CN114620745A - Comprehensive recycling method for alkyl dichlorophosphine production byproducts - Google Patents
Comprehensive recycling method for alkyl dichlorophosphine production byproducts Download PDFInfo
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- CN114620745A CN114620745A CN202011434507.XA CN202011434507A CN114620745A CN 114620745 A CN114620745 A CN 114620745A CN 202011434507 A CN202011434507 A CN 202011434507A CN 114620745 A CN114620745 A CN 114620745A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- chloride
- sodium chloride
- flame retardant
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 alkyl dichlorophosphine Chemical compound 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 239000006227 byproduct Substances 0.000 title claims abstract description 51
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 202
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 193
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000011574 phosphorus Substances 0.000 claims abstract description 106
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 106
- 239000011780 sodium chloride Substances 0.000 claims abstract description 101
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 92
- 239000003063 flame retardant Substances 0.000 claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 75
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 238000001914 filtration Methods 0.000 claims abstract description 42
- 239000000706 filtrate Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 27
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 12
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 abstract 1
- 229940063656 aluminum chloride Drugs 0.000 description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 238000011084 recovery Methods 0.000 description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000012024 dehydrating agents Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000004255 ion exchange chromatography Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 238000002798 spectrophotometry method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 1
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- 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
- C01D3/14—Purification
-
- 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
- C01F7/62—Purification
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/306—Arylalkanephosphinic acids, e.g. Ar-(CH2)n-P(=X)(R)(XH), (X = O,S, Se; n>=1)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Geology (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a comprehensive recycling method of alkyl dichlorophosphine production byproducts, which comprises the following steps: reacting aldehyde compounds with alkyl dichlorophosphine in a byproduct to generate a phosphorus-containing flame retardant or an intermediate thereof, obtaining a reacted mixture, gradually separating sodium chloride and a precipitate in the form of aluminum trichloride hydrate by increasing the content of hydrogen chloride in the system step by step in a grading manner, obtaining a mixture containing the phosphorus-containing flame retardant or the intermediate thereof, a small amount of aluminum chloride, sodium chloride and hydrochloric acid, adding sodium hydroxide after distillation and concentration, filtering, acidifying and concentrating a filtrate, extracting, and purifying; the method of the invention obtains pure sodium chloride, pure aluminum chlorohydrate and phosphorus-containing flame retardant or intermediate thereof, has clear and definite steps and functions, is simple and easy to control, and completely solves the problem of comprehensive utilization of the composite salt in the production process of the methyldichlorophosphine.
Description
Technical Field
The invention relates to the technical field of recycling of phosphorus-containing byproducts in the production process of alkyl dichlorophosphine serving as an organic phosphine intermediate, in particular to a comprehensive utilization method of a phosphorus-containing composite salt.
Background
Alkyl dichlorophosphine, also known as alkyl dichlorophosphine, is an important intermediate of organic phosphine compounds, particularly methyl dichlorophosphine, and is a core raw material for synthesizing herbicide glufosinate-ammonium intermediate diethyl methylphosphonite. Currently, the mainstream production methods of methyldichlorophosphine mainly comprise the following three methods:
1. phosphorus trichloride and methane pass through a tubular reactor, a condenser and a fractionating device in the presence of a high-temperature high-pressure catalyst to obtain methyldichlorophosphine, deposits are easily generated in the method to cause the blockage of the tubular reactor and the condenser, so that the production is interrupted, the product conversion rate is low, and the energy consumption is high.
2. Phosphorus trichloride, aluminum trichloride and chloromethane are subjected to complex reaction in a pressure kettle to generate a ternary complex, the ternary complex is reduced by aluminum powder to obtain a complex of methyldichlorophosphine and aluminum trichloride, the complex is dissociated into the methyldichlorophosphine under the action of sodium chloride, and a byproduct of composite salt of sodium chloride and aluminum chloride is remained.
3. Methyl chloride reacts with aluminum alloy to generate a mixture of methyl dichloroaluminum and dimethyl aluminum chloride, the mixture reacts with phosphorus trichloride to generate a complex of methyl dichlorophosphine and aluminum chloride, the complex reacts with sodium chloride to dissociate the methyl dichlorophosphine, and a byproduct of a complex salt of the sodium chloride and the aluminum chloride is remained.
In the above methods, methods 2 and 3 do not have high temperature and high pressure, but the dissociation of sodium chloride to methyldichlorophosphine and aluminum trichloride is insufficient, so that the content of the residual methyldichlorophosphine in the aluminum chloride and sodium chloride composite salt is relatively high, and the aluminum chloride and sodium chloride composite salt cannot be well recycled, which is a great obstacle in the production of methyldichlorophosphine. To address this problem, the prior art proposes a number of different solutions, for example:
the Chinese patent CN105217667B mentions that the sodium chloride and the aluminum chloride are decomplexed by a mixture of decomplexer alcohol and ether to obtain the aluminum chloride for reuse, and the method does not mention the treatment of the phosphorus-containing compound and the sodium chloride in the sodium chloride and the compound salt sodium tetrachloroaluminate, so that the phosphorus-containing compound and the sodium chloride cannot be recovered.
Chinese patent CN108238621A discloses a method for preparing polyaluminium chloride by dissolving compound salt, adding ferric chloride, hydrochloric acid, sodium hydroxide, sodium metaaluminate and the like to carry out polymerization reaction, cooling and filtering to obtain polyaluminium chloride solution.
