CN114620745B - Comprehensive recycling method for alkyl dichlorophosphine production byproducts - Google Patents
Comprehensive recycling method for alkyl dichlorophosphine production byproducts Download PDFInfo
- Publication number
- CN114620745B CN114620745B CN202011434507.XA CN202011434507A CN114620745B CN 114620745 B CN114620745 B CN 114620745B CN 202011434507 A CN202011434507 A CN 202011434507A CN 114620745 B CN114620745 B CN 114620745B
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- chloride
- hydrochloric acid
- dichlorophosphine
- sodium chloride
- 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 117
- 238000000034 method Methods 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 239000006227 byproduct Substances 0.000 title claims abstract description 47
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 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 197
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 107
- 239000011574 phosphorus Substances 0.000 claims abstract description 107
- 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 93
- 239000003063 flame retardant Substances 0.000 claims abstract description 81
- 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 77
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000000706 filtrate Substances 0.000 claims abstract description 40
- 238000001914 filtration Methods 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 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000543 intermediate Substances 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007789 gas 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
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000011084 recovery Methods 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
- 239000003960 organic solvent Substances 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
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- 238000005266 casting Methods 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
- 238000002156 mixing Methods 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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 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 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 229940063656 aluminum chloride Drugs 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- 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
- 238000004255 ion exchange chromatography Methods 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
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000005303 weighing 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
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 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
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 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
- 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
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 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
- 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
- 229940050176 methyl chloride Drugs 0.000 description 2
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical compound Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-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
- 239000002699 waste material Substances 0.000 description 2
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-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
- 239000005561 Glufosinate Substances 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 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
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 description 1
- HZHUAESPXGNNFV-UHFFFAOYSA-N diethyl(methyl)phosphane Chemical compound CCP(C)CC HZHUAESPXGNNFV-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
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 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
- 230000020477 pH reduction Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium 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
- 238000001291 vacuum drying Methods 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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 byproducts to generate a phosphorus-containing flame retardant or an intermediate thereof, obtaining a mixture after reaction, then gradually separating sodium chloride and precipitate in the form of hydrated aluminum trichloride by gradually increasing the content of hydrogen chloride in the system in a step-by-step 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, distilling and concentrating, adding sodium hydroxide, filtering, acidifying and concentrating the filtrate, extracting, and purifying; the method provided by the invention obtains pure sodium chloride and pure aluminum chloride hydrate, and obtains the phosphorus-containing flame retardant or the intermediate thereof, the steps are clear, the functions are clear, the method is simple and easy to control, and the comprehensive utilization problem of the compound salt in the production process of the methyl dichlorophosphine is completely solved.
Description
Technical Field
The invention relates to the technical field of recycling of phosphorus-containing byproducts in the production process of an organic phosphine intermediate alkyl dichlorophosphine, in particular to a comprehensive utilization method of phosphorus-containing compound salt.
Background
Alkyl dichlorophosphine is also called alkyl dichlorophosphine, is an important intermediate of an organic phosphine compound, particularly methyl dichlorophosphine, and is a core raw material for synthesizing herbicide glufosinate intermediate diethyl methylphosphine. The main production methods of the methyl dichlorophosphine at present mainly comprise the following three methods:
1. the phosphorus trichloride and methane pass through a tubular reactor, a condenser and a fractionating device under the existence of a high-temperature high-pressure catalyst to obtain methyl dichlorophosphine, and the method is easy to produce sediment to cause the blockage of the tubular reactor and the condenser, so that the production is interrupted, the conversion rate of the product is lower, and the energy consumption is higher.
2. And carrying out complexing reaction on phosphorus trichloride, aluminum trichloride and methyl chloride in an autoclave to generate a ternary complex, reducing the ternary complex by aluminum powder to obtain a complex of methyl dichlorophosphine and aluminum trichloride, and dissociating the complex under the action of sodium chloride to obtain a composite salt of the methyl dichlorophosphine and the residual byproduct sodium chloride and aluminum chloride.
3. Methyl chloride reacts with aluminum alloy to generate a mixture of methyl aluminum dichloride and dimethyl aluminum chloride, the mixture reacts with phosphorus trichloride to generate a complex of methyl phosphine dichloride and aluminum chloride, the complex reacts with sodium chloride to dissociate methyl phosphine dichloride, and the residual byproduct sodium chloride and aluminum chloride is a compound salt.
In the above method, although the methods 2 and 3 do not have high temperature and high pressure, the content of the residual methyl dichlorophosphine in the aluminum chloride and sodium chloride composite salt is higher due to insufficient dissociation of sodium chloride to the methyl dichlorophosphine and aluminum trichloride, so that the composite salt of the aluminum chloride and the sodium chloride cannot be recycled well, and the method is a huge obstacle for the production of the methyl dichlorophosphine. In view of this problem, the prior art proposes a number of different solutions, such as:
the Chinese patent No. 105217667B discloses that the mixture of the alcohol and the ether serving as a decomposition agent is used for decomposing sodium chloride and aluminum chloride to obtain aluminum chloride, and the aluminum chloride is reused, and the method does not refer to the treatment of the phosphorus-containing compound and sodium chloride in sodium chloride and sodium tetrachloroaluminate serving as a compound salt, so that the phosphorus-containing compound and the sodium chloride cannot be recovered.
