071 phase 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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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, relate in particular to the novel process that cupric chloride high performance liquid phase catalyzed oxidation phosphuret-(t)ed hydrogen prepares fire retardant THPC.
Background technology
THPC preparation technology reacts under the condition of mixing with hydrochloric acid and formaldehyde by phosphuret-(t)ed hydrogen substantially at present, and then concentrating under reduced pressure obtains product THPC.Patents CN 102167709 A report adds the gas-liquid cycle mixed reactor with phosphuret-(t)ed hydrogen, carry out the synthetic of THPC, in the absorption tower, carry out the Gas-Liquid Contacting of hydrochloric acid, formaldehyde and phosphuret-(t)ed hydrogen in patent CN 101224378A and the patent CN101134763A report sodium hypophosphite production course middle and high concentration waste gas treatment process and synthesize THPC.Because do not report in these 2 pieces of patents and adopt catalyzer, the transformation efficiency of phosphuret-(t)ed hydrogen is not high in reaction process, the productive rate of THPC is lower.Need to add conversion unit, carry out multistage absorption and phosphuret-(t)ed hydrogen could be removed fully.Patent CN 88101082A report is by adopting zinc, aluminium, tin ion to carry out catalysis phosphuret-(t)ed hydrogen and prepare THPC, though this technique adopts catalyzer to carry out catalyzed reaction, has the difficult problem of separating of product and zinc, aluminium, tin ion.
Consider the catalysis characteristics of catalyzer and the separating difficulty of product THPC and catalyzer, the THPC industrial production does not adopt catalyzer at present, the transformation efficiency of phosphuret-(t)ed hydrogen is 60%～70%, therefore need to find efficient in the reaction and be easy to 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, and preparation fire retardant THPC, the phosphuret-(t)ed hydrogen transformation efficiency is up to 99%, and because catalyzer is solid phase, product is easy to separate.Not only can process high density phosphatization hydrogen waste gas, more can realize the effective separation 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 effective separation, one time catalyzed oxidation can almost completely absorb phosphuret-(t)ed hydrogen, the multistage absorption tower need be set, greatly reduce the feasibility of process costs and raising technique.
The present invention is that carrier gas is under the catalyzer condition with protection gas, cupric chloride at nitrogen, phosphine gas and formaldehyde and hydrochloric acid reaction, and the product suction filtration makes the liquid product Tetrakis hydroxymethyl phosphonium chloride after separating.
The inventive method concrete operations are as follows: pass into air 20-30min in the nitrogen purging reaction system, make Bas Discharged; Nitrogen and phosphuret-(t)ed hydrogen gas mixture are passed in the reaction system, and phosphine gas concentration is 50,000-300 in the gas mixture, 000ppm, phosphine gas acts in the synthesis reactor and formaldehyde, hydrochloric acid reaction through copper chloride catalyst, and temperature of reaction is 45-65 ℃, and air speed is 100-200h
-1, gas enters and discharges after absorption bottle further absorbs through the vitriol oil after reacting, and then catalyst solid is carried out suction filtration with product THPC and separates, and obtains liquid product and is Tetrakis hydroxymethyl phosphonium chloride, and wherein catalyzer cupric chloride addition is 0.05～0.25g CuCl
2/ g formaldehyde, the mol ratio of formaldehyde and hydrochloric acid are 4-4.5:1.
The building-up reactions chemical equation is among the present invention: 4HCHO+HCl+PH
3 
(HOCH
2)
4PCl
Utilize N
2Pressure phosphine gas and hydrochloric acid and formaldehyde solution reaction are generated fire retardant THPC.
The mass percent concentration of formaldehyde is 30-38% among the present invention, 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 the THPC preparation process, the phosphine gas transformation efficiency is up to 99%, and because cupric chloride is solid phase, generation THPC is liquid phase, behind suction filtration, these two kinds of liquid-solid two-phases of product THPC and catalyzer get final product effective separation.This compares with present THPC industrial production, has not only reduced the generation of phosphine waste gas, and product is easy to separate; And only the one-level resorber need be set, can greatly reduce cost of investment and improve the technological operation accessibility, the method is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the THPC preparation flow synoptic diagram of this patent.
Among the figure: the 1st, under meter I; The 2nd, T-valve; The 3rd, under meter II; The 4th, absorption reactor thermally; The 5th, the waste gas absorption bottle.
