CN113372387A - Process for preparing hydrocarbyl-phosphonium halides and reactor therefor - Google Patents
Process for preparing hydrocarbyl-phosphonium halides and reactor therefor Download PDFInfo
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- CN113372387A CN113372387A CN202110735269.4A CN202110735269A CN113372387A CN 113372387 A CN113372387 A CN 113372387A CN 202110735269 A CN202110735269 A CN 202110735269A CN 113372387 A CN113372387 A CN 113372387A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 181
- 239000000956 alloy Substances 0.000 claims abstract description 181
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 146
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 230000007797 corrosion Effects 0.000 claims abstract description 88
- 238000005260 corrosion Methods 0.000 claims abstract description 88
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 229910000792 Monel Inorganic materials 0.000 claims description 27
- 229910000856 hastalloy Inorganic materials 0.000 claims description 27
- 229910001026 inconel Inorganic materials 0.000 claims description 27
- 229910001293 incoloy Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 239000006184 cosolvent Substances 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 7
- 229910018054 Ni-Cu Inorganic materials 0.000 claims description 6
- 229910018481 Ni—Cu Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910019819 Cr—Si Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [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
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 238000005536 corrosion prevention Methods 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 30
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 25
- 239000011651 chromium Substances 0.000 description 18
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 17
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 229910052715 tantalum Inorganic materials 0.000 description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 10
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 10
- -1 alkyl halogenated phosphine Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 229910001252 Pd alloy Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229910001362 Ta alloys Inorganic materials 0.000 description 7
- 238000009776 industrial production Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007787 solid Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ANUQVPMOKIYKBZ-UHFFFAOYSA-N [Ti].[Ni].[Mo] Chemical compound [Ti].[Ni].[Mo] ANUQVPMOKIYKBZ-UHFFFAOYSA-N 0.000 description 1
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HCBPHBQMSDVIPZ-UHFFFAOYSA-N methylcyclohexatriene Chemical compound CC1=CC=C=C[CH]1 HCBPHBQMSDVIPZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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Classifications
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for producing compounds of the formulae (I) and (II) in which X is a halogen and R is a hydrocarbon radical, and a reactor for carrying out said method, comprising reacting yellow phosphorus with a compound of the formula (III) in the absence of a catalyst in a reactor, characterized in that the surface of the reactor that is in contact with the reaction space is made of a nickel-based alloy as a corrosion-resistant alloy or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the thickness direction of the reactor wall. The present invention enables to realize an improved corrosion prevention effect as compared with the existing reactor and its parts and an acceptable cost due to the use of the nickel-based alloy as the corrosion-resistant alloy as the material of the reactor and its parts, thereby making it possible to realize the aforementioned method on an industrial scale.
Description
Technical Field
The invention relates to a method for directly synthesizing alkyl halogenated phosphine under the condition of no catalyst, and a reactor specially used for implementing the method.
Background
Diphenyl phosphine chloride and phenyl phosphine dichloride are important monomers for synthesizing various organic phosphorus compounds, are intermediates for preparing pesticides, plasticizers, phosphorus flame retardants, ultraviolet initiators and the like, and have wide market demands.
The conventional process for preparing phenylphosphine dichloride is to react benzene and phosphorus trichloride for 2-6 hours at elevated temperature in the presence of anhydrous aluminum trichloride catalyst. Cooling to separate out liquid organic phase, successively vacuum distilling to obtain excessive benzene and phosphorus trichloride, and final vacuum rectifying to obtain the product phenylphosphonic dichloride. In this method, aluminum trichloride and phenyl phosphine dichloride form a complex to lose activity, and therefore aluminum trichloride is added in an amount equimolar or more to benzene. This consumes a large amount of catalyst, and also produces a large amount of solid waste, which seriously pollutes the environment. Since the aluminum trichloride cannot be separated off by hydrolysis or acidolysis after the reaction, as in the case of the other Friedel-Crafts reactions, the desired product cannot be distilled directly from the reaction mixture. The product can be separated after adding decomplexer such as phosphorus oxychloride, phosphorus pentoxide and pyridine, but the method has the defects that a large amount of complex solid waste of aluminum trichloride is generated, the solid waste is difficult to treat, and the environmental protection pressure is high.
The synthesis of diphenyl phosphonium chloride is substantially similar to phenyl phosphine dichloride. The conventional method is also obtained by adopting excessive benzene and phosphorus trichloride to react at high temperature in the presence of an anhydrous aluminum trichloride catalyst. The disadvantage is that a large amount of complex solid waste of aluminum trichloride is generated, and the environmental protection pressure is large (see http:// www.docin.com/p-1372117195. html).
Many research and patented techniques have been directed to the isolation of products using various decomplexers. The organic decomplexer comprises phosphorus trichloride, phosphorus pentoxide, pyridine organic alkali, ethyl acetate, beta-triethyl chlorophosphate, dioxane, etc. The inorganic salt decomplexer is ground sodium chloride or potassium chloride. However, these approaches all introduce a large amount of solid waste that is difficult to dispose of. In addition, it has been reported that phenyl phosphine dichloride and diphenyl phosphine chloride are synthesized by using ionic liquid, but there is a problem that a large amount of solid waste is difficult to treat (Wangzaiwei, Zhang, Liushang, et al, fine and special chemicals 2014, (10): 29-35).
Chinese patent application CN201110426418.5 discloses that benzene, phosphorus trichloride and aluminum trichloride are mixed and then stirred vigorously, and the temperature is raised to 140 ℃ and 150 ℃ for reaction; after the reaction is finished, cooling to room temperature, and dropwise adding beta-triethyl chlorophosphate serving as a decomplexer; and (3) separating the lower decomplexer layer, and distilling the upper organic layer under reduced pressure to obtain the diphenyl phosphonium chloride.
Chinese patent application CN201210473945.6 discloses a synthesis method of diphenyl phosphine chloride. The method is to synthesize diphenyl phosphonium chloride by catalyzing the reaction of benzene and phosphorus trichloride with Lewis acid room temperature ionic liquid. The method takes phosphorus trichloride and excessive benzene as raw materials to react under the catalysis of Lewis acid ionic liquid. After the reaction is finished, the reaction liquid is divided into two layers, wherein one layer is an ionic liquid layer, and the other layer is a mixed liquid layer. Directly separating liquid, extracting an ionic liquid layer, combining an extract liquid and a mixed liquid layer, and respectively distilling under normal pressure and reduced pressure to obtain a target product, namely diphenyl phosphine chloride and a byproduct, namely phenyl phosphine dichloride. The ionic liquid is recovered after removing impurities by atmospheric pressure and reduced pressure distillation.
