CN1735460A - 制备用于烯烃氢氰化反应的镍/含磷配体催化剂的方法 - Google Patents
制备用于烯烃氢氰化反应的镍/含磷配体催化剂的方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 239000003446 ligand Substances 0.000 title claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000005669 hydrocyanation reaction Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000001336 alkenes Chemical class 0.000 title description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000002825 nitriles Chemical class 0.000 claims abstract description 7
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 6
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims description 21
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 125000005538 phosphinite group Chemical group 0.000 claims description 6
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims 2
- PWHVEHULNLETOV-UHFFFAOYSA-N Nic-1 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC2=C3)C1C2=CC=C3C(C)C1OC(O)C2(C)OC2(C)C1 PWHVEHULNLETOV-UHFFFAOYSA-N 0.000 claims 1
- 238000006263 metalation reaction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- -1 nickelous compound Chemical class 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005337 ground glass Substances 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 150000002738 metalloids Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract
用于制备氢氰化反应催化剂的方法，其包括在腈溶剂和还原金属存在下使二齿含磷配体与氯化镍接触，所述还原金属与镍相比是更电正性的，所述氯化镍作为水溶液引入，并且水通过共沸蒸馏随着还原反应同时地除去。
Description
技术领域
本发明涉及用于制备氢氰化反应催化剂的方法，该催化剂是镍和二齿磷化合物的配合物。
背景技术
在现有技术中，众所周知，镍与含磷配体的配合物可用作氢氰化反应中的催化剂。已知，这类使用单齿亚磷酸酯的镍配合物能够催化丁二烯的氢氰化反应，产生戊烯腈的混合物。这些催化剂还可用于随后的戊烯腈的氢氰化反应，产生己二腈，这是生产尼龙的重要中间体。还已知，二齿亚磷酸酯和卑磷酸酯(phosphinite)配体可用于形成用于进行这种氢氰化反应的镍-基催化剂。
美国专利3,903,120公开了用于制备零价镍配合物的方法，包括使元素镍与通式PZ3的单齿含磷配体反应，其中Z是烷基或者烷氧基，或者优选地芳氧基基团。该方法使用细分散的元素镍，并且优选在腈溶剂存在下进行。该反应在过量配体存在下进行。
美国专利3,846,461公开了用于制备亚磷酸三有机酯的零价镍配合物的方法，包括在细分散的还原金属存在下和在促进剂存在下使亚磷酸三有机酯化合物与氯化镍反应，所述还原金属与镍相比是更电正性的，所述促进剂选自NH3、NH4X、Zn(NH3)2X2以及NH4X和ZnX2的混合物，其中X是卤素。还原金属包括Na、Li、Mg、Ca、Ba、Sr、Ti、V、Fe、Co、Cu、Zn、Cd、Al、Ga、In、Sn、Pb和Th，Zn是优选的。
美国专利5,523,453公开了制备包含二齿含磷配体的镍氢氰化反应催化剂的方法。包含能够被二齿含磷配体置换的配体的零价镍化合物是优选的镍源。两种这类化合物是Ni(COD)2，其中COD是1，5-环辛二烯，和(oTTP)2Ni(C2H4)，其中oTTP是P(O-邻-C6H4CH3)3。
待定美国申请09/994,102描述了通过将二价镍化合物与还原剂接触来生产催化剂的方法。在公开的方法中，镍化合物在引入反应器之前被干燥。该申请描述了随着温度的提高，催化剂生产的速度提高，但是配体降解和副产品形成的量还增加。因此，需要这样一种方法，该方法具有高的反应速率、低的降解和副产品形成，并且具有干燥设备价格比较低廉的优点。