The Chinese patent No. 108238621A discloses a method for preparing polyaluminum chloride by using composite salt, which comprises the steps of dissolving the composite salt, adding ferric chloride, hydrochloric acid, sodium hydroxide, sodium metaaluminate and the like for polymerization reaction, cooling and filtering to obtain polyaluminum chloride solution, wherein the method provides a method for preparing the polyaluminum chloride by using the composite salt, but the method can lead a large amount of sodium chloride and a small amount of phosphorus-containing compound to enter a polyaluminum chloride system, and the use field of the polyaluminum chloride produced by the method is limited because the phosphorus-containing compound is contained in the polyaluminum chloride.
The Chinese patent No. 111187297A discloses a method for recycling phosphine-containing industrial byproducts, which comprises the steps of placing byproducts generated in the production process of methyl diethyl phosphite in a reaction vessel, adding phenolic compounds or binary or more aromatic amine compounds or compounds containing oxirane functional groups, heating and reacting 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 an exothermic process; cooling, filtering, using the obtained filter residue as a phosphorus flame retardant, and continuously performing solid-liquid separation on the obtained first filtrate, wherein the first filtrate is heated to 100-120 ℃ until crystals appear, the heating is stopped when the amount of the crystals is not increased, and the obtained solid is sodium chloride crystals; slowly adding water into the obtained second filtrate, cooling to room temperature, adjusting the pH of the second filtrate to prepare polyaluminum chloride, specifically adding ferric chloride and hydrochloric acid into the second filtrate, stirring and mixing uniformly, controlling the temperature of a reaction solution to be more than 85 ℃, sequentially adding aluminum hydroxide and calcium metaaluminate, controlling the reaction temperature to be 100 ℃, and reacting to obtain the polyaluminum chloride. The method can recycle methyl dichlorophosphine, but the added phenolic substances or binary or more aromatic amine compounds or epoxy compounds can enter a polyaluminium system to cause the polyaluminium to be polluted without application value, and in addition, the phenolic substances can be dissolved in the filtrate in a large amount to cause new waste liquid treatment problems. In addition, the method has the advantages of complex process, high control difficulty and inconvenient operation.
Chinese patent No. 111689508A discloses a method for treating sodium tetrachloroaluminate solid slag, which comprises (1) mixing sodium tetrachloroaluminate solid slag with water for dissociation, adding a separating agent to separate out aluminum chloride hexahydrate, or directly mixing sodium tetrachloroaluminate solid slag with the separating agent for dissociation, separating out aluminum chloride hexahydrate, and 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 carrying out secondary solid-liquid separation to obtain sodium chloride solid and secondary filtrate, and returning the secondary filtrate to the step (1) to provide the separating agent required by precipitation of aluminum chloride hexahydrate. The process has proven to separate sodium chloride from aluminum chloride, however, the solution reported in this patent has errors, in particular, in step (1) it is not the aluminum chloride hexahydrate that is first obtained, but the sodium chloride that is finally obtained, sodium chloride and aluminum chloride, which do not meet the standard requirements due to contamination from phosphorus compounds in the solid residual mother liquor.
In summary, in the prior art, the utilization of the complex salt generated in the production process of the methyl dichlorophosphine cannot be fully and effectively achieved, and some utilization methods have the problems of complex process, high control difficulty and the like.
Disclosure of Invention
The invention provides a comprehensive utilization method of byproducts in the production process of methyl dichlorophosphine, which can fully and effectively recycle the byproducts in the production process of methyl dichlorophosphine, and has the advantages of simple process and easy control.
In order to solve the problems, the invention adopts the following technical scheme:
the comprehensive recycling method of the alkyl dichlorophosphine production byproducts comprises sodium chloride and aluminum chloride composite salt and alkyl dichlorophosphine, and comprises the following steps:
s1, reacting alkyl dichlorophosphine in the alkyl dichlorophosphine production byproducts with an aldehyde compound in the presence of water to generate a phosphorus-containing flame retardant or an intermediate thereof, and obtaining 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 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, phosphorus-containing flame retardant or an intermediate thereof and hydrochloric acid;
s3, introducing hydrogen chloride gas and/or adding hydrochloric acid into the filtrate obtained after the filtration in the step S2, so that the mass content of the hydrogen chloride in the mixture solution is more than or equal to 35%, separating out aluminum chloride 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 phosphorus-containing flame retardant or an intermediate thereof, aluminum chloride, sodium chloride and hydrochloric acid;
s4, distilling and concentrating the third mixture in the step S3 to obtain concentrated hydrochloric acid and a phosphorus-containing flame retardant or an intermediate thereof mixed with aluminum chloride and sodium chloride;
s5, separating and removing the aluminum chloride and the sodium chloride from the phosphorus-containing flame retardant or the intermediate thereof mixed with the aluminum chloride and the sodium chloride to obtain the phosphorus-containing flame retardant or the intermediate thereof.