Chinese patent application CN201310099065.1 proposes a method for synthesizing phenyl phosphine dichloride. Benzene and phosphorus trichloride are taken as raw materials, sodium chloride and aluminum trichloride are added as catalysts at the same time, and phenyl phosphine dichloride, mixed liquor of benzene and phosphorus trichloride and solid residues are obtained through reaction. Treating the solid residue with an extractant, mixing with the mixed liquor, oftenDistilling under reduced pressure to obtain pure phenyl phosphine dichloride. AlCl catalyst3The XNaCl complex can be recycled.
The method takes benzene and phosphorus trichloride as raw materials and adopts aluminum trichloride as a catalyst, and the key point of the solution lies in the subsequent treatment problem of an aluminum trichloride complex. However, none of these methods have the exception of producing large amounts of solid waste that is difficult to dispose of and thus, impacts the environment.
The company HOECHST, germany, in US5587517 proposes reacting triphenylphosphine and phosphorus trichloride at elevated temperatures above 350 ℃ to form phenylphosphonic dichloride and a small amount of diphenylphosphinic chloride. 2051 g of phosphorus trichloride and 816 g of triphenylphosphine were charged to give 1284 g of phenylphosphonic dichloride and a small amount of diphenylphosphine chloride. This process is not commercially viable due to the high price of triphenylphosphine.
U.S. Pat. No. 3,34958 discloses that chlorobenzene and yellow phosphorus are used as raw materials, the temperature is raised to 340 ℃ in a tantalum autoclave in the presence of phenyl phosphine dichloride for reaction for 4 hours, the mixture containing phosphorus trichloride, chlorobenzene, phenyl phosphine dichloride and diphenyl phosphine chloride is obtained after cooling, and the product, namely diphenyl phosphine chloride, is obtained by atmospheric pressure rectification and reduced pressure rectification. Phosphorus trichloride, phenyl phosphine dichloride and diphenyl phosphine chloride have strong corrosivity, and a tantalum material has certain corrosion resistance to the phosphorus trichloride, the phenyl phosphine dichloride and the diphenyl phosphine chloride at a high temperature, but the tantalum material is expensive and cannot realize industrialization, and a tantalum-based alloy with a slightly low price cannot realize effective corrosion prevention.
Since US3734958 discloses the above mentioned method for the direct synthesis of diphenyl phosphonium chloride without catalyst for nearly half a century, there have been attempts to find industrialization of the method, however, suitable reactor materials have not been found, resulting in that the method has not been commercialized. For example, the corrosion resistance effect of the reactor made of the corresponding material is not as good as expected according to the reaction environment adapted by the existing corrosion-resistant material.
Therefore, there is still a need to find a reactor and its fittings suitable for carrying out the process disclosed in US3734958, which are not only sufficiently corrosion resistant, but also cost effective and capable of industrial production.
Disclosure of Invention
In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies on materials for a reactor and its fittings for directly synthesizing a hydrocarbon-based phosphine halide from yellow phosphorus and a halogenated hydrocarbon as raw materials in the absence of a catalyst, and have found that the above-mentioned disadvantages of the prior art can be overcome by using a reactor and its fittings of a specific corrosion-resistant material. The inventors of the present invention have unexpectedly found that a nickel-based alloy as a corrosion resistant alloy has an excellent corrosion preventing effect on both the reaction raw materials and the reaction products of the above reaction, and a reactor and its parts made of the corrosion resistant alloy can effectively perform a process for directly synthesizing a phosphine halide with a hydrocarbon group from yellow phosphorus and a halogenated hydrocarbon as raw materials. The present invention has been completed based on the above findings.
It is therefore an object of the present invention to provide a process for the synthesis of hydrocarbyl-halogenated phosphines starting from yellow phosphorus and a halogenated hydrocarbon in a single step in the absence of a catalyst. The method can achieve an improved corrosion prevention effect compared to the existing reactor and its parts and is acceptable in cost due to the use of the nickel-based alloy as a corrosion-resistant alloy as a material of the reactor and its parts, so that the aforementioned method can be implemented on an industrial scale.
It is another object of the present invention to provide a reactor specially adapted for carrying out the preparation method of the present invention, which employs a nickel-based alloy as a corrosion-resistant alloy as a material of the reactor, so that an improved corrosion prevention effect can be achieved as compared with the existing reactors, thereby allowing the aforementioned method to be carried out on an industrial scale.
It is a further object of the present invention to provide the use of a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor and its fittings according to the invention.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. a process for the preparation of compounds of the formulae (I) and (II),
wherein
X is halogen, preferably chlorine or bromine, and when two X's are present in the same molecule, they may be the same or different, and
r is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and when two R's are present in the same molecule, R's may be the same or different,
comprising reacting yellow phosphorus with a compound of formula (III) in the absence of a catalyst in a reactor,
X-R
(III)
wherein X and R are each as defined for formula (I) and formula (II),
characterized in that the surface of the reactor in contact with the reaction space is made of a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
2. The method according to item 1, wherein the nickel-based alloy as the corrosion-resistant alloy is one or more alloys selected from the group consisting of:
1) a Ni-Cu based alloy comprising 20 to 30% by weight of Cu and 70 to 80% of Ni based on the total weight thereof;
2) an Ni-Mo based alloy comprising 50-75 wt% Ni and 15-50 wt% Mo, preferably 28-50 wt% Mo, based on the total weight of the alloy;
3) a Ni — Cr-based alloy containing 50 to 65 wt% of Ni and 15 wt% or more of Cr, preferably 25 wt% or more of Cr, more preferably 35 to 50 wt% of Cr, based on the total weight of the alloy; and
4) other nickel-base corrosion resistant alloys selected from the group consisting of: a Ni-Si alloy comprising 70-85 wt% Ni and 3-10 wt% Si based on the total weight thereof, and a Ni-Cr-Si alloy which is a D-205 alloy comprising 20 wt% Cr, 5 wt% Si and 65 wt% Ni based on the total weight thereof.