Chinese invention patent CN111187297A discloses a method for recovering and treating phosphine-containing industrial by-products, which comprises placing the by-products generated in the production process of diethyl methylphosphite into a reaction vessel, adding phenolic compounds or binary and above arylamine compounds or compounds containing oxirane functional groups, heating to react under the condition of isolating air, cooling to room temperature, slowly dissolving the obtained solid in water, and controlling the adding speed and stirring uniformly because the process of dissolving water is a heat release process; cooling and filtering, wherein the obtained filter residue is used as a phosphorus flame retardant, the obtained first filtrate is continuously subjected to solid-liquid separation, specifically, the first filtrate is heated to 100-120 ℃ until crystals appear and the amount of the crystals is not increased any more, the heating is stopped, the hot first filtrate is filtered, and the obtained solid is sodium chloride crystals; and (3) slowly adding water into the obtained second filtrate, cooling to room temperature, adjusting the pH value of the second filtrate to prepare the polyaluminium chloride, specifically, adding ferric chloride and hydrochloric acid into the second filtrate, stirring and mixing uniformly, controlling the temperature of the reaction solution to be more than 85 ℃, then sequentially adding aluminum hydroxide and calcium metaaluminate, and controlling the reaction temperature to be 100 ℃ to react to obtain the polyaluminium chloride. Although the method can recycle the methyldichlorophosphine, the added phenolic substances or binary and above aromatic amine compounds or epoxy compounds enter a polyaluminum system, so that polyaluminum is polluted, and the application value is not high. Moreover, the method has the disadvantages of complex process, high control difficulty and inconvenient operation.
Chinese patent CN111689508A discloses a method for treating tetrachloro sodium aluminate solid slag, which comprises (1) mixing tetrachloro sodium aluminate solid slag with water for dissociation, then adding a separating agent to separate out aluminum chloride hexahydrate, or directly mixing tetrachloro sodium aluminate solid slag with the separating agent for dissociation, separating out aluminum chloride hexahydrate, and then carrying out primary solid-liquid separation to obtain aluminum chloride hexahydrate solid and primary filtrate; (2) and (3) concentrating and crystallizing the primary filtrate obtained in the step (1), and performing secondary solid-liquid separation to obtain sodium chloride solid and secondary filtrate, and returning the secondary filtrate to the step (1) to provide a separating agent required by precipitation of aluminum chloride hexahydrate. The process has proved to be capable of separating sodium chloride and aluminium chloride, however, the solution reported in this patent has errors, in particular, in step (1) it is not aluminium chloride hexahydrate but sodium chloride which is obtained first, and the sodium chloride and aluminium chloride which are finally obtained are not up to standard because of contamination from phosphorus-containing compounds in the solid residual mother liquor.
In conclusion, in the prior art, the utilization of the composite salt generated in the production process of the methyl dichlorophosphine cannot be fully and effectively realized, and some utilization methods have the problems of complex process, high control difficulty and the like.
Disclosure of Invention
In order to solve the technical problem of the comprehensive utilization of byproducts in the production of methyldichlorophosphine, the invention provides a comprehensive utilization method of the byproducts in the production process of the methyldichlorophosphine, and the method can fully and effectively recycle the byproducts in the production of the methyldichlorophosphine and has simple process and easy control.
In order to solve the problems, the invention adopts the following technical scheme:
a method for the integrated recovery and utilization of alkyl dichlorophosphine production byproducts, wherein the alkyl dichlorophosphine production byproducts comprise sodium chloride and aluminum chloride composite salts and alkyl dichlorophosphine, and the method comprises the following steps:
s1, reacting the alkyl dichlorophosphine in the alkyl dichlorophosphine production by-product with an aldehyde compound in the presence of water to generate a phosphorus-containing flame retardant or an intermediate thereof, so as to obtain a first mixture containing the phosphorus-containing flame retardant or the intermediate thereof, sodium chloride and aluminum chloride;
s2, introducing hydrogen chloride and/or adding hydrochloric acid into the first mixture to enable the mass percentage of the hydrogen chloride in the mixture solution to reach 5% -15%, crystallizing and separating out sodium chloride, filtering, washing a filter cake with the hydrochloric acid to obtain pure sodium chloride solid, wherein the filtrate is a second mixture containing a very small amount of sodium chloride, aluminum trichloride, a phosphorus-containing flame retardant or an intermediate thereof and the hydrochloric acid;
s3, introducing hydrogen chloride gas and/or adding hydrochloric acid into the filtrate obtained after filtration in the step S2 to ensure that the mass content of the hydrogen chloride in the mixture solution is more than or equal to 35 percent, precipitating aluminum chloride in the form of aluminum trichloride hydrate, filtering, washing a filter cake with hydrochloric acid, and drying to obtain the aluminum trichloride hydrate, wherein the filtrate is a third mixture containing a phosphorus-containing flame retardant or an intermediate thereof, aluminum chloride, sodium chloride and hydrochloric acid;
s4, distilling and concentrating the third mixture obtained in the step S3 to obtain concentrated hydrochloric acid and a phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or an intermediate thereof;
s5, separating and removing aluminum chloride and sodium chloride from the phosphorus-containing flame retardant mixed with the aluminum chloride and the sodium chloride or the intermediate thereof to obtain the phosphorus-containing flame retardant or the intermediate thereof.
Further, in step S1, mixing the alkyl dichlorophosphine production byproduct, the aldehyde compound and dilute hydrochloric acid, and reacting at 40-100 ℃, wherein the mass percentage of the dilute hydrochloric acid is less than or equal to 10%.
According to a preferred aspect of the present invention, in step S1, the alkyl dichlorophosphine production byproduct is added to the diluted hydrochloric acid in batches, the system temperature is maintained at 40-100 ℃ during the addition process, and after the addition of the alkyl dichlorophosphine production byproduct is completed, an aldehyde compound or an aqueous solution in which the aldehyde compound is dispersed is added, and the mixture is stirred for reaction, so as to obtain the first mixture.
In steps S2 and S3, the hydrochloric acid for washing is concentrated hydrochloric acid with a mass percentage of 30% to 37%, respectively.