In step S1, the alkyl dichlorophosphine production byproducts, aldehyde compounds and dilute hydrochloric acid are mixed and reacted at the temperature of 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 kept 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 stirring reaction is performed to obtain the first mixture.
Further, in the steps S2 and S3, the hydrochloric acid for washing is concentrated hydrochloric acid with a mass percentage of 30% -37%, respectively.
Further, in step S1, the aldehyde compound preferably has a structure represented by the following general formula (1):
wherein R is 1 Is hydrogen, C1-C12 branched or straight chain alkyl, 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), R 1 Can be hydrogen, methyl, ethyl and propylA group, 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 a combination of more selected from acetaldehyde, benzaldehyde and phenylacetaldehyde.
According to some preferred aspects of the present invention, the content of the alkyl dichlorophosphine in the phosphorus-containing composite salt is obtained before step S1 is performed, and in step S1, the molar ratio of the alkyl dichlorophosphine to the aldehyde compound is 1:1.01 to 1.3.
Further preferably, in step S1, the molar ratio of alkyl dichlorophosphine to aldehyde compound is 1:1.01 to 1.1.
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 that of the phosphorus-containing compound salt. Further preferably, in step S1, the amount of the diluted hydrochloric acid used is 1 to 5 times that of the phosphorus-containing compound salt.
According to some preferred aspects of the present invention, in step S1, the mass percentage of the diluted hydrochloric acid is 2% to 5%; in the step S2, the mass percentage of the hydrochloric acid used for washing the filter cake is 30-37%.
According to some preferred aspects of the invention, in step S2, hydrogen chloride is introduced to bring the mass percentage of hydrogen chloride in the mixture solution to 6% -10%; and/or, in the 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 methyl dichlorophosphine and the phosphorus-containing complex salt is a byproduct from the production of methyl dichlorophosphine. The comprehensive recycling method of the alkyl dichlorophosphine production byproducts also comprises the following steps: s6, using the sodium chloride solid obtained in the step S2 in the production process of the methyl dichlorophosphine.
According to some preferred aspects of the present invention, the method for comprehensive recycling of alkyl dichlorophosphine production byproducts further comprises: and S7, using the aluminum chlorohydrate obtained in the step S3 in the casting and sewage treatment industry.
According to some preferred aspects of the present invention, the method for comprehensive recycling of alkyl dichlorophosphine production byproducts further comprises: and 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.
Further, in step S8, the method for separating the concentrated hydrochloric acid is a calcium chloride method or a sulfuric acid method; the calcium chloride method is to continuously separate out hydrogen chloride by using a calcium chloride solution as a dehydrating agent, and continuously distill 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 process includes continuously separating hydrogen chloride with concentrated sulfuric acid as dewatering agent, and continuously distilling sulfuric acid solution to obtain dilute hydrochloric acid and concentrated sulfuric acid as dewatering agent to separate hydrogen chloride continuously.
Preferably, in step S1, after precipitation of sodium chloride crystals and before filtration, the system is incubated at 70 to 90℃for 1 to 2 hours. The subsequent filtering and separating operation of sodium chloride can be easier by heat preservation.
According to a preferred aspect of the present invention, step S5 further comprises:
s50: adding sodium hydroxide into the phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or the intermediate thereof obtained in the step S4 to enable the aluminum chloride in a dissolved state to generate sodium chloride and aluminum hydroxide, obtaining a mixture containing aluminum hydroxide, sodium chloride, the phosphorus-containing flame retardant or the sodium salt of the intermediate thereof, and filtering, wherein the filtrate is an aqueous solution of the phosphorus-containing flame retardant or the sodium salt of the intermediate thereof and the sodium chloride;
s51: adding hydrochloric acid into the filtrate obtained in the step S50 to acidify to enable the phosphorus-containing flame retardant or the intermediate sodium salt to be dissociated into the phosphorus-containing flame retardant or the intermediate, concentrating to be anhydrous to obtain the phosphorus-containing flame retardant or the phosphorus-containing flame retardant intermediate and sodium chloride, adding an organic solvent to stir uniformly, filtering, concentrating the filtrate, distilling under reduced pressure or recrystallizing to obtain the phosphorus-containing flame retardant or the intermediate, washing the filter cake with the organic solvent, and drying to obtain the sodium chloride.