3. The method according to item 1, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: monel alloys (e.g. Monel)
And Monel K500), Inconel (Inconel) alloys (e.g., Inconel
Inconel
And Inconel
) Incoloy (Incoloy) alloy (Incoloy)
And Incoloy
) And Hastelloy (e.g., Hastelloy)
Hastelloy
And Hastelloy
)。
4. The method according to any one of items 1 to 3, wherein an inner wall of the pipe in contact with the reaction raw material or the reaction product or the pipe is entirely made of a nickel-based alloy as a corrosion resistant alloy in a wall thickness direction, and/or a valve in contact with the reaction raw material or the reaction product or those surfaces of the valve in contact with the reaction raw material or the reaction product are made of a nickel-based alloy as a corrosion resistant alloy.
5. The process according to any one of items 1 to 4, wherein R is the same or different and each independently represents a linear or branched alkyl group containing 1 to 20, preferably 1 to 8, carbon atoms (such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl), C6-C10Aryl, preferably C6-C8Aryl groups (e.g., phenyl, o-tolyl, m-tolyl, and p-tolyl), and C6-C10Aralkyl, preferably C6-C8Aralkyl (e.g., benzyl).
6. The process according to any one of items 1 to 5, wherein the molar ratio of the yellow phosphorus to the compound of formula (III) is fed in the range of from 1:6 to 1:12, preferably from 1:6 to 1:10, more preferably from 1:6 to 1: 8.
7. The process according to any one of items 1 to 6, wherein the reaction of yellow phosphorus with the compound of formula (III) is carried out in the presence of one or more compounds selected from the group consisting of the compounds of formulae (I), (II) and (IV) as co-solvent, preferably in the presence of the compound of formula (I) and/or (II) as co-solvent,
wherein R is as defined for compounds of formula (I) and formula (II); preferably, the co-solvent is used in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the total weight of yellow phosphorus and the compound of formula (III).
8. The process according to any one of items 1 to 7, wherein X is chlorine and R in each formula is phenyl or tolyl.
9. The method according to any one of items 1 to 8, wherein the reaction is carried out at a temperature of 200-; and/or the reaction pressure is autogenous, for example the reaction is carried out at a gauge pressure of 0.01 to 8.0MPa, preferably 0.01 to 6.0MPa, more preferably 0.05 to 5.0 MPa; and/or the reaction time is 2-10h, preferably 2-6 h.
10. A reactor for carrying out the method according to any one of claims 1 to 9, the reactor being a tank reactor comprising: 1) stirrer, 2) a cover, and 3) a body, 4) heating means located outside and/or inside the reaction vessel, and 5) cooling means located outside and/or inside the reaction vessel, wherein the cover and optionally the body of the reaction vessel are provided with openings in the upper part thereof, and the chamber formed by the connection of the cover and the body constitutes the reaction space of the reactor, characterized in that: the material in contact with the reaction space in the reactor is nickel-based alloy as corrosion-resistant alloy, or the reactor is entirely made of nickel-based alloy as corrosion-resistant alloy in the whole thickness direction of the reactor wall, and preferably the volume of the reaction kettle is 300L-5000L.
11. The reactor according to item 10, wherein the vessel lid is a flange lid, and the flange lid is connected to the vessel body through a flange plate.
12. The reactor according to item 10 or 11, wherein the nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:
1) a Ni-Cu based alloy comprising 20 to 30% by weight of Cu and 70 to 80% of Ni based on the total weight thereof;
2) an Ni-Mo based alloy comprising 50-75 wt% Ni and 15-50 wt% Mo, preferably 28-50 wt% Mo, based on the total weight of the alloy;
3) a Ni — Cr-based alloy containing 50 to 65 wt% of Ni and 15 wt% or more of Cr, preferably 25 wt% or more of Cr, more preferably 35 to 50 wt% of Cr, based on the total weight of the alloy; and
4) other nickel-base corrosion resistant alloys selected from the group consisting of: a Ni-Si alloy comprising 70-85 wt% Ni and 3-10 wt% Si based on the total weight thereof, and a Ni-Cr-Si alloy which is a D-205 alloy comprising 20 wt% Cr, 5 wt% Si and 65 wt% Ni based on the total weight thereof.
13. The reactor according to any of claims 10 to 12, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: monel alloys (e.g. Monel)
Monel K500), Inconel (Inconel) alloys (e.g., Inconel
Inconel
Inconel
) Incoloy (Incoloy) alloy (Incoloy)
Incoloy
) And Hastelloy (e.g., Hastelloy)
Hastelloy
Hastelloy
)。
14. Use of a nickel base alloy as a corrosion resistant alloy in the manufacture of a reactor as claimed in any one of claims 10 to 12 and fittings thereof such as pipes and valves.
Drawings
FIG. 1 is a nickel-base alloy Hastelloy
And Monel
Photographs of the respective coupons after etching in the gas phase.
FIG. 2 is a nickel-base alloy Hastelloy
And Monel
Pictures of the respective coupons after etching in liquid phase.
FIG. 3 is a photograph of coupons of tantalum, tantalum alloy Ta-2.5W, and titanium palladium alloy TA9, respectively, after etching in the vapor phase.
FIG. 4 is a photograph of coupons of tantalum, tantalum alloy Ta-2.5W, and titanium palladium alloy TA9, respectively, after etching in the liquid phase.
Detailed Description
According to one aspect of the present invention, there is provided a process for the preparation of compounds of the following formulae (I) and (II),
wherein
X is halogen, and when two X's are present in the same molecule, X's may be the same or different, and
r is a hydrocarbon group, and when two R are present in the same molecule, R may be the same or different,
comprising reacting yellow phosphorus with a compound of formula (III) in the absence of a catalyst in a reactor,
X-R
(III)
wherein X and R are each as defined for formula (I) and formula (II),
characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
The reaction of yellow phosphorus with compounds of the formula (III) in the absence of catalysts to give compounds of the formula (I) and (II) in the process of the present invention is known per se, see for example U.S. Pat. No. 3,34958. This document is incorporated herein by reference in its entirety.