发明内容
一种用于制备氢氰化反应催化剂的方法，其包括使至少一种选自二齿亚磷酸酯和二齿卑磷酸酯的二齿含磷配体与氯化镍在腈溶剂和还原金属存在下接触，所述还原金属与镍相比是更电正性的，其中氯化镍作为水溶液引入，其中(i)水随着氯化镍的还原通过共沸蒸馏被同时除去，或者(ii)水通过共沸蒸馏被除去，然后进行NiCl2的还原。
具体实施方式
本发明的催化剂可以通过在腈溶剂和还原金属存在下使氯化镍与二齿含磷配体接触来制备。氯化镍作为水溶液引入，并且水随着NiCl2还原被同时除去。还原金属可以是任何金属，其与镍相比是更电正性的。这类金属包括Na、Li、K、Mg、Ca、Ba、Sr、Ti、V、Fe、Co、Cu、Zn、Cd、Al、Ga、In和Sn。最优选的是Fe和Zn。还原金属(以下称“MET”)优选是精细粉碎的。措辞“精细粉碎的”指金属具有小于20目的颗粒尺寸。
本发明的镍源是溶于水的镍(II)氯化物或NiCl2。商业上可利用的水溶液是大约29重量百分数NiCl2水溶液。然而，可以相信，本发明不局限于该重量百分数，并且可以使用具有不同重量百分数NiCl2的水溶液。因为实用的原因，优选的水溶液包含20到31重量百分数NiCl2。下限取决于将稀释的溶液进行干燥的成本有效性。上限取决于在环境温度下NiCl2的溶解度，特别地取决于NiCl2(H2O)6的沉淀。
与无水NiCl2不同，因为NiCl2已经溶解，因此反应速率是很快的。令人遗憾地，配体易于水解，因此必须除去水以防止配体降解。已经发现，通过与腈溶剂共沸蒸馏，可以随着NiCl2还原反应同时地将水从反应体系中除去。这通常在低于大气压力下进行，以便降低共沸混合物的沸点并且限制配体和催化剂降解。优选的压力范围为大约0.01psia到3psia(0.07到20kPa)。最优选的压力范围为0.01psia到1.5psia(0.07到10kPa)。用于在反应之前干燥NiCl2的其他方法描述于待定美国申请09/994,102。
催化剂生成反应在溶剂存在下进行，所述溶剂是腈，优选3-戊烯腈或者2-甲基-3-丁烯腈。配体的浓度可以为大约1％到90％重量。因为实用性原因，配体浓度的优选范围是5％到50％。反应程度可以通过使NiCl2或者还原金属(MET)成为限制试剂来控制。MET的优选的量通常为反应物质的0.1％到5％。NiCl2与MET的摩尔比为0.1∶1到100∶1。优选的NiCl2∶MET比例为0.5∶1到2∶1。反应温度可以为0℃到80℃。优选的温度范围是20℃到60℃。反应可以间歇或者连续方式进行。
用于本发明的适合的配体是二齿含磷配体，其选自二齿亚磷酸酯和二齿卑磷酸酯。优选的配体是二齿亚磷酸酯配体。
优选的二齿亚磷酸酯配体具有以下结构式：
其中，R1是未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的苯基；或者未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的萘基；并且Z和Z1独立地选自结构式IV、V、VI、VII和VIII：
和其中
R2、R3、R4、R5、R6、R7、R8和R9独立地选自H、C1到C12烷基和C1到C12烷氧基；
X是O、S或者CH(R10)；
R10是H或者C1到C12烷基；
和其中
R11和R12独立地选自H、C1到C12烷基和C1到C12烷氧基；和CO2R13，
R13是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C6到C10芳基；
Y是O、S或者CH(R14)；
R14是H或者C1到C12烷基；
其中
R15选自H、C1到C12烷基和C1到C12烷氧基和CO2R16；
R16是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C6到C10芳基。
在结构式I到VIII中，C1到C12烷基和C1到C12烷氧基可以是直链或者支链的。
可用于本发明方法的二齿亚磷酸酯配体的实例包括具有以下通式IX到XXXII的那些，其中对于每个通式，R17选自甲基、乙基或者异丙基，并且R18和R19独立地选自H或者甲基：
其他适合的二齿亚磷酸酯是公开于以下专利中的类型：美国专利5,512,695；5,512,696；5,663,369；5,688,986；5,723,641；5,847,101；5,959,135；6,120,700；6,171,996；6,171,997；6,399,534；其中公开的内容引入本文作为参考。适合的二齿卑磷酸酯是公开于以下专利的类型：美国专利5,523,453和5,693,843，其中公开的内容引入本文作为参考。
反应可以以这样一种方式进行，使得未反应的过量NiCl2或者MET可以通过过滤或者离心或者通过沉淀和倾滤与反应产物分离。然后收集的过量的氯化镍或者MET可以循环回到催化剂制备反应器。本发明催化剂可以与3-戊烯腈和HCN一起使用，以生产己二腈。
实施例
本发明通过以下非限制性实施例举例说明。
实施例1举例说明了含水NiCl2的共沸干燥，继之以使用零价铁进行还原，以生产活性催化剂。实施例2举例说明含水NiCl2的同时干燥和使用零价铁进行还原以生产活性催化剂。
实施例1