According to some preferred aspects of the present invention, the method for comprehensive recycling of alkyl dichlorophosphine production byproducts further comprises one or more steps of:
s9, dissolving the sodium chloride obtained in the step S5 with water to obtain a sodium chloride aqueous solution, and returning to the step S1 to be mixed with dilute hydrochloric acid for dissolving the compound salt;
s10, returning the filter cake filtered in the step S50, namely 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 byproducts containing the alkyl dichlorophosphine,
(2) The comprehensive recycling method of the alkyl dichlorophosphine production byproducts is adopted to recycle and obtain sodium chloride, aluminum chlorohydrate, phosphorus-containing flame retardant or an intermediate thereof.
Further, the production method further comprises (3) using the sodium chloride recovered in (2) above as a raw material in step (1).
In one embodiment according to the present invention, the alkyl dichlorophosphine includes methyl dichlorophosphine, phenyl dichlorophosphine, and the like.
In the invention, if the mass percentage concentration is not specified, the mass percentage content of hydrogen chloride and sulfuric acid in the related dilute hydrochloric acid and concentrated sulfuric acid are all within the conventional definition range of 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 a phosphorus-containing flame retardant or an intermediate thereof with higher added value; sodium chloride with the content of 99.5 percent or more can be obtained and can be recycled in the production process of the methyl dichlorophosphine; and aluminum chloride hydrate with the content of 97 percent or more can be obtained, and the standard of the aluminum chloride hydrate superior product is completely met; the hydrochloric acid used can be separated to obtain hydrogen chloride and dilute hydrochloric acid, and the hydrogen chloride and the dilute hydrochloric acid are reused for the treatment of the composite salt. Compared with the prior art, the method can realize the efficient recovery of all useful substances, has no waste liquid, has lower recovery cost, simple process and simple and convenient operation, and can truly and thoroughly solve the comprehensive utilization problem of the byproduct in the production of the alkyl dichlorophosphine.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a phosphine spectrum of the flame retardant prepared in example 1.
Detailed Description
The invention will be described in further detail by taking a comprehensive utilization method of byproducts (phosphorus-containing compound salts) in the production process of methyl dichlorophosphine as an example.
According to some embodiments of the present invention, a method for comprehensively utilizing byproducts in a production process of methyl dichlorophosphine includes the steps of:
s1, adding an alkyl dichlorophosphine production byproduct into dilute hydrochloric acid in batches, keeping the temperature of a system at 40-100 ℃ in the adding process, and adding an aldehyde compound or an aqueous solution dispersed with the aldehyde compound after the addition of the alkyl dichlorophosphine production byproduct is finished, and stirring for reaction to obtain a first mixture; in this step, the amount of the aldehyde compound to be fed is preferably excessive relative to the phosphorus-containing component such as methyl dichlorophosphine, and the molar ratio of the aldehyde compound to methyl dichlorophosphine 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 temperature of the reaction is 40 to 100 degrees celsius, more preferably 40 to 70 degrees celsius, still more preferably 45 to 60 degrees celsius. The concentration of the diluted hydrochloric acid used is preferably 10% or less, more preferably 5% or less, and the amount thereof is generally 1 to 10 times, preferably 1 to 5 times, the amount of the phosphorus-containing compound salt; in addition, the diluted hydrochloric acid used may be produced by separation from the concentrated hydrochloric acid obtained in the subsequent step.
S2, supplementing a certain amount of hydrogen chloride into the first mixture by utilizing an ion effect, sufficiently reducing the solubility of sodium chloride by utilizing a mode of increasing chloride ions, crystallizing, separating out, preferably preserving heat (enabling the sodium chloride to be subjected to crystal form conversion to facilitate subsequent filtration), filtering, washing a filter cake by 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 methyl dichlorophosphine, wherein the filtrate is a second mixture containing a very small amount of sodium chloride, aluminum trichloride, phosphorus-containing flame retardant or an intermediate thereof and hydrochloric acid. Preferably, the hydrogen chloride is supplemented to a concentration of 6% -10% of the hydrogen chloride in the mixture solution. The temperature of the heat preservation can be 70-90 ℃, the heat preservation time can be 1-2 hours, the hydrochloric acid concentration for washing is preferably concentrated hydrochloric acid, and the specific concentration is 30-37 percent.
And S3, continuously introducing hydrogen chloride gas into the second mixture obtained in the step S2, continuously increasing the chloride ion content, enabling the hydrogen chloride content to be more than 35%, separating out aluminum chloride in the form of aluminum trichloride hydrate, filtering, washing a filter cake with concentrated hydrochloric acid, merging the filtrate, and drying the filter cake to obtain the aluminum trichloride hydrate. The filtrate is a third mixture containing phosphorus-containing flame retardant or intermediate thereof, a small amount of aluminum chloride and sodium chloride, and hydrochloric acid. The hydrogen chloride introduced may be hydrogen chloride produced by separating concentrated hydrochloric acid obtained in a subsequent step. Preferably, the hydrogen chloride is introduced to make the content of the hydrogen chloride 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 or an intermediate thereof mixed with a small amount of aluminum chloride and sodium chloride. Preferably, wherein the distillative concentration is reduced pressure multi-effect distillative concentration;
s5, separating 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, wherein the method specifically comprises the following steps of:
s50: neutralizing the phosphorus-containing flame retardant or the intermediate thereof mixed with a small amount of aluminum chloride and sodium chloride obtained in the step S4 with sodium hydroxide (preparing the aluminum chloride in a dissolved state 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, and filtering, wherein the filtrate is an aqueous solution of the phosphorus-containing flame retardant or the intermediate sodium salt 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), concentrating until no water exists, obtaining 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, and performing reduced pressure distillation (mainly suitable for liquid low-boiling flame retardants) or selecting a proper solvent for recrystallization (mainly suitable for solid flame retardants), obtaining the phosphorus-containing flame retardant, washing a filter cake by the organic solvent, and drying to obtain the sodium chloride. The organic solvent is not limited to one or a mixture of several organic solvents, and can be selected appropriately for different phosphorus-containing flame retardants.