Since the reaction of yellow phosphorus with the compound of formula (III) to give the compounds of formula (I) and (II) does not employ any catalyst and is carried out in one step, the reaction is sometimes referred to as "direct synthesis".
The variables X and R in formula (III) are transferred to the compounds of formula (I) and formula (II) respectively after reaction, so that the definitions of the variables X and R in formula (III) correspond to the corresponding definitions in the compounds of formula (I) and formula (II). If a compound of formula (I) is to be prepared in which two R's are different from each other, two compounds of formula (III) in which R's are different from each other may be dosed. If a compound of the formula (II) in which two xs are different from each other is to be prepared, two compounds of the formula (III) in which two xs are different from each other may be dosed.
In one embodiment of the process of the invention, all R in the compound of formula (I) are the same and/or all X in the compound of formula (II) are the same.
In the compounds of formulae (I), (II) and (III), X is halogen, preferably chlorine or bromine, and when two X's are present in the same molecule, they may be the same or different.
In the compounds of formulae (I), (II) and (III), R is a hydrocarbon group, and when two R are present in the same molecule, R may be the same or different. Preferably, R is the same or different and each is independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When R is an aliphatic hydrocarbon group, it may be the same or different, and each independently represents a straight-chain or branched alkyl group having 1 to 20, preferably 1 to 8, carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl. When R is an aromatic hydrocarbon group, it may be the same or different, and each independently represents C6-C10Aryl, preferably C6-C8Aryl radicals, such as the phenyl, o-tolyl, m-tolyl and p-tolyl radical, and C6-C10Aralkyl, preferably C6-C8Aralkyl radicals, such as benzyl.
In a particularly preferred embodiment of the process according to the invention, X is chlorine and R in each formula is phenyl or tolyl.
The direct reaction of yellow phosphorus with a compound of formula (III) to give compounds of formula (I) and (II) in the absence of a catalyst is conventional and can be carried out under conventional reaction conditions.
The reaction of yellow phosphorus with the compound of the formula (III) can advantageously be carried out in the presence of a cosolvent. The yellow phosphorus is solid at normal temperature, and the cosolvent can dissolve the yellow phosphorus. As co-solvent, it is advantageous to use one or more compounds selected from the compounds of formulae (I), (II) and (IV) as described above,
wherein R is as defined for compounds of formula (I) and formula (II). For example, the co-solvent may be selected from one or more of triphenylphosphine, diphenylchlorophosphine, and phenyldichlorophosphine, especially when the compounds to be prepared are diphenylchlorophosphine and phenyldichlorophosphine. The amount of the co-solvent is not particularly limited as long as the yellow phosphorus raw material to be used can be dissolved. Preferably, the co-solvent is used in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the total weight of yellow phosphorus and the compound of formula (III).
It is to be noted that although the process of the invention may be carried out in the presence of one or more compounds selected from the group of compounds of formula (I), (II) and (IV) as co-solvent, it is preferred that the variables X and R in the co-solvent compound are in agreement with the corresponding variables X and R in the compound of formula (I) and (II) to be prepared. For example, for the preparation of phenylphosphonic dichloride and diphenylphosphine chloride, the co-solvent selected is preferably one or more of triphenylphosphine, phenylphosphonic dichloride and diphenylphosphine chloride, especially phenylphosphonic dichloride and/or diphenylphosphine chloride. This can reduce the cost of separating the individual components after the reaction is complete.
In the reaction of the process of the present invention, the amounts of the reactants are conventional. Generally, the feeding molar ratio of the yellow phosphorus (chemical formula is P4) to the compound of formula (III) is 1:6 to 1:12, preferably 1:6 to 1:10, more preferably 1:6 to 1: 8.
In the reaction of the method of the present invention, the reaction temperature is conventional, and the reaction can be carried out at a temperature of 200-800 deg.C, preferably 200-600 deg.C, more preferably 300-500 deg.C, and particularly preferably 300-400 deg.C. The reaction pressure is also conventional and is generally carried out under autogenous pressure. The reaction may be carried out at a gauge pressure of 0.01 to 8.0MPa, preferably 0.01 to 6.0MPa, more preferably 0.05 to 5.0 MPa. The reaction times are also conventional, the reaction generally lasting from 2 to 10h, preferably from 2 to 6 h. Whether the reaction is complete can be judged by sampling and detecting yellow phosphorus.
After completion of the reaction, a reaction mixture is obtained comprising the compounds of formula (I) and formula (II), optionally unreacted white phosphorus, optionally the compound of formula (III) and optionally a co-solvent. To obtain the desired compounds of formula (I) and formula (II), the reaction mixture needs to be worked up. This work-up is conventional, as long as the compounds of formula (I) and formula (II) can be isolated. For this purpose, the reaction mixture obtained in the reaction is usually cooled to room temperature and then transferred to a distillation still for separation by distillation, for example, distillation under atmospheric pressure followed by rectification under reduced pressure, to give the compounds of the formula (I) and (II).
Phosphorus trichloride, phenylphosphine dichloride and diphenylphosphine chloride are very corrosive. The method of the invention has the following important characteristics: the material for the surface in contact with the reaction space in the reactor used in the process of the present invention is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
The prior art has various corrosion resistant material recommendations for various corrosive work or operating environments. As the metal corrosion-resistant material, an iron-based alloy such as corrosion-resistant stainless steel is mainly used. The active metals also have good corrosion resistance, and are typically represented by Ti, Zr, Ta, and the like. The reactor used is taught in US3734958 as a tantalum autoclave. However, the present inventors have found that when a tantalum autoclave is used for the production of a hydrocarbon-based phosphine halide, although it has some corrosion resistance, it is insufficient in corrosion resistance and durability and also high in cost when it is used for the production on an industrial scale, and thus, it is impossible to realize the industrial production of a hydrocarbon-based phosphine halide.
The present inventors have found that if the surface of the reactor which is in contact with the reaction space or even the entire thickness of the reactor wall is made entirely of a nickel-based alloy as a corrosion-resistant alloy, the corrosion resistance of the reactor thus constructed is greatly improved, sufficient corrosion resistance is obtained, and the price thereof is far lower than that of a tantalum material, providing a feasible reaction apparatus for realizing industrialization of the hydrocarbon-based phosphine halide.