Further, in step S1, the aldehyde compound preferably has a structure represented by the following general formula (1):
wherein R is1Hydrogen, C1-C12 branched or straight chain alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with a C1-C12 alkyl side chain, phenyl which is unsubstituted or substituted with one or more C1-C12 branched or straight chain alkyl groups. Further, in the general formula (1), R1There may be mentioned hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl and the like.
According to some specific and preferred aspects of the present invention, in step S1, the aldehyde compound is one or more selected from acetaldehyde, benzaldehyde, and phenylacetaldehyde.
According to some preferred aspects of the present invention, before performing step S1, the content of the alkyl dichlorophosphine in the phosphorus-containing composite salt is obtained, and in step S1, the content of the alkyl dichlorophosphine in the phosphorus-containing composite salt is determined according to the feeding molar ratio of the alkyl dichlorophosphine to the aldehyde compound of 1: 1.01-1.3, feeding.
Further preferably, in step S1, the molar ratio of alkyl dichlorophosphine to aldehyde compound is 1: 1.01-1.1, feeding.
According to some preferred aspects of the present invention, in step S1, the diluted hydrochloric acid is used in an amount of 1 to 10 times the amount of the phosphorus-containing complex salt. Further preferably, in step S1, the diluted hydrochloric acid is used in an amount of 1-5 times the amount of the phosphorus-containing complex salt.
According to some preferred aspects of the present invention, in step S1, the diluted hydrochloric acid is 2% to 5% by mass; in step S2, the mass percentage of hydrochloric acid used for washing the filter cake is 30% to 37%.
According to some preferred aspects of the invention, in step S2, hydrogen chloride is introduced to make the mass percentage of hydrogen chloride in the mixture solution reach 6% -10%; and/or in step S3, introducing hydrogen chloride to ensure that the mass content of the hydrogen chloride in the mixture solution is 35-45%.
According to some preferred aspects of the invention, the alkyl dichlorophosphine is methyldichlorophosphine and the phosphorus-containing complex salt is a by-product from the production of methyldichlorophosphine. The comprehensive recycling method of the alkyl dichlorophosphine production byproduct also comprises the following steps: s6, the sodium chloride solid obtained in the step S2 is used in the methyl dichlorophosphine production process.
According to some preferred aspects of the present invention, the integrated recycling method of the alkyl dichlorophosphine production by-product further comprises: s7, the aluminum chlorohydrate obtained in the step S3 is used for casting and sewage treatment industries.
According to some preferred aspects of the present invention, the integrated recycling method of the alkyl dichlorophosphine production by-product further comprises: s8, the concentrated hydrochloric acid obtained in step S4 is further separated into hydrogen chloride gas and dilute hydrochloric acid, and used in step S1.
Further, in step S8, the method of separating concentrated hydrochloric acid is a calcium chloride method or a sulfuric acid method; the calcium chloride method comprises the steps of taking a calcium chloride solution as a dehydrating agent, continuously separating out hydrogen chloride, and continuously distilling the calcium chloride solution to obtain dilute hydrochloric acid; the calcium chloride concentrated solution is continuously used as a dehydrating agent to separate hydrogen chloride; the sulfuric acid method is characterized in that concentrated sulfuric acid is used as a dehydrating agent to continuously separate hydrogen chloride, and a sulfuric acid solution is continuously distilled to obtain dilute hydrochloric acid and concentrated sulfuric acid, and the concentrated sulfuric acid is used as the dehydrating agent to continuously separate the hydrogen chloride.
Preferably, in step S1, the system is kept at 70 to 90 ℃ for 1 to 2 hours after the precipitation of sodium chloride crystals and before filtration. The subsequent filtering and separating operation of the sodium chloride can be easier through heat preservation.
According to a preferred aspect of the present invention, the step S5 further includes:
s50: adding sodium hydroxide to the phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or the intermediate thereof obtained in step S4 to allow the aluminum chloride in a dissolved state to generate sodium chloride and aluminum hydroxide, thereby obtaining a mixture containing aluminum hydroxide, sodium chloride, a sodium salt of the phosphorus-containing flame retardant or the intermediate thereof, and filtering the mixture, wherein the filtrate is an aqueous solution of the phosphorus-containing flame retardant or the intermediate sodium salt thereof and sodium chloride;
s51: and (4) adding hydrochloric acid into the filtrate obtained in the step (S50) for acidification so as to enable the phosphorus-containing flame retardant or the intermediate sodium salt thereof to be dissociated into the phosphorus-containing flame retardant or the intermediate thereof, then concentrating until no water exists to obtain the phosphorus-containing flame retardant or the phosphorus-containing flame retardant intermediate and sodium chloride, adding an organic solvent, uniformly stirring, filtering, concentrating the filtrate, carrying out reduced pressure distillation or recrystallization to obtain the phosphorus-containing flame retardant or the intermediate thereof, washing the filter cake with the organic solvent, and drying to obtain sodium chloride.
According to some preferred aspects of the present invention, the integrated recycling process for the alkyl dichlorophosphine production by-product further comprises one or more of the following steps:
s9, dissolving the sodium chloride obtained in the step S5 in water to obtain a sodium chloride aqueous solution, returning to the step S1, mixing the sodium chloride aqueous solution with dilute hydrochloric acid, and dissolving the complex salt;
s10, returning the filter cake filtered in the step S50, namely the aluminum hydroxide, to the step S2 for generating aluminum chloride;
s11, further preparing the phosphorus-containing flame retardant intermediate obtained in the step S51 into a phosphorus-containing flame retardant.
The invention also provides a production method of alkyl dichlorophosphine, which comprises the following steps:
(1) to obtain alkyl dichlorophosphine and sodium chloride and aluminum chloride composite salt by-products containing the alkyl dichlorophosphine,
(2) the comprehensive recycling method of the alkyl dichlorophosphine production by-product is adopted to recycle and obtain sodium chloride, aluminum chlorohydrate, phosphorus-containing flame retardant or an intermediate thereof.