在250毫升圆底烧瓶上安装用于液体脱除的冷凝器、配体加入漏斗、搅拌器、隔膜口、热电偶、压力传感器和控制压力的真空节流阀。电加热套为圆底烧瓶提供热量。所有附件都由真空密封磨口玻璃接头连接。在氮气下，将120ml新鲜的3-戊烯腈加入加入漏斗。将1.4克30wt％的NiCl2水溶液加入气密的注射器，在针头和注射器之间带有阀门。将120克3-戊烯腈加16.24克具有以上结构IX的配体(其中R17是异丙基、R18是H和R19是甲基)加入圆底烧瓶。泵抽和用氮气吹扫三次，将系统脱气。在搅拌下对烧瓶进行加热。将压力调节到～1.7psia(11.7kPa)。在该压力下3-戊烯腈在～80.2℃下开始回流。通过隔膜将气密注射器上的针头刺入反应器的顶部空间。将含水NiCl2滴加到沸腾的3-戊烯腈中。通过冷凝器将水和3-戊烯腈脱除到空的量筒中。从加入漏斗周期地加入新鲜的3-戊烯腈，以弥补与水馏出造成的3-戊烯腈的损失。NiCl2的滴加持续到所有NiCl2被加入到反应罐中。在氮气覆盖层下将反应罐冷却到62℃。将5.11克铁加10.1克3-戊烯腈的浆液加入该反应罐。泵抽和用氮气吹扫三次，将系统脱气。再次对系统施加真空，并且在65℃和0.7psia(4.8kPa)的压力下脱除3-戊烯腈。在2小时之后，溶液已经变成暗褐色。
在6小时之后，溶液是带有红色色调的暗褐色。停止搅拌，并且允许残余固体沉淀。从反应罐中排出清液。用CO处理从该清液取样的样品并且通过IR分析。在1987和2040cm-1处的吸附表明Ni[0]的摩尔浓度为0.022摩尔/升。LC分析显示不存在明显的配体降解。在50℃下用另外的3-戊烯腈和HCN处理透明溶液的样品产生了己二腈，其速度与通过替代方法生产的催化剂相似。
实施例2
在250毫升圆底烧瓶上安装用于液体脱除的冷凝器、液体加入漏斗、搅拌器、隔膜口、热电偶、压力传感器和控制压力的真空节流阀。电加热套为圆底烧瓶提供热量。所有附件都由真空密封磨口玻璃接头连接。在氮气下，将120ml新鲜的3-戊烯腈加入加入漏斗。将1.44克30wt％的NiCl2水溶液加入气密的注射器，在针头和注射器之间带有阀门。将120克3-戊烯腈加16.49克具有以上结构IX的配体(其中R17是异丙基、R18是H和R19是甲基)加6.59克铁加入圆底烧瓶。泵抽和用氮气吹扫三次，将系统脱气。在搅拌下对烧瓶进行加热。将压力调节到～0.1psia(0.7kPa)。通过隔膜将气密注射器上的针头刺入反应器的顶部空间。将含水NiCl2滴加到沸腾的3-戊烯腈中。通过冷凝器将水和3-戊烯腈脱除到空的量筒中。在～0.1psia(0.7kPa)压力下，温度在30.4℃到41.5℃之间变化。从加入漏斗周期地加入新鲜的3-戊烯腈，以弥补与水馏出造成的3-戊烯腈的损失。NiCl2的滴加持续到所有NiCl2被加入到反应罐中。在69分钟之后，NiCl2加入完成。溶液呈暗褐色-黄色颜色。将对反应罐的加热和抽真空关闭。在氮气覆盖层下将反应罐搅拌过夜，而不加热。在早上停止搅拌，并且允许残余固体沉淀。从反应罐中排出清液。用CO处理从该清液取样的样品并且通过IR分析。在1987和2040cm-1处的吸附表明Ni[0]的摩尔浓度为0.013摩尔/升。LC分析显示不存在明显的液体降解。在50℃下用另外的3-戊烯腈和HCN处理透明溶液的样品产生了己二腈，其速度与通过替代方法生产的催化剂相似。
Claims (11)
1.一种用于制备氢氰化反应催化剂的方法，其包括使至少一种选自二齿亚磷酸酯和二齿卑磷酸酯的二齿含磷配体与氯化镍在腈溶剂和还原金属存在下接触，所述还原金属与镍相比是更电正性的，其中氯化镍作为水溶液引入，其中(i)水随着氯化镍的还原通过共沸蒸馏被同时除去，或者(ii)水通过共沸蒸馏被除去，然后进行NiCl2的还原。
2.权利要求1的方法，其中二齿含磷配体是二齿亚磷酸酯。
3.权利要求2的方法，其中还原金属选自Na、Li、K、Mg、Ca、Ba、Sr、Ti、V、Fe、Co、Cu、Zn、Cd、Al、Ga、In和Sn。
4.权利要求3的方法，其还包括将未反应的氯化镍或者还原金属与氢氰化反应催化剂分离。
5.权利要求3的方法，其中还原金属是Zn或者Fe。
6.权利要求2的方法，其中催化剂制备在0℃到80℃的温度下和在大约0.07kPa到大约20kPa的压力下进行。
7.权利要求6的方法，其中催化剂制备在大约20℃到大约60℃的温度下进行。
8.权利要求2的方法，其中NiC12与还原金属的摩尔比是0.1∶1到100∶1。
9.权利要求8的方法，其中NiCl2与还原金属的摩尔比是0.5∶1到2∶1。
10.权利要求9的方法，其中二齿含磷配体是具有以下通式的化合物
(R1O)2P(OZO)P(OR1)2，
I
其中，R1是未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的苯基；或者未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的萘基；并且Z和Z1独立地选自结构式IV、V、VI、VII和VIII：
和其中
R2、R2、R3、R5、R6、R7、R4和R9独立地选自H、C1到C12烷基和C1到C12烷氧基；
X是O、S或者CH(R10)；
R10是H或者C1到C12烷基；
和其中
R11和R12独立地选自H、C1到C12烷基和C1到C12烷氧基；和CO2R13，
R13是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C6到C10芳基；
Y是O、S或者CH(R14)；