In the process of the present invention, a reactor is used in which the surface in contact with the reaction space is made of a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. In the present invention, the reaction space of the reactor has the meaning generally understood by a person skilled in the art. For example, taking a reaction kettle as an example, the reaction space refers to a three-dimensional space formed by the kettle cover and the kettle body of the reaction kettle. In the present invention, the reactor may be made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. Alternatively, for reasons of cost, strength or other considerations, it is also possible to make only those surfaces of the reactor which are in contact with the reaction space of a nickel-based alloy as corrosion-resistant alloy. The thickness of these surfaces can be determined by routine experimentation based on actual operating conditions and the design life of the reactor.
The nickel-based alloy as the corrosion-resistant alloy generally contains 30 wt% or more of Ni, and the Ni content of the usual nickel-based alloy reaches 50 wt% or more. Since nickel-based alloys have superior high temperature mechanical strength and corrosion resistance properties, they are collectively referred to as superalloys with iron-based alloys and cobalt-based alloys.
In one embodiment of the present invention, the nickel-based alloy as the corrosion-resistant alloy may be selected from one or more of the following group:
1) a Ni-Cu based alloy comprising 20-30% by weight of Cu and 70-80% of Ni based on the total weight of the alloy. The Ni-Cu alloy is represented by Monel (Monel) alloy, which combines many advantages of Ni and Cu and can maintain a constant metallic luster in the atmosphere. The Monel alloy is mainly used for high-temperature and load-bearing corrosion-resistant parts and equipment. As examples of Monel alloys, mention may be made of Monel
And Monel K500.
2) An Ni-Mo based alloy comprising 50-75 wt.% Ni and 15-50 wt.% Mo, preferably 28-50 wt.% Mo, based on the total weight of the alloy. The addition of molybdenum in such alloys greatly improves the corrosion resistance, strength and high temperature processability of the nickel base (solid solution). The addition of more than 15% of Mo into Ni can make the alloy have high oxidation and acid resistance. Research has shown that Ni-Mo alloys containing about 28% Mo are resistant to hydrochloric acid attack at any temperature and concentration at atmospheric pressure, as well as to corrosion by sulfuric acid, acetic acid, phosphoric acid, formic acid, and hydrogen chloride gas. The Ni-Mo corrosion resistant alloy comprises a Hastelloy alloy. As an example of Hastelloy, mention may be made of Hastelloy
Hastelloy
And Hastelloy
3) A Ni-Cr-based alloy comprising 50 to 65 wt% of Ni and 15 wt% or more of Cr, preferably 25 wt% or more of Cr, more preferably 35 to 50 wt% of Cr, based on the total weight of the alloy. The addition of chromium significantly increases the nickel's ability to resist oxidizing acids, salts and high temperature oxidation, sulfidation, vanadium corrosion. The Ni can be passivated in dilute sulphuric acid by containing 15 weight percent of Cr; more than 25 weight percent of Cr can be passivated in aerated nitric acid; if corrosion resistance in hot concentrated nitric acid is required, 35-50 wt% chromium is required. Typical Ni-Cr corrosion resistant alloys are Inconel (Inconel) alloy and Incoloy (inflixoy) alloy. Mention may be made, as examples of Inconel alloys, of Inconel
Inconel
And Inconel
Inconel
The composite material is not only resistant to high-temperature oxidation, but also can be used in aqueous solution, especially strong-oxidizing aqueous solution, can be used in environments of room-temperature sulfuric acid, phosphoric acid, low-concentration hydrochloric acid, hydrofluoric acid and the like, has excellent corrosion resistance in atmosphere, water, steam and alkali, and is widely used in chemical industry, nuclear power industry and the like. As an example of Incoloy (Brillouin) alloy, mention may be made of Incoloy
And Incoloy
4) Other nickel-base corrosion resistant alloys. For example, Ni-Si alloys (70-85 wt% Ni and 3-10 wt% Si) are resistant to oxidation, sulfuric acid (any concentration and boiling point temperature) corrosion, and organic acids and salts. There is also the Ni-Cr-Si alloy D-205, in which Cr is 20% by weight, Si is 5% by weight and Ni is 65% by weight, which is mainly used in the environment where superoxide is present.
In a preferred embodiment of the method of the present invention, the inner wall of the pipe or the pipe in contact with the reaction raw material or the reaction product is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the wall thickness direction. In another preferred embodiment of the method of the present invention, the valve in contact with the reaction raw material or the reaction product or those surfaces of the valve in contact with the reaction raw material or the reaction product are made of a nickel-based alloy as the corrosion-resistant alloy.
Since the material of those surfaces of the reactor of the invention and optionally of the reaction partners which come into contact with the reaction raw materials or reaction products is sufficiently resistant to corrosion by the reaction raw materials or reaction products of the invention, the process of the invention can be carried out not only in the laboratory, but also industrially on a large scale. The reactor of the present invention may be designed to have a volume of 300L to 5000L, that is, a volume of the inner space of the reaction vessel is 300L to 5000L.
According to another aspect of the invention there is provided a reactor for carrying out the process of the invention, the reactor being a tank reactor comprising: 1) stirrer, 2) a cover, and 3) a body, 4) heating means located outside and/or inside the reaction vessel, and 5) cooling means located outside and/or inside the reaction vessel, wherein the cover and optionally the body of the reaction vessel are provided with openings in the upper part thereof, and the chamber formed by the connection of the cover and the body constitutes the reaction space of the reactor, characterized in that: the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire reactor wall thickness direction.
The reactor of the invention is provided with a stirrer and is used for uniformly stirring materials in the reactor. Any stirrer capable of performing a stirring or agitating function may be used, including mechanical stirrers, magnetic stirrers, and the like. The stirrer is preferably a magnetic stirrer in consideration of toxicity and corrosiveness of the reaction raw materials and products, which require the reactor to be kept in a sealed state. The kettle type reaction kettle becomes a magnetic reaction kettle. In order to regulate the stirring speed, the stirrer is usually provided with a motor reducer. The stirrer is usually fixed on the kettle cover, and the magnetic force sheet or the stirring blade or the stirring belt of the stirrer is positioned in the reaction kettle.