The invention obtains pure sodium chloride and pure aluminum chloride hydrate through the steps, and obtains the phosphorus-containing flame retardant or the intermediate thereof, the steps are clear and the functions are clear, and the sodium chloride can be used for the production of methyl dichlorophosphine; the aluminum chloride hydrate has high purity, reaches the standard of high-grade aluminum chloride hydrate products, and can be used in the industries of casting and sewage treatment. The method completely solves the problem of comprehensive utilization of the compound salt in the production process of the methyl dichlorophosphine, solves the industrial problem, and lays a foundation for large-scale industrialization of the methyl dichlorophosphine.
The comprehensive utilization method of the present invention preferably further comprises one or more steps of:
s6, using the sodium chloride solid obtained in the step S2 in the production process of the methyl dichlorophosphine.
And S7, using the aluminum chlorohydrate obtained in the step S3 in the casting and sewage treatment industry.
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 to use a calcium chloride solution as a dehydrating agent, continuously separate hydrogen chloride, and continuously distill 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 process includes continuously separating hydrogen chloride with concentrated sulfuric acid as dewatering agent, and continuously distilling sulfuric acid solution to obtain dilute hydrochloric acid and concentrated sulfuric acid as dewatering agent to separate hydrogen chloride continuously.
S9, dissolving the sodium chloride obtained in the step S51 with water to obtain a sodium chloride aqueous solution, and returning to the step S1;
and S10, returning the filter cake obtained in the step S50, namely 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.
According to a preferred aspect of the present invention, the aldehyde compound according to step S1 of the present invention is an aldehyde compound as follows:
wherein in the general formula (1), R 1 Is hydrogen, C1-C12 branched or straight-chain alkyl, 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, or the like, preferably hydrogen, C1-C6 branched or straight-chain alkyl, cyclohexenyl, cyclopentyl, phenyl, or the like. Further, R 1 Is hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl.
The reaction of aldehyde compounds with methyl dichlorophosphine to produce a phosphorus-containing flame retardant or intermediate thereof has the following equation:
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 the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, phenylacetaldehyde.
The inventor has innovatively found a comprehensive utilization method of the byproducts through a large number of experimental verification, experimental optimization and simplified operation. The invention is not only suitable for the compound salt generated in the production process of the methyl dichlorophosphine, but also suitable for the compound salt generated in the production process of the phenyl dichlorophosphine by similar Pack reaction.
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "comprises" and "comprising," along with any variations thereof, are intended to cover a non-exclusive inclusion, such that a composition, process, method, apparatus, article, or device that comprises a list of elements, steps, or units, is not necessarily limited to those steps or units that are expressly listed or inherent to such process, method, article, or device.
In the following examples, the implementation conditions employed may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments. All the raw materials used in the examples were industrial products unless otherwise specified. The percent% of the stage refers to mass percent when not specifically stated.
In the following examples, phosphorus-containing complex salts are by-products from the production process of methyldichlorophosphine, and include complexes of sodium chloride and aluminum chloride, methyldichlorophosphine, and the like.
The components of the phosphorus-containing compound salt and the content of phosphorus are detected as follows: 1.05 g of the compound salt sample is weighed, dissolved in 50 ml of water, and fixed in a 100 ml volumetric flask, 1 ml of water is measured again, the phosphorus content is measured to be 0.205 mg/l by an ammonium molybdate spectrophotometry, and the phosphorus content of the compound salt sample is converted to be 19.5 g/kg. The reduced phosphorus content was 0.629 mol/kg. The content of sodium ions measured by ion chromatography is 12.23%, the reduced sodium chloride content is 31.11%, and the content of aluminum chloride measured by titration is 61.53%.