Further, the production method also comprises (3) using the sodium chloride recovered in the above (2) as a raw material in the step (1).
In one embodiment according to the present invention, the alkyl dichlorophosphines include methyldichlorophosphine, phenyldichlorophosphine, and the like.
In the invention, if the mass percent concentration is not specified, the mass percent contents of the hydrogen chloride and the sulfuric acid in the related dilute hydrochloric acid and concentrated sulfuric acid are all the conventional definition ranges in the prior art.
The technical scheme provided by the invention has the following beneficial effects:
the treatment method can prepare the residual alkyl dichlorophosphine in the composite salt into the phosphorus-containing flame retardant with higher added value or the intermediate thereof; sodium chloride with the content of 99.5 percent or more can be obtained and can be reused in the production process of the methyldichlorophosphine; and can obtain the hydrated aluminum chloride with the content of 97 percent or more, which completely accords with the standard of the superior product of the hydrated aluminum chloride; the hydrochloric acid used can be separated to obtain hydrogen chloride and dilute hydrochloric acid, and the hydrogen chloride and dilute hydrochloric acid can be reused for treating the compound salt. Compared with the prior art, the method can realize the high-efficiency recovery of all useful substances, has no waste liquid in the whole process, lower recovery cost, simple process and simple and convenient operation, and can really and completely solve the problem of comprehensive utilization of byproducts in the production of alkyl dichlorophosphine.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a phosphine spectrum of the flame retardant prepared in example 1.
Detailed Description
The present invention will be described in further detail below by taking a method of comprehensively utilizing a by-product (phosphorus-containing complex salt) in the production process of methyldichlorophosphine as an example.
According to some embodiments of the present invention, a method for the integrated utilization of byproducts in a methyldichlorophosphine production process comprises the steps of:
s1, adding the alkyl dichlorophosphine production by-product into dilute hydrochloric acid in batches, keeping the system temperature at 40-100 ℃ in the adding process, adding an aldehyde compound or an aqueous solution in which the aldehyde compound is dispersed after the alkyl dichlorophosphine production by-product is added, and stirring for reaction to obtain a first mixture; in this step, the amount of the aldehyde compound to be charged is preferably excessive relative to phosphorus-containing components such as methyldichlorophosphine, and the molar ratio of the aldehyde compound to the methyldichlorophosphine to be charged is preferably 1.01 to 1.3: 1, more preferably 1.01 to 1.1: 1, more preferably 1.03 to 1.05: 1. preferably, the reaction temperature is 40-100 ℃, more preferably 40-70 ℃, and still more preferably 45-60 ℃. The concentration of the dilute hydrochloric acid used is preferably 10% or less, more preferably 5% or less, and the amount used is generally 1 to 10 times, preferably 1 to 5 times, that of the phosphorus-containing complex salt; furthermore, the dilute hydrochloric acid used can be produced by separation from the concentrated hydrochloric acid obtained in the subsequent step.
S2, supplementing certain hydrogen chloride into the first mixture by using an ionic effect, fully reducing the solubility of sodium chloride by using a mode of increasing chloride ions, crystallizing and separating out, preferably performing heat preservation (so that the sodium chloride is subjected to crystal form transformation to facilitate subsequent filtration), filtering, washing a filter cake by using hydrochloric acid with a certain concentration to obtain pure sodium chloride solid, drying and then using the pure sodium chloride solid in the production of methyldichlorophosphine, wherein the filtrate is a second mixture containing a small amount of sodium chloride, aluminum trichloride, phosphorus-containing flame retardant or intermediate thereof and hydrochloric acid. Preferably, the hydrogen chloride is supplemented to make the concentration of the hydrogen chloride in the mixture solution reach 6-10%. The temperature of the heat preservation can be 70-90 ℃, the heat preservation time can be 1-2 hours, and the hydrochloric acid concentration for washing is preferably concentrated hydrochloric acid, and specifically 30-37%.
S3, continuously introducing hydrogen chloride gas into the second mixture obtained in the step S2, continuously increasing the content of chloride ions, enabling the content of hydrogen chloride to be more than 35%, enabling aluminum chloride to be precipitated in the form of aluminum trichloride hydrate, filtering, washing a filter cake with concentrated hydrochloric acid, combining filter liquor, and drying the filter cake to obtain the aluminum trichloride hydrate. The filtrate is a third mixture comprising the phosphorus-containing flame retardant or its intermediate, a small amount of aluminum chloride and sodium chloride, hydrochloric acid. The hydrogen chloride introduced may be hydrogen chloride produced by separating concentrated hydrochloric acid obtained in the subsequent step. Preferably, introducing hydrogen chloride to ensure that the content of the hydrogen chloride is 35-45%;
s4, distilling and concentrating the third mixture obtained in the step S3 to obtain concentrated hydrochloric acid and a phosphorus-containing flame retardant mixed with a small amount of aluminum chloride and sodium chloride or an intermediate thereof. Preferably, the distillation concentration is reduced pressure multi-effect distillation concentration;
s5, separating and obtaining the phosphorus-containing flame retardant or the intermediate thereof from the phosphorus-containing flame retardant or the intermediate thereof mixed with a small amount of aluminum chloride and sodium chloride, which specifically comprises the following steps:
s50: neutralizing the phosphorus-containing flame retardant mixed with a small amount of aluminum chloride and sodium chloride or the intermediate thereof obtained in the step S4 with sodium hydroxide (preparing the dissolved aluminum chloride into sodium chloride and aluminum hydroxide to effectively separate the phosphorus-containing flame retardant and inorganic salt substances) to obtain a mixture of the aluminum hydroxide, the sodium chloride, the phosphorus-containing flame retardant or the intermediate sodium salt thereof, and filtering to obtain a filtrate which is an aqueous solution of the phosphorus-containing flame retardant or the intermediate sodium salt thereof and the sodium chloride;
s51: adding hydrochloric acid into the filtrate obtained in the previous step for acidification (hydrochloric acid is used for dissociating sodium salt of the phosphorus-containing flame retardant into the phosphorus-containing flame retardant or an intermediate thereof so as to facilitate solvent extraction), then concentrating until no water exists to obtain the phosphorus-containing flame retardant or the phosphorus-containing flame retardant intermediate and sodium chloride, adding an organic solvent, uniformly stirring, filtering, concentrating the filtrate, carrying out reduced pressure distillation (mainly suitable for liquid low-boiling point flame retardants) or selecting a suitable solvent for recrystallization (mainly suitable for solid flame retardants) to obtain the phosphorus-containing flame retardant, washing a filter cake with the organic solvent, and drying to obtain the sodium chloride. The organic solvent is not limited to a certain organic solvent or a mixture of several organic solvents, and can be properly selected according to different phosphorus-containing flame retardants.