The kettle cover can be plane or protrude outwards. In order to better seal the reaction space of the reactor, the vessel cover is preferably a flange cover, which is connected to the vessel body via a flange. Accordingly, the agitator is fixed to the flange cover. At the moment, the reactor comprises a flange cover, a flange plate and a kettle body from top to bottom. The flange cover is connected with the kettle body through a flange plate to form a closed chamber to form a reaction space of the reactor. The kettle cover can be provided with other openings, such as a manhole, a feeding hole and a discharging hole, besides the opening for arranging the stirrer, for the purposes of feeding, discharging, sampling measurement, maintenance and the like. Similarly, the upper part of the kettle body of the reactor can be provided with a hole, such as for feeding and discharging, sampling detection and the like. According to the invention, the reaction vessel is preferably a vertical reaction vessel.
The reactions involved in the process of the present invention are generally carried out at elevated temperatures. For this purpose, the reactor needs to be equipped with heating and cooling means. As a heating device for the reactor, it is located outside and/or inside the reaction vessel, preferably outside. As cooling means for the reactor, it is located outside and/or inside the reaction vessel, preferably outside. The heating device can be heated by a molten salt electric heater or a far infrared heating plate. The cooling device can be air-cooled or circulated water cooled.
The materials for the reactor according to the invention are suitable for the above description of the materials for the reactor according to the process of the invention and are not described in detail here. The industrial production of the process according to the invention is possible because the contact surface of the reactor according to the invention with the material flow or the entire reactor is made of a specific corrosion-resistant alloy. In one embodiment of the reactor of the invention, the working volume of the reactor is from 300L to 5000L.
According to a final aspect of the invention, there is provided the use of a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor and its fittings of the invention. The description of the nickel-base alloy as corrosion-resistant alloy applies to the above description of the material of the reactor involved in the process of the present invention, and will not be described in detail here. The fittings of the reactor include all pipes and valves and the like which are in contact with the reaction raw materials or the reaction products.
The method and the reactor have very important practical significance for the industrial production of the alkyl phosphine halide, the industrial production technology is not available at home and abroad at present, and the industrial production of the alkyl phosphine halide is successfully realized in an environment-friendly manner. The advantages of the invention include:
1. the production process for directly synthesizing the alkyl phosphine halide (especially the phenyl phosphine dichloride) without the catalyst is green and environment-friendly, does not generate waste gas, waste liquid and waste residue, and meets the requirement of realizing modern green and environment-friendly chemical production.
2. The nickel-based alloy used as the corrosion-resistant alloy is used as the material of the reactor and the fittings thereof or the material of the material contact surface of the reactor, so that the excellent corrosion resistance is obtained, and the industrial production of 300-5000L each batch can be successfully realized.
Examples
The present invention is described in detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereto.
In this specification, all "parts" refer to parts by weight unless otherwise specified.
In each example of the present invention, yellow phosphorus was used, purchased from yunnan co-production limited, and had a purity of 95%; chlorobenzene was purchased from wuhanfeng chemicals ltd, with a purity of 98%.
Examples 1-10 and comparative examples 1-6: corrosion resistance of various corrosion-resistant metals
Each corrosion-resistant metal is made into two identical metal pendants, and the size of each pendant is
A wire of 10cm × 10cm × 0.3cm, or 10cm × 3cm × 0.3cm, or 10cm × Φ 0.2 cm. Two pendants of each corrosion-resistant metal were placed in the gas phase and the liquid phase, respectively, of a 5L closed pressure kettle containing a mixture of 20 wt% of phosphorus trichloride, 40 wt% of phenylphosphonic dichloride and 40 wt% of diphenylphosphine chloride, at a test temperature of 500 ℃, a pressure (gauge pressure) of 0.5MPa, and the test lasted for 10 hours. And after the testing time is finished, taking out the pendant, photographing and weighing, and evaluating the anticorrosion effect.
The corrosion resistant metals tested included: pure tantalum metal sheet, tantalum alloy Ta-2.5W, pure metal zirconium sheet, Zr702 zirconium plate, titanium-molybdenum-nickel alloy TA10 and titanium-palladium alloy TA 9.
FIG. 1 shows a nickel-base alloy Hastelloy
And Monel
Photographs of the respective coupons after etching in the gas phase, wherein FIG. 1(a) is Hastelloy
Alloy, FIG. 1(b) is Monel
And (3) alloying.
FIG. 2 shows a nickel-base alloy Hastelloy
And Monel
Photographs of the respective coupons after etching in the liquid phase, wherein FIG. 2(a) is a Hastelloy
Alloy, FIG. 2(b) is Monel
And (3) alloying.
FIG. 3 shows photographs of coupons of tantalum, tantalum alloy Ta-2.5W, and titanium palladium alloy TA9, respectively, after etching in the vapor phase, where FIG. 3(a) is tantalum, FIG. 3(b) is tantalum alloy Ta-2.5W, and FIG. 3(c) is titanium palladium alloy TA 9.
FIG. 4 shows photographs of coupons of tantalum, tantalum alloy Ta-2.5W, and titanium palladium alloy TA9, respectively, after etching in the liquid phase, where FIG. 4(a) is tantalum, FIG. 4(b) is tantalum alloy Ta-2.5W, and FIG. 4(c) is titanium palladium alloy TA 9.
The corrosion rate of each pendant, i.e., the percentage of the weight corroded to the original weight before corrosion, was calculated as the weight loss before and after corrosion. The corrosion resistance results of each corrosion resistant metal are summarized in table 1 below.
TABLE 1
Example 11: production in a 500L reactor
35 kg (0.282kmol) of yellow phosphorus, 200 kg (1.777kmol) of chlorobenzene and 20 kg (0.112kmol) of phenylphosphonic dichloride are placed in a 500L closed autoclave from Hastelloy
Is made of alloy. The temperature is raised to 300 ℃, after 3 hours of reaction under autogenous pressure, the reaction kettle is cooled to room temperature, the material is discharged, the unreacted chlorobenzene is evaporated out through atmospheric distillation, and then the decompression rectification is carried out, thereby producing 100 kg (0.453kmol) of diphenyl phosphine chloride and 127.6 kg (0.713kmol) of phenyl phosphine dichloride.