Example 1
The embodiment provides a recycling method of phosphorus-containing compound salt, which is implemented as follows:
s1, weighing 1000 g of phosphorus-containing compound salt in the same batch as a detection sample, adding the 1000 g of phosphorus-containing compound 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 compound salt is completely added, and continuously stirring for 30 minutes to obtain a first mixture, wherein the reaction equation is as follows:
s2, introducing 105 g of hydrogen chloride into the first mixture, continuously stirring for 30 minutes to separate out sodium chloride, heating to 80 ℃, preserving heat for 1 hour, filtering, pulping and washing a filter cake by using 650 g of 20% hydrochloric acid, filtering, drying to obtain 305 g of sodium chloride, detecting the content of sodium chloride to be 99.56% by using ion chromatography, detecting the content of phosphorus to be 14.5ppm by using an ammonium molybdate spectrophotometry, and recovering 98% of sodium chloride;
s3, merging the filtered filtrate obtained in the step S2, continuing to introduce 720 g of hydrogen chloride, filtering, washing a filter cake with 1100 g of 35% hydrochloric acid, weighing 1098.5 g of the filter cake after drying, detecting the content of aluminum chloride hydrate to be 98.5% by using a complexation method, detecting the content of sodium ions to be 0.42% by using an ion chromatography, detecting the content of phosphorus to be 13.5ppm by using an ammonium molybdate spectrophotometry method, and recovering the aluminum chloride to be 98.7%;
s4, combining the filtrate and the washing liquid obtained in the step S3, performing 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 obtained after distillation in the step S4 with sodium hydroxide, filtering, adding concentrated hydrochloric acid into filtrate to acidify to pH value of 1, distilling under reduced pressure, evaporating to dry water, adding 100 g of ethanol to dissolve residues, filtering, washing solids with 40 g of ethanol to obtain sodium chloride solids and an ethanol solution of the phosphorus-containing flame retardant, distilling under reduced pressure after evaporating ethanol, collecting liquid at 154-156 ℃ under vacuum degree of 30Pa to obtain 71.2 g of liquid flame retardant (compound I-1), wherein the recovery rate of folded phosphorus is 92%, and the phosphorus spectrum of the flame retardant is shown as figure 1, thus indicating that the prepared flame retardant has high purity.
Example 2
The embodiment provides a recycling method of phosphorus-containing compound salt, which is implemented as follows:
s1, weighing 1000 g of compound salt in the same batch as a 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 continuously stirring for 30 minutes to obtain a first mixture, wherein the reaction equation is as follows:
s2, introducing 105 g of hydrogen chloride into the first mixture, continuously stirring for 30 minutes, heating to 70 ℃, preserving heat for 1.5 hours, filtering, pulping and washing a filter cake by using 650 g of 20% hydrochloric acid, filtering and drying to obtain 298.5 g of sodium chloride, detecting the sodium ion by ion chromatography to calibrate the content of the sodium chloride to 99.47%, detecting the phosphorus content by using an ammonium molybdate spectrophotometry to 17.6ppm, and recovering the sodium chloride to 95.9%;
s3, merging the filtered filtrate obtained in the step S2, continuing to introduce 720 g of hydrogen chloride, filtering, washing a filter cake with 1100 g of 36.7% hydrochloric acid, weighing 1089 g of the filter cake after drying, detecting the content of aluminum chloride hydrate to be 98.2% by using a complexation method, detecting the content of sodium ions to be 0.45% by using an ion chromatography, detecting the content of phosphorus to be 18.3ppm by using an ammonium molybdate spectrophotometry method, and recovering the aluminum chloride to be 97.8%;
s4, combining the filtrate and the washing liquid obtained in the step S3, performing 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 obtained after distillation 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 dry water, adding 150 g of acetone to dissolve residues, filtering while hot, washing solids with 50 g of hot acetone to obtain sodium chloride solids and a phosphorus-containing flame retardant acetone solution, cooling to 10 ℃, filtering, and vacuum drying to obtain 111.2 g (Mp 94-96 ℃) of solid flame retardant (compound I-2), wherein the recovery rate of the reduced phosphorus is 95.5%.
Flame retardancy test
Flame retardancy test: in order to conveniently test the flame retardant performance of the flame retardant, epoxy resin is used as a high polymer base material, specifically bisphenol A epoxy resin (CYD-127) and diaminodiphenyl methane (DDM) as curing agents, 100 g of the epoxy resin is taken and added into the flame retardant obtained in the embodiment, the addition amount of the flame retardant is respectively 10% and 15%, a high-speed dispersing machine is adopted, 26 g of the curing agent is added after the dispersion, the temperature is raised to 145 ℃, the high-speed dispersing machine is continuously used for dispersing, after the dispersion is uniform, the mixture is poured into a mold, the mold is put into an oven, the heat is preserved for 4 hours at 160 ℃, after the temperature is reduced, a sample is taken out from the mold for testing, and flame retardant data (600 ℃ carbon residue rate and oxygen index) 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 the flame retardant performance of the same flame retardant which is normally produced.