Pure sodium chloride, pure aluminum chloride hydrate and phosphorus-containing flame retardant or an intermediate thereof are obtained through the steps, the steps are clear, the function is clear, and the sodium chloride can be used for producing the methyldichlorophosphine; the aluminum chlorohydrate has high purity, reaches the standard of high-grade aluminum chlorohydrate, and can be used in casting and sewage treatment industries. The method of the invention completely solves the problem of comprehensive utilization of the composite salt in the production process of the methyldichlorophosphine, solves the industrial problem and lays a foundation for large-scale industrialization of the methyldichlorophosphine.
The comprehensive utilization method of the present invention preferably further comprises one or more of the following steps:
s6, the sodium chloride solid obtained in the step S2 is used in the methyl dichlorophosphine production process.
S7, the aluminum chlorohydrate obtained in the step S3 is used for casting and sewage treatment industries.
S8, further separating the concentrated hydrochloric acid obtained in the step S4 into hydrogen chloride gas and dilute hydrochloric acid, and using the hydrogen chloride gas and the dilute hydrochloric acid in the step S1, wherein the method for separating the concentrated hydrochloric acid can be, for example, a calcium chloride method or a sulfuric acid method, specifically, the calcium chloride method is a method of continuously separating hydrogen chloride by using a calcium chloride solution as a dehydrating agent, and continuously distilling the calcium chloride solution to obtain the dilute hydrochloric acid; the calcium chloride concentrated solution is continuously used as a dehydrating agent to separate hydrogen chloride; the sulfuric acid method is characterized in that concentrated sulfuric acid is used as a dehydrating agent to continuously separate hydrogen chloride, and a sulfuric acid solution is continuously distilled to obtain dilute hydrochloric acid and concentrated sulfuric acid, and the concentrated sulfuric acid is used as the dehydrating agent to continuously separate the hydrogen chloride.
S9, dissolving the sodium chloride obtained in the step S51 in water to obtain a sodium chloride aqueous solution, and returning to the step S1;
s10, the aluminum hydroxide obtained in the step S50 is returned to the step S2 to produce aluminum chloride.
S11, further preparing the phosphorus-containing flame retardant intermediate obtained in the step S51 into a phosphorus-containing flame retardant.
According to a preferred aspect of the present invention, the aldehyde compound according to step S1 of the present invention is the aldehyde compound as follows:
wherein in the general formula (1), R1Hydrogen, C1-C12 branched or straight chain alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with C1-C12 alkyl side chain, phenyl which is unsubstituted or substituted with one or more C1-C12 branched or straight chain alkyl, etc., preferably hydrogen, C1-C6 branched or straight chain alkyl, cyclohexyl, cyclopentyl, phenyl, etc. Further, R1Hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl.
The equation for the reaction of the aldehyde compound with methyldichlorophosphine to form the phosphorus-containing flame retardant or the intermediate thereof is as follows:
according to still another preferred aspect of the present invention, the aldehyde compound in step S1 of the present invention is preferably one or more selected from acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and phenylacetaldehyde.
The inventor innovatively discovers the comprehensive utilization method of the byproducts through a large number of experimental verifications and experimental optimization and simplification operations. The invention is not only suitable for the composite salt generated in the production process of methyldichlorophosphine, but also suitable for the composite salt generated in the production process of phenyl dichlorophosphine with similar friedel-crafts reaction.
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a composition, process, method, apparatus, article, or apparatus that comprises a list of elements, steps, or components is not necessarily limited to those elements or components expressly listed, but may include other elements or steps not expressly listed or inherent to such process, method, article, or apparatus.
In the following examples, the conditions used may be further adjusted according to specific requirements, and the conditions not specified are generally those in routine experiments. The raw materials used in the examples are all industrial products unless otherwise specified. The percentage% of the grade means mass% when not particularly stated.
In the following examples, the phosphorus-containing complex salt is a by-product from the production of methyldichlorophosphine, and includes a complex of sodium chloride and aluminum chloride, methyldichlorophosphine, and the like.
The components and phosphorus content of the phosphorus-containing composite salt are detected as follows: weighing 1.05 g of the compound salt sample, dissolving in 50 ml of water, fixing the volume in a 100 ml volumetric flask, measuring 1 ml of the volumetric flask, fixing the volume in a 1 l volumetric flask with water, measuring the phosphorus content by an ammonium molybdate spectrophotometry to be 0.205 mg/l, and converting the phosphorus content of the compound salt sample to be 19.5 g/kg. The reduced phosphorus content was 0.629 mol/kg. The sodium ion content was 12.23% as determined by ion chromatography, the reduced sodium chloride content was 31.11%, and the aluminum chloride content was 61.53% as determined by titration.