R14是H或者C1到C12烷基；
其中
R15选自H、C1到C12烷基和C1到C12烷氧基和CO2R16；
R16是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C8到C10芳基，
其中在结构式I到VIII中，C1到C12烷基和C1到C12烷氧基是直链或者支链的。
11.权利要求2的方法，其中所述方法还包括使催化剂与3-戊烯腈和氰化氢接触以生产己二腈。
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| US10/341,860 US6897329B2 (en) | 2003-01-14 | 2003-01-14 | Process for the preparation of nickel/phosphorous ligand catalyst for olefin hydrocyanation |
| US10/341,860 | 2003-01-14 |
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| EP (1) | EP1587621B1 (zh) |
| CN (1) | CN100348322C (zh) |
| AT (1) | ATE334745T1 (zh) |
| DE (1) | DE602004001755T2 (zh) |
| ES (1) | ES2270333T3 (zh) |
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| US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
| US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
| US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
| US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
| US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
| US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
| CN107008500A (zh) * | 2012-12-07 | 2017-08-04 | 因温斯特技术公司 | 用于改善镍‑配体的溶解性的组合物 |
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| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
| US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
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| CN107020150B (zh) * | 2011-06-10 | 2019-11-29 | 英威达纺织（英国）有限公司 | 镍金属配体催化剂形成上的改进 |
| CN107008500A (zh) * | 2012-12-07 | 2017-08-04 | 因温斯特技术公司 | 用于改善镍‑配体的溶解性的组合物 |
| CN109999913A (zh) * | 2012-12-07 | 2019-07-12 | 英威达纺织（英国）有限公司 | 用于改善镍-配体的溶解性的组合物 |
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| Publication number | Publication date |
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| TW200508181A (en) | 2005-03-01 |
| ES2270333T3 (es) | 2007-04-01 |
| EP1587621B1 (en) | 2006-08-02 |
| ATE334745T1 (de) | 2006-08-15 |
| WO2004064994A3 (en) | 2004-09-30 |
| EP1587621A2 (en) | 2005-10-26 |
| US6897329B2 (en) | 2005-05-24 |
| US20040138494A1 (en) | 2004-07-15 |
| TWI312343B (en) | 2009-07-21 |
| MY134482A (en) | 2007-12-31 |
| DE602004001755D1 (de) | 2006-09-14 |
| WO2004064994A2 (en) | 2004-08-05 |
| CN100348322C (zh) | 2007-11-14 |
| DE602004001755T2 (de) | 2007-08-09 |
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