Comparative example 1
The treatment of the phosphorus-containing complex salt was carried out according to the method reported in CN111689508A, the procedure being as follows:
2000 g of water is weighed, the temperature is raised to 80 ℃, 500 g of phosphorus-containing compound salt is taken, 2000 g of water is added in batches, the temperature of a reaction system is controlled to be 80 ℃, the reaction system is kept for 1 hour, 350 g of hydrogen chloride is introduced, solids are separated out, the solid is filtered, the weight of the solid is 102.6 g after being dried in vacuum for 7 hours at 70 ℃, the analyzed sodium chloride content is 95.5%, the aluminum chloride hydrate content is 3.8%, the total phosphorus content is 0.278%, the total phosphorus content is 2780ppm, the filtrate is concentrated and crystallized at normal pressure, when the system temperature is 110 ℃, the concentration is stopped, cooling and crystallization are carried out, the filtration is carried out, the solid is dried in vacuum for 7 hours at 70 ℃, the weight of 494.6 g, the analyzed sodium chloride content is 8.68%, the aluminum chloride hydrate content is 90.0%, and the total phosphorus content is 0.52% and the total phosphorus content is 5200ppm.
Comparative example 2
The same procedure as in example 1 was followed, except that the substance added in S1 was not acetaldehyde but p-methylphenol. The specific implementation process is as follows.
S1, weighing 1000 grams of phosphorus-containing compound salts in the same batch as a detection sample, adding the 1000 grams of phosphorus-containing compound salts into 2100 grams of 4% hydrochloric acid solution in batches, and then adding 100 grams of p-methylphenol, wherein the temperature of the system is kept at about 50 ℃ in the adding process, so as 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 by using 650 g of 20% hydrochloric acid, filtering, and drying to obtain 295.3 g of sodium chloride, wherein the content of sodium chloride is 99.38% by detecting sodium ions through ion chromatography, the phosphorus content is 19.2ppm by using an ammonium molybdate spectrophotometry, and the recovery rate of the sodium chloride is 94.9%;
s3, merging the filtrate obtained in the filtering step in the step S2, continuing to introduce 720 g of hydrogen chloride, filtering, washing a filter cake by 1100 g of 35% hydrochloric acid, drying, weighing 1046.9 g of the filter cake, namely aluminum chloride hydrate, detecting the content of the aluminum chloride hydrate to be 97.9% by using a complexation method, detecting the content of sodium ions to be 0.41% by using ion chromatography, detecting the content of phosphorus to be 15.4ppm by using an ammonium molybdate spectrophotometry, and recovering the aluminum chloride hydrate to be 94.1%;
s4, combining the filtrate filtered in the step S3 with the washing liquid, performing reduced pressure distillation, 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 in the reduced pressure distillation in the step S4 with sodium hydroxide, filtering, adding concentrated hydrochloric acid into filtrate to acidify until the pH value is 1, performing reduced pressure distillation, evaporating water, adding 100 g of ethanol to dissolve residues, filtering, and washing a filter cake with 40 g of ethanol to obtain sodium chloride solid; and combining the filtrate and the washing liquid to obtain a phosphorus-containing flame retardant ethanol solution, evaporating ethanol, distilling under reduced pressure to obtain 90.5 g of p-methylphenol, collecting 175-178 ℃ fractions under the vacuum degree of 5Pa, wherein the fractions are 12.4 g of the liquid flame retardant, and the residual high-boiling point fraction is 60.2 g, so that the recovery rate of phosphorus is 11.6%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (14)
1. The comprehensive recycling method of the alkyl dichlorophosphine production byproducts comprises sodium chloride and aluminum chloride composite salt and alkyl dichlorophosphine, and is characterized by comprising the following steps:
s1, mixing the alkyl dichlorophosphine production byproducts, aldehyde compounds and dilute hydrochloric acid, and reacting at the temperature of 40-100 ℃ to generate a phosphorus-containing flame retardant or an intermediate thereof, thereby obtaining a first mixture containing the phosphorus-containing flame retardant or the intermediate thereof, sodium chloride and aluminum chloride;
the mass percentage of the dilute hydrochloric acid is less than or equal to 10%;
the aldehyde compound has a structure shown in the following general formula (1):
wherein R is 1 Is hydrogen, C1-C12 branched or straight chain alkyl, 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;
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 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, phosphorus-containing flame retardant or an intermediate thereof and hydrochloric acid;
s3, introducing hydrogen chloride gas and/or adding hydrochloric acid into the filtrate obtained after the filtration in the step S2, so that the mass content of the hydrogen chloride in the mixture solution is more than or equal to 35%, separating out aluminum chloride 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 phosphorus-containing flame retardant or an intermediate thereof, aluminum chloride, sodium chloride and hydrochloric acid;
s4, distilling and concentrating the third mixture in the step S3 to obtain concentrated hydrochloric acid and a phosphorus-containing flame retardant or an intermediate thereof mixed with aluminum chloride and sodium chloride;
s5, adding sodium hydroxide into the phosphorus-containing flame retardant or the intermediate thereof mixed with aluminum chloride and sodium chloride, and separating and removing aluminum hydroxide and sodium chloride to obtain the phosphorus-containing flame retardant or the intermediate thereof.