Example 12: production in 300L reactor
20 kg of yellow phosphorus (0.161kmol), 150 kg of chlorobenzene (1.333kmol) and 20 kg of triphenylphosphine (0.076kmol) are placed in a 500L closed autoclave, made of Monel K500. The temperature is raised to 330 ℃, after 5 hours of reaction under the autogenous pressure, the reaction kettle is cooled to room temperature, the material is discharged, the unreacted chlorobenzene is distilled out under normal pressure and recovered for standby, and then 60 kg (0.272kmol) of diphenyl phosphine chloride and 73.4 kg (0.410kmol) of phenyl phosphine dichloride are produced through reduced pressure rectification.
Example 13: production in a 500L reactor
40 kg (0.323kmol) of yellow phosphorus, 236 kg (2.097kmol) of chlorobenzene and 30 kg (0.168kmol) of phenylphosphonic dichloride were placed in a 500L closed autoclave from Inconel
And (4) preparing. The temperature is raised to 360 ℃, after 3 hours of reaction under autogenous pressure, the reaction kettle is cooled to room temperature, the chlorobenzene is distilled out under normal pressure, and then the vacuum rectification is carried out, thereby producing 134.1 kg (0.608kmol) of diphenyl phosphine chloride and 152.30 kg (0.851kmol) of phenyl phosphine dichloride.
Example 14: production in a 500L reactor
40 kg (0.323kmol) of yellow phosphorus, 280 kg (2.488kmol) of chlorobenzene and 40 kg (0.181kmol) of diphenylphosphinochloride were placed in a 500L closed autoclave from Hastelloy
And (4) preparing. The temperature is raised to 350 ℃, after 3 hours of reaction under autogenous pressure, the reaction kettle is cooled to room temperature, the material is discharged, chlorobenzene which is not completely reacted is evaporated under normal pressure, and the decompression and rectification are carried out, thereby producing 120 kg (0.544kmol) of diphenyl phosphine chloride and 152.6 kg (0.853kmol) of phenyl phosphine dichloride.
Example 15: production in 1000L reactor
80 kg (0.646kmol) of yellow phosphorus, 600 kg (5.330kmol) of chlorobenzene and 50 kg (0.279kmol) of phenylphosphonic dichloride were charged into a 1000L closed autoclave consisting of Incoloy
And (4) preparing. The temperature is raised to 380 ℃,after 4 hours of reaction under autogenous pressure, the reactor was cooled to room temperature, discharged and subjected to rectification under reduced pressure to yield 219.5 kg (0.995kmol) of diphenyl phosphine chloride and 300 kg (1.676kmol) of phenyl phosphine dichloride.
Example 16: production in 1000L reactor
100 kg (0.807kmol) of yellow phosphorus, 600 kg (5.330kmol) of chlorobenzene and 80 kg (0.305kmol) of triphenylphosphine were placed in a 1000L closed autoclave, which was made of Monel K500. The temperature is raised to 400 ℃, after 4 hours of reaction under autogenous pressure, the reaction kettle is cooled to room temperature, and then discharge is carried out, and the diphenyl phosphine chloride 355 kg (1.609kmol) and the phenyl phosphine dichloride 310 kg (1.732kmol) are produced after rectification under reduced pressure.
Example 17: production in a 5000L reactor
500 kg (4.036kmol) of yellow phosphorus, 3000 kg (26.652kmol) of chlorobenzene and 300 kg (1.144kmol) of triphenylphosphine were placed in a 5000L closed autoclave from Inconel
And (4) preparing. The temperature is raised to 430 ℃, after 10 hours of reaction under the autogenous pressure, the reaction kettle is cooled to room temperature, the material is discharged, unreacted chlorobenzene is evaporated under normal pressure, and then the distillation is carried out under reduced pressure, thereby producing 1881 kg (8.525kmol) of diphenyl phosphine chloride and 1500 kg (8.380kmol) of phenyl phosphine dichloride.
Example 18: production in a 5000L reactor
500 kg (4.036kmol) of yellow phosphorus, 2800 kg (24.875kmol) of chlorobenzene and 300 kg (1.360kmol) of diphenylphosphinochloride were placed in a 5000L closed autoclave from Inconel
And (4) preparing. The temperature is raised to 380 ℃, after 8 hours of reaction under the autogenous pressure, the reaction kettle is cooled to room temperature, the chlorobenzene which is not completely reacted is evaporated out under normal pressure, and the chlorobenzene is rectified under reduced pressure to produce 1789 kg (8.108kmol) of diphenyl phosphine chloride and 1600 kg (8.939kmol) of phenyl phosphine dichloride.
Claims (15)
1. A process for the preparation of compounds of the formulae (I) and (II),
wherein
X is halogen, preferably chlorine or bromine, and when two X's are present in the same molecule, they may be the same or different, and
r is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and when two R's are present in the same molecule, R's may be the same or different,
comprising reacting yellow phosphorus with a compound of formula (III) in a reactor,
X-R
(III)
wherein X and R are each as defined for formula (I) and formula (II),
characterized in that the surface of the reactor in contact with the reaction space is made of a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
2. A process for the preparation of compounds of the formulae (I) and (II),
wherein
X is halogen, preferably chlorine or bromine, and when two X's are present in the same molecule, they may be the same or different, and
r is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and when two R's are present in the same molecule, R's may be the same or different,
comprising reacting yellow phosphorus with a compound of formula (III) in the absence of an aluminum trichloride catalyst in a reactor,
X-R
(III)
wherein X and R are each as defined for formula (I) and formula (II),
characterized in that the surface of the reactor in contact with the reaction space is made of a nickel-based alloy as a corrosion-resistant alloy, or the reactor is made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
3. The method according to claim 1 or 2, wherein the nickel-based alloy as the corrosion-resistant alloy is one or more alloys selected from the group consisting of:
1) a Ni-Cu based alloy comprising 20 to 30% by weight of Cu and 70 to 80% of Ni based on the total weight thereof;
2) an Ni-Mo based alloy comprising 50-75 wt% Ni and 15-50 wt% Mo, preferably 28-50 wt% Mo, based on the total weight of the alloy;
3) a Ni — Cr-based alloy containing 50 to 65 wt% of Ni and 15 wt% or more of Cr, preferably 25 wt% or more of Cr, more preferably 35 to 50 wt% of Cr, based on the total weight of the alloy; and
4) other nickel-base corrosion resistant alloys selected from the group consisting of: a Ni-Si alloy comprising 70-85 wt% Ni and 3-10 wt% Si based on the total weight thereof, and a Ni-Cr-Si alloy which is a D-205 alloy comprising 20 wt% Cr, 5 wt% Si and 65 wt% Ni based on the total weight thereof.