Example 1
The embodiment provides a recycling method of phosphorus-containing composite salt, which comprises the following steps:
s1, weighing 1000 g of phosphorus-containing composite salt in the same batch as the detection sample, adding the phosphorus-containing composite salt into 2100 g of 4% hydrochloric acid solution in batches, keeping the temperature of the system at about 50 ℃ in the adding process, adding 70 g of aqueous solution containing 28 g of acetaldehyde after the phosphorus-containing composite salt is completely added, and continuing stirring for 30 minutes to obtain a first mixture, wherein the related reaction equation is as follows:
s2, introducing 105 g of hydrogen chloride into the first mixture, continuously stirring for 30 minutes to precipitate sodium chloride, heating to 80 ℃, preserving heat for 1 hour, filtering, pulping and washing a filter cake by 650 g of 20% hydrochloric acid, filtering and drying to obtain 305 g of sodium chloride, calibrating the content of the sodium chloride to 99.56% by detecting sodium ions by using an ion chromatography, measuring the phosphorus content to 14.5ppm by using an ammonium molybdate spectrophotometry, and obtaining the recovery rate of the sodium chloride of 98%;
s3, combining the filtrates obtained after filtration in the step S2, continuously introducing 720 g of hydrogen chloride, filtering, washing a filter cake with 1100 g of 35% hydrochloric acid, drying the filter cake, weighing 1098.5 g, detecting the content of aluminum chlorohydrate to be 98.5% by a complexation method, detecting the content of sodium ions to be 0.42% by an ion chromatography, detecting the content of phosphorus to be 13.5ppm by an ammonium molybdate spectrophotometry, and determining the recovery rate of aluminum chloride to be 98.7%;
s4, combining the filtrate and the washing liquid obtained in the step S3, carrying out reduced pressure distillation, and absorbing vacuum tail gas by cooled distilled hydrochloric acid to obtain 3550 g of 36.7% hydrochloric acid;
s5, neutralizing 93.5 g of residual liquid after distillation in the step S4 with sodium hydroxide, filtering, adding concentrated hydrochloric acid into the filtrate to acidify until the pH value is 1, distilling under reduced pressure, evaporating water, adding 100 g of ethanol to dissolve the residue, filtering, washing the solid with 40 g of ethanol to obtain sodium chloride solid and phosphorus-containing flame retardant ethanol solution, distilling under reduced pressure after removing the ethanol, collecting liquid at 156 ℃ under the vacuum degree of 30Pa to obtain 71.2 g of liquid flame retardant (compound I-1), wherein the recovery rate of phosphorus is reduced to 92%, and the phosphorus spectrum of the flame retardant is shown in figure 1, which indicates that the prepared flame retardant has high purity.
Example 2
The embodiment provides a recycling method of phosphorus-containing composite salt, which comprises the following steps:
s1, weighing 1000 g of compound salt in the same batch as the detection sample, adding the compound salt into 2100 g of 3.5% hydrochloric acid solution in batches, keeping the temperature of the system at about 50 ℃ in the adding process, adding 70 g of benzaldehyde after the compound salt is completely added, and continuing stirring for 30 minutes to obtain a first mixture, wherein the related reaction equation is as follows:
s2, introducing 105 g of hydrogen chloride into the first mixture, continuously stirring for 30 minutes to precipitate sodium chloride, heating to 70 ℃, preserving heat for 1.5 hours, filtering, pulping and washing a filter cake by 650 g of 20% hydrochloric acid, filtering and drying to obtain 298.5 g of sodium chloride, detecting the content of sodium chloride in the sodium ion calibration by using an ion chromatography to obtain 99.47%, detecting the content of phosphorus by using an ammonium molybdate spectrophotometry to obtain 17.6ppm, and obtaining the recovery rate of the sodium chloride of 95.9%;
s3, combining the filtrates obtained after filtration in the step S2, continuously introducing 720 g of hydrogen chloride, washing filter cakes by 1100 g of 36.7% hydrochloric acid after filtration, weighing 1089 g of the dried filter cakes, detecting the content of aluminum chlorohydrate to be 98.2% by a complexation method, detecting the content of sodium ions to be 0.45% by ion chromatography, detecting the content of phosphorus to be 18.3ppm by an ammonium molybdate spectrophotometry, and recovering the recovery rate of aluminum chloride to be 97.8%;
s4, combining the filtrate and the washing liquid obtained in the step S3, carrying out reduced pressure distillation, and absorbing vacuum tail gas by cooled distilled hydrochloric acid to obtain 3565 g of 36.6% hydrochloric acid;
s5, neutralizing 135 g of residual liquid distilled in the step S4 with sodium hydroxide, filtering, adding concentrated hydrochloric acid into filtrate to acidify until the pH value is 1, distilling under reduced pressure, evaporating to remove water, adding 150 g of acetone, refluxing to dissolve the residue, filtering while the solution is hot, washing the solid with 50 g of hot acetone to obtain sodium chloride solid and phosphorus-containing flame retardant acetone solution, cooling to 10 ℃, filtering, and drying in vacuum to obtain 111.2 g (Mp94-96 ℃) of the solid flame retardant (compound I-2), wherein the recovery rate is 95.5% in terms of phosphorus.
Flame retardancy test
And (3) testing the flame retardance: in order to test the flame retardant performance of the flame retardant conveniently, epoxy resin is used as a polymer base material, specifically, bisphenol A epoxy resin (CYD-127) and a curing agent diaminodiphenylmethane (DDM) are taken, 100 g of the epoxy resin is added into the flame retardant obtained in the embodiment, the addition amounts of the flame retardant are respectively 10% and 15%, a high-speed dispersion machine is used for dispersing, 26 g of the curing agent is added, the temperature is raised to 145 ℃, the high-speed dispersion machine is used for dispersing continuously, the mixture is uniformly dispersed, the mixture is poured into a mold and placed into an oven, the temperature is kept at 160 ℃ for 4 hours, a sample is taken out of the mold after cooling, the sample is tested, and the flame retardant data (the carbon residue rate and the oxygen index at 600 ℃) are measured as shown in the following table 1.