2. The method for comprehensively recycling the alkyl dichlorophosphine production byproducts according to claim 1, wherein in the step S1, the alkyl dichlorophosphine production byproducts are added into 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 stirring reaction is carried out to obtain the first mixture.
3. The method for comprehensively recycling the by-product of the production of the alkyl dichlorophosphine according to claim 1, wherein in the steps S2 and S3, the hydrochloric acid for washing is concentrated hydrochloric acid with the mass percent of 30% -37% respectively.
4. The method for the comprehensive recycling of alkyl dichlorophosphine production byproducts according to claim 1, wherein in the general formula (1), R1 is hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl or ethylphenyl.
5. The method for comprehensive recycling of alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the aldehyde compound is one or a combination of more selected from acetaldehyde, benzaldehyde and phenylacetaldehyde.
6. The comprehensive recycling method of the byproduct of the production of the alkyl dichlorophosphine according to claim 1, wherein the content of the alkyl dichlorophosphine in the phosphorus-containing composite salt is obtained before the step S1, and in the step S1, the feeding mole ratio of the alkyl dichlorophosphine to the aldehyde compound is 1:1.01 to 1.3.
7. The method for comprehensive recycling of alkyl dichlorophosphine production byproducts according to claim 6, wherein in step S1, the molar ratio of alkyl dichlorophosphine to aldehyde compound is 1:1.01 to 1.1.
8. The method for comprehensive recycling of alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S1, the usage amount of the diluted hydrochloric acid is 1-10 times of that of the phosphorus-containing compound salt; and/or the reaction temperature is 45-60 ℃.
9. The method for comprehensively recycling the byproduct in the production of the alkyl dichlorophosphine according to claim 1, wherein in the step S1, the mass percentage of the dilute hydrochloric acid is 2% -5%; and/or, in the step S2, introducing hydrogen chloride to enable the mass percentage of the hydrogen chloride in the mixture solution to reach 6% -10%; and/or, in the step S3, introducing hydrogen chloride to ensure that the mass content of the hydrogen chloride in the mixture solution is 35-45%.
10. The method for comprehensive recycling of alkyl dichlorophosphine production byproducts according to claim 1, wherein in step S2, after crystallization of sodium chloride and before filtration, the system is kept at 70-90 ℃ for 1-2 hours.
11. The method for the integrated recycling of alkyl dichlorophosphine production byproducts of claim 1, wherein step S5 further comprises:
s50: adding sodium hydroxide into the phosphorus-containing flame retardant mixed with aluminum chloride and sodium chloride or the intermediate thereof obtained in the step S4 to enable the aluminum chloride in a dissolved state to generate sodium chloride and aluminum hydroxide, obtaining a mixture containing aluminum hydroxide, sodium chloride, the phosphorus-containing flame retardant or the sodium salt of the intermediate thereof, and filtering, wherein the filtrate is an aqueous solution of the phosphorus-containing flame retardant or the sodium salt of the intermediate thereof and the sodium chloride;
s51: adding hydrochloric acid into the filtrate obtained in the step S50 to acidify to enable the phosphorus-containing flame retardant or the intermediate sodium salt to be dissociated into the phosphorus-containing flame retardant or the intermediate, concentrating to be anhydrous to obtain the phosphorus-containing flame retardant or the phosphorus-containing flame retardant intermediate and sodium chloride, adding an organic solvent to stir uniformly, filtering, concentrating the filtrate, distilling under reduced pressure or recrystallizing to obtain the phosphorus-containing flame retardant or the intermediate, washing the filter cake with the organic solvent, and drying to obtain the sodium chloride.
12. The method for the comprehensive recycling of byproducts of the production of alkyl dichlorophosphine according to claim 1, wherein the alkyl dichlorophosphine is methyl dichlorophosphine, and the method for the comprehensive recycling further comprises: s6, using the sodium chloride solid obtained in the step S2 in the production process of the methyl dichlorophosphine.
13. The integrated recovery and utilization method of alkyl dichlorophosphine production byproducts of claim 11, further comprising one or more of the following steps:
s7, using the aluminum chlorohydrate obtained in the step S3 in the casting and sewage treatment industry;
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;
s9, dissolving the sodium chloride obtained in the step S5 with water to obtain a sodium chloride aqueous solution, and returning to the step S1 to be mixed with dilute hydrochloric acid for dissolving the compound salt;
s10, returning the filter cake filtered in the step S50, namely 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.
14. A process for the production of an alkyl dichlorophosphine comprising: (1) Obtaining alkyl dichlorophosphine and sodium chloride and aluminum chloride composite salt byproducts containing the alkyl dichlorophosphine, and is characterized in that the production method further comprises (2): recovery of sodium chloride, aluminum chlorohydrate, phosphorus-containing flame retardants or intermediates thereof using the integrated recovery process of any one of claims 1 to 13.
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