Embodiment
Below by drawings and Examples the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, and particular content is as follows:
At first pass into nitrogen purging reaction system 30min, then the gas mixing with nitrogen and phosphuret-(t)ed hydrogen passes in the reaction system after under meter I 1 and under meter II 3 meterings, phosphine gas concentration is 500 in the mixed gas, 000ppm, 38% formaldehyde and 38% hydrochloric acid are added respectively evenly mixing in the absorption reactor thermally 4, the mol ratio of formaldehyde and hydrochloric acid is 4:1, wherein catalyzer cupric chloride addition is 0.05g/g formaldehyde, phosphine gas acts in the absorption reactor thermally and formaldehyde through copper chloride catalyst, hydrochloric acid reaction, the vitriol oil of gas in waste gas absorption bottle 5 effluxes after further absorbing after the reaction.At 45 ℃, air speed is 200h
-1Under the condition, the phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction finished, products therefrom left standstill, and then solid catalyst was separated through suction filtration with product THPC, obtained liquid product and was Tetrakis hydroxymethyl phosphonium chloride, and product purity is 98%.
Embodiment 2: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, and particular content is as follows:
Pass into nitrogen purging reaction system 25min, to pass in the reaction system after nitrogen and the phosphine gas mixing, phosphine gas concentration is 150 in the mixed gas, 000ppm, 36% formaldehyde and 37% hydrochloric acid are added respectively evenly mixing in the absorption reactor thermally, the mol ratio of formaldehyde and hydrochloric acid is 4.25:1, wherein catalyzer cupric chloride addition is 0.1g/g formaldehyde, phosphine gas acts in the absorption reactor thermally and formaldehyde, hydrochloric acid reaction through copper chloride catalyst, and the vitriol oil of gas in the waste gas absorption bottle effluxes after further absorbing after the reaction.At 50 ℃, air speed is 150h
-1Under the condition, the phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction finished, products therefrom left standstill, and then solid catalyst is carried out suction filtration with product THPC and separates, and obtains liquid product and is Tetrakis hydroxymethyl phosphonium chloride, and product purity is 98%.
Embodiment 3: the technique of this cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine, and particular content is as follows:
Pass into nitrogen purging reaction system 20min, make Bas Discharged, and will pass in the reaction system after nitrogen and the phosphine gas mixing, phosphine gas concentration is 300 in the mixed gas, 000ppm, 30% formaldehyde and 31% hydrochloric acid are added respectively evenly mixing in the absorption reactor thermally, the mol ratio of formaldehyde and hydrochloric acid is 4.5:1, wherein catalyzer cupric chloride addition is 0.25g/g formaldehyde, phosphine gas acts in the absorption reactor thermally and formaldehyde, hydrochloric acid reaction through copper chloride catalyst, and the vitriol oil of gas in the waste gas absorption bottle effluxes after further absorbing after the reaction.At 65 ℃, air speed is 100h
-1Under the condition, the phosphuret-(t)ed hydrogen transformation efficiency is 99%.After reaction finished, products therefrom left standstill, and then solid catalyst is carried out suction filtration with product THPC and separates, and obtains liquid product and is Tetrakis hydroxymethyl phosphonium chloride, and product purity is 98%.
Claims (3)
1. the technique of a cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine; it is characterized in that: be that carrier gas and protection gas, cupric chloride are under the catalyzer condition at nitrogen; make phosphuret-(t)ed hydrogen and formaldehyde and hydrochloric acid reaction, product makes the liquid product Tetrakis hydroxymethyl phosphonium chloride after suction filtration separates.
2. the technique of described cupric chloride catalysis preparing tetrakis (hydroxymethyl) phosphonium chloride from phosphine according to claim 1, it is characterized in that concrete operations are as follows: pass into the air 20-30min in the nitrogen purging pipeline, the gas of nitrogen and phosphine containing is passed in the reaction system, phosphine gas concentration is 50 in the mixed gas, 000-300,000ppm, phosphine gas acts in the synthesis reactor and formaldehyde, hydrochloric acid reaction through copper chloride catalyst, temperature of reaction is 45-65 ℃, and air speed is 100-200h
-1, gas enters and discharges after absorption bottle further absorbs through the vitriol oil after reacting, and then catalyst solid is carried out suction filtration with product THPC and separates, and obtains liquid product and is Tetrakis hydroxymethyl phosphonium chloride, and wherein catalyzer cupric chloride addition is 0.05-0.25g CuCl
2/ g formaldehyde, the mol ratio of formaldehyde and hydrochloric acid are 4-4.5:1.
3. the technique of described 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%.
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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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| 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 true CN102924517A (en) | 2013-02-13 |
| CN102924517B CN102924517B (en) | 2015-06-03 |
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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 |
|---|
| 宁平等: "PdCl2-CuCl2液相催化氧化净化黄磷尾气中PH3", 《中南大学学报(自然科学版)》 * |
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