TABLE 1
The flame retardant test data show that the flame retardant recovered by the method has excellent flame retardant performance which is equivalent to that of the same flame retardant produced normally.
Comparative example 1
The treatment of the phosphorus-containing complex salt was carried out according to the method reported in CN111689508A, as follows:
weighing 2000 g of water, heating to 80 ℃, taking 500 g of phosphorus-containing composite salt, adding the phosphorus-containing composite salt into 2000 g of water in batches, controlling the temperature of a reaction system to be 80 ℃, carrying out heat preservation reaction for 1 hour, introducing 350 g of hydrogen chloride, separating out solids, filtering, drying the solids at 70 ℃ in vacuum for 7 hours to obtain 102.6 g of solids, analyzing the weight of the solids to be 95.5 percent, the content of aluminum chlorohydrate to be 3.8 percent, the content of total phosphorus to be 0.278 percent, converting the solids into 2780ppm, concentrating and crystallizing the filtrate at normal pressure, stopping concentrating the filtrate at 110 ℃, cooling the crystals, filtering, drying the solids at 70 ℃ in vacuum for 7 hours to obtain 494.6 g of solids, analyzing the content of sodium chloride to be 8.68 percent, the content of aluminum chlorohydrate to be 90.0 percent, the content of total phosphorus to be 0.52 percent and converting the solids into 5200 ppm.
Comparative example 2
Substantially the same procedure as in example 1 was followed, except that the substance charged in S1 was not acetaldehyde, but p-methylphenol. The specific implementation process is as follows.
S1, weighing 1000 g of phosphorus-containing composite salt in the same batch as the detection sample, adding the phosphorus-containing composite salt into 2100 g of 4% hydrochloric acid solution in batches, adding 100 g of p-methylphenol, and keeping the system temperature at about 50 ℃ in the adding process to obtain a first mixture;
s2, introducing 105 g of hydrogen chloride into the first mixture, continuously stirring for 30 minutes, heating to 80 ℃, preserving heat for 1 hour, filtering, pulping and washing a filter cake with 650 g of 20% hydrochloric acid, filtering, and drying to obtain 295.3 g of sodium chloride, wherein the sodium chloride content is 99.38% by detecting sodium ions through ion chromatography, the phosphorus content is 19.2ppm by ammonium molybdate spectrophotometry, and the recovery rate of the sodium chloride is 94.9%;
s3, combining the filtrate of the filtering step in the S2 step, continuously introducing 720 g of hydrogen chloride, filtering, washing a filter cake by 1100 g of 35% hydrochloric acid, drying, weighing 1046.9 g of the dried filter cake to obtain aluminum chlorohydrate, detecting the content of the aluminum chlorohydrate to be 97.9% by using a complex method, detecting the content of sodium ions reduced to 0.41% by using an ion chromatography, detecting the content of phosphorus to be 15.4ppm by using an ammonium molybdate spectrophotometry, and recovering 94.1% of the aluminum chlorohydrate;
s4, combining the filtrate filtered in S3 with a washing solution, distilling under reduced pressure, and absorbing vacuum tail gas by cooled distilled hydrochloric acid to obtain 3542 g of 36.7% hydrochloric acid;
s5, neutralizing 196.5 g of residual liquid obtained by reduced pressure distillation in S4 with sodium hydroxide, filtering, adding concentrated hydrochloric acid into filtrate to acidify until the pH value is 1, carrying out reduced pressure distillation, evaporating water, adding 100 g of ethanol to dissolve residues, filtering, and washing filter cakes with 40 g of ethanol to obtain sodium chloride solid; the filtrate and the washing liquid are combined to obtain phosphorus-containing fire retardant ethanol solution, after ethanol is evaporated, 90.5 g of p-methylphenol is obtained by reduced pressure distillation, the fraction at 175 ℃ and 178 ℃ is collected under the vacuum degree of 5Pa to obtain 12.4 g of liquid fire retardant, the residual high boiling point fraction is 60.2 g, and the recovery rate of the converted phosphorus is 11.6%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (16)
1. A method for comprehensively recycling alkyl dichlorophosphine production byproducts, wherein the alkyl dichlorophosphine production byproducts comprise sodium chloride and aluminum chloride composite salts and alkyl dichlorophosphine, and the method is characterized by comprising the following steps of:
s1, reacting the alkyl dichlorophosphine in the alkyl dichlorophosphine production byproduct with an aldehyde compound in the presence of water to generate a phosphorus-containing flame retardant or an intermediate thereof, so as to obtain a first mixture containing the phosphorus-containing flame retardant or the intermediate thereof, sodium chloride and aluminum chloride;
s2, introducing hydrogen chloride and/or adding hydrochloric acid into the first mixture to enable the mass percentage of the hydrogen chloride in the mixture solution to reach 5% -15%, crystallizing and separating out sodium chloride, filtering, washing a filter cake with the hydrochloric acid to obtain pure sodium chloride solid, wherein the filtrate is a second mixture containing a very small amount of sodium chloride, aluminum trichloride, a phosphorus-containing flame retardant or an intermediate thereof and the hydrochloric acid;
s3, introducing hydrogen chloride gas and/or adding hydrochloric acid into the filtrate obtained after filtration in the step S2 to enable the mass content of hydrogen chloride in the mixture solution to be more than or equal to 35%, enabling aluminum chloride to be precipitated in the form of aluminum trichloride hydrate, filtering, washing a filter cake with hydrochloric acid, and drying to obtain aluminum trichloride hydrate, wherein the filtrate is a third mixture containing a phosphorus-containing flame retardant or an intermediate thereof, aluminum chloride, sodium chloride and hydrochloric acid;
s4, distilling and concentrating the third mixture obtained in the step S3 to obtain concentrated hydrochloric acid and a phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or an intermediate thereof;
s5, adding sodium hydroxide into the phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or the intermediate thereof, and separating and removing the aluminum hydroxide and the sodium chloride to obtain the phosphorus-containing flame retardant or the intermediate thereof.
2. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the alkyl dichlorophosphine production byproducts, the aldehyde compound and the dilute hydrochloric acid are mixed and reacted at a temperature of 40-100 ℃, and the mass percentage of the dilute hydrochloric acid is less than or equal to 10%.
3. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 2, wherein in step S1, the alkyl dichlorophosphine production byproducts are added to the dilute hydrochloric acid in batches, the system temperature is kept at 40-100 ℃ in the adding process, and after the addition of the alkyl dichlorophosphine production byproducts is finished, an aldehyde compound or an aqueous solution in which the aldehyde compound is dispersed is added, and the mixture is stirred for reaction to obtain the first mixture.
4. The method for comprehensively recycling alkyl dichlorophosphine production byproducts as claimed in claim 1, wherein in the steps S2 and S3, the hydrochloric acid used for washing is concentrated hydrochloric acid with the mass percentage of 30-37%.
5. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the aldehyde compound has a structure represented by the following general formula (1):
wherein R is1Hydrogen, C1-C12 branched or straight chain alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl with a C1-C12 alkyl side chain, phenyl which is unsubstituted or substituted with one or more C1-C12 branched or straight chain alkyl groups.
6. The method for comprehensively recycling alkyl dichlorophosphine production by-products according to claim 5, wherein in the general formula (1), R is1Hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl.
7. The method of claim 5, wherein in step S1, the aldehyde compound is one or more selected from acetaldehyde, benzaldehyde, and phenylacetaldehyde.
8. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 1, wherein the content of alkyl dichlorophosphine in the phosphorus-containing composite salt is obtained before step S1, and in step S1, the ratio of the alkyl dichlorophosphine to the aldehyde compound is 1: 1.01-1.3, feeding.
9. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 8, wherein in step S1, the molar ratio of alkyl dichlorophosphine to aldehyde compounds is 1: 1.01-1.1, feeding.
10. The method for comprehensively recycling alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the usage amount of the dilute hydrochloric acid is 1-10 times that of the phosphorus-containing composite salt; and/or the reaction temperature is 45-60 ℃.
11. The comprehensive recycling method of alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the mass percentage of the dilute hydrochloric acid is 2-5%; and/or in step S2, introducing hydrogen chloride to make the mass percentage of the hydrogen chloride in the mixture solution reach 6-10%; and/or in step S3, introducing hydrogen chloride to ensure that the mass content of the hydrogen chloride in the mixture solution is 35-45%.
12. The method for comprehensively recycling alkyl dichlorophosphine production byproducts as claimed in claim 1, wherein in step S1, after the sodium chloride is crystallized and precipitated and before filtration, the system is kept at 70-90 ℃ for 1-2 hours.
13. The method for comprehensively recycling the alkyl dichlorophosphine production byproduct as claimed in claim 1, wherein the step S5 further comprises:
s50: adding sodium hydroxide to the phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or the intermediate thereof obtained in step S4 to allow the aluminum chloride in a dissolved state to generate sodium chloride and aluminum hydroxide to obtain a mixture containing aluminum hydroxide, sodium chloride, a phosphorus-containing flame retardant or a sodium salt of the intermediate thereof, and filtering to obtain a filtrate which is an aqueous solution of the phosphorus-containing flame retardant or the sodium salt of the intermediate thereof and sodium chloride;
s51: and (4) adding hydrochloric acid into the filtrate obtained in the step (S50) for acidification so as to enable the phosphorus-containing flame retardant or the intermediate sodium salt thereof to be dissociated into the phosphorus-containing flame retardant or the intermediate thereof, then concentrating until no water exists to obtain the phosphorus-containing flame retardant or the phosphorus-containing flame retardant intermediate and sodium chloride, adding an organic solvent, uniformly stirring, filtering, concentrating the filtrate, carrying out reduced pressure distillation or recrystallization to obtain the phosphorus-containing flame retardant or the intermediate thereof, washing the filter cake with the organic solvent, and drying to obtain sodium chloride.
14. The method of claim 1, wherein said alkyl dichlorophosphine is methyl dichlorophosphine, and further comprising: s6, the sodium chloride solid obtained in the step S2 is used in the methyl dichlorophosphine production process.
15. The integrated recycling method of alkyl dichlorophosphine production byproducts according to claim 13, further comprising one or more of the following steps:
s7, the aluminum chlorohydrate obtained in the step S3 is used for casting and sewage treatment industries;
s8, further separating the concentrated hydrochloric acid obtained in the step S4 into hydrogen chloride gas and dilute hydrochloric acid for use in a step S1;
s9, dissolving the sodium chloride obtained in the step S5 in water to obtain a sodium chloride aqueous solution, returning to the step S1, mixing the sodium chloride aqueous solution with dilute hydrochloric acid, and dissolving the complex salt;
s10, returning the filter cake filtered in the step S50, namely the aluminum hydroxide, to the step S2 for generating aluminum chloride;
s11, further preparing the phosphorus-containing flame retardant intermediate obtained in the step S51 into a phosphorus-containing flame retardant.
16. A method for producing an alkyl dichlorophosphine comprising: (1) obtaining an alkyl dichlorophosphine and a sodium chloride-aluminium chloride complex salt by-product containing the alkyl dichlorophosphine, characterized in that the production method also comprises (2): the comprehensive recycling method of any one of claims 1 to 15 is adopted to recover and obtain sodium chloride, aluminum chlorohydrate, phosphorus-containing flame retardant or intermediate thereof.
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