4. The method according to claim 1 or 2, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: monel (Monel) alloys (e.g. of the Monel type)
And MonelK500), Inconel (Inconel) alloys (e.g. monel (r) alloy
And
incoloy (Incoloy) alloy (Incoloy)
And
and Hastelloy (e.g., Hastelloy)
And
5. the method according to any one of claims 1 to 4, wherein the inner wall of the pipe or the pipe in contact with the reaction raw material or the reaction product is entirely made of a nickel-based alloy as a corrosion resistant alloy in the wall thickness direction, and/or the valve or those surfaces of the valve in contact with the reaction raw material or the reaction product are made of a nickel-based alloy as a corrosion resistant alloy.
6. Process according to any one of claims 1 to 5, wherein R is the same or different and each independently represents a linear or branched alkyl group containing from 1 to 20, preferably from 1 to 8, carbon atoms (such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl), C6-C10Aryl, preferably C6-C8Aryl groups (e.g., phenyl, o-tolyl, m-tolyl, and p-tolyl), and C6-C10Aralkyl, preferably C6-C8Aralkyl (e.g., benzyl).
7. The process according to any of claims 1 to 6, wherein the molar ratio of the yellow phosphorus to the compound of formula (III) fed is from 1:6 to 1:12, preferably from 1:6 to 1:10, more preferably from 1:6 to 1: 8.
8. A process according to any one of claims 1 to 7, wherein the reaction of yellow phosphorus with the compound of formula (III) is carried out in the presence of one or more compounds selected from the group consisting of the compounds of formulae (I), (II) and (IV) as co-solvent, preferably in the presence of the compound of formula (I) and/or (II) as co-solvent,
wherein R is as defined for compounds of formula (I) and formula (II); preferably, the co-solvent is used in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the total weight of yellow phosphorus and the compound of formula (III).
9. The process of any one of claims 1 to 8 wherein X is chlorine and R in each formula is phenyl or tolyl.
10. The process according to any one of claims 1 to 9, wherein the reaction is carried out at a temperature of 200-; and/or the reaction pressure is autogenous, for example the reaction is carried out at a gauge pressure of 0.01 to 8.0MPa, preferably 0.01 to 6.0MPa, more preferably 0.05 to 5.0 MPa; and/or the reaction time is 2-10h, preferably 2-6 h.
11. A reactor for carrying out the method according to any one of claims 1 to 10, the reactor being a tank reactor comprising: 1) stirrer, 2) a cover, and 3) a body, 4) heating means located outside and/or inside the reaction vessel, and 5) cooling means located outside and/or inside the reaction vessel, wherein the cover and optionally the body of the reaction vessel are provided with openings in the upper part thereof, and the chamber formed by the connection of the cover and the body constitutes the reaction space of the reactor, characterized in that: the material in contact with the reaction space in the reactor is nickel-based alloy as corrosion-resistant alloy, or the reactor is entirely made of nickel-based alloy as corrosion-resistant alloy in the whole thickness direction of the reactor wall, and preferably the volume of the reaction kettle is 300L-5000L.
12. The reactor of claim 11, wherein the vessel lid is a flange lid, and the flange lid is connected to the vessel body by a flange.
13. The reactor according to claim 11 or 12, wherein the nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:
1) a Ni-Cu based alloy comprising 20 to 30% by weight of Cu and 70 to 80% of Ni based on the total weight thereof;
2) an Ni-Mo based alloy comprising 50-75 wt% Ni and 15-50 wt% Mo, preferably 28-50 wt% Mo, based on the total weight of the alloy;
3) a Ni — Cr-based alloy containing 50 to 65 wt% of Ni and 15 wt% or more of Cr, preferably 25 wt% or more of Cr, more preferably 35 to 50 wt% of Cr, based on the total weight of the alloy; and
4) other nickel-base corrosion resistant alloys selected from the group consisting of: a Ni-Si alloy comprising 70-85 wt% Ni and 3-10 wt% Si based on the total weight thereof, and a Ni-Cr-Si alloy which is a D-205 alloy comprising 20 wt% Cr, 5 wt% Si and 65 wt% Ni based on the total weight thereof.
14. The reactor according to any of claims 11-13, wherein the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of: monel alloys (e.g. Monel)
Monel K500), Inconel (Inconel) alloys (e.g., Inconel
Inconel
Inconel
Incoloy (Incoloy) alloy (Incoloy)
Incoloy
And Hastelloy (e.g., Hastelloy)
Hastelloy
Hastelloy
15. Use of a nickel base alloy as a corrosion resistant alloy in the manufacture of a reactor according to any of claims 11-14 and its fittings such as pipes and valves.
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|---|---|---|---|---|
| US3734958A (en) * | 1968-09-09 | 1973-05-22 | Rhone Poulenc Sa | Process for the preparation of diorganochlorophines |
| US20090264689A1 (en) * | 2006-06-27 | 2009-10-22 | E.I. Du Pont De Nemours And Company | Tetrafluoropropene Production Processes |
| CN107912446A (en) * | 2017-12-02 | 2018-04-17 | 南通江山农药化工股份有限公司 | Recycling salt containing glyphosate, Trimethyl phosphite prepares the method and its device of glufosinate-ammonium composite pesticide |
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| US3734958A (en) * | 1968-09-09 | 1973-05-22 | Rhone Poulenc Sa | Process for the preparation of diorganochlorophines |
| US20090264689A1 (en) * | 2006-06-27 | 2009-10-22 | E.I. Du Pont De Nemours And Company | Tetrafluoropropene Production Processes |
| CN107912446A (en) * | 2017-12-02 | 2018-04-17 | 南通江山农药化工股份有限公司 | Recycling salt containing glyphosate, Trimethyl phosphite prepares the method and its device of glufosinate-ammonium composite pesticide |
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