CN1216034A - 制备1,3-丙二醇的方法 - Google Patents
制备1,3-丙二醇的方法 Download PDFInfo
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- CN1216034A CN1216034A CN97193774A CN97193774A CN1216034A CN 1216034 A CN1216034 A CN 1216034A CN 97193774 A CN97193774 A CN 97193774A CN 97193774 A CN97193774 A CN 97193774A CN 1216034 A CN1216034 A CN 1216034A
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- water
- cobalt
- solvent
- catalyst
- organic phase
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title abstract 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 3
- 229940035437 1,3-propanediol Drugs 0.000 title abstract 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 title abstract 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 50
- 239000010941 cobalt Substances 0.000 claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
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- 230000008569 process Effects 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 17
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- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 4
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- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- 239000002184 metal Substances 0.000 description 4
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- 239000000376 reactant Substances 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
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- -1 cobalt carbonyl compound Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- ONNUYWHIJSKABC-UHFFFAOYSA-N 2-methylpropoxybenzene Chemical compound CC(C)COC1=CC=CC=C1 ONNUYWHIJSKABC-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZRGHTFCHVAZSMM-UHFFFAOYSA-N [P].C(CCC)OC(C(CCCC)(CCCC)CCCC)=O Chemical compound [P].C(CCC)OC(C(CCCC)(CCCC)CCCC)=O ZRGHTFCHVAZSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical group CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 230000007420 reactivation Effects 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract
通过如下方法制备1,3-丙二醇,其中,将环氧乙烷与一氧化碳和氢气在基本上与水不相混溶的溶剂中、在有效量非膦配位的钴催化剂和有效量助催化剂存在下、在能够有效生成含有低于15%(重量)3-羟基丙醛的中间体产物混合物的反应条件下反应。将3-羟基丙醛从产物混合物中以更浓的形式萃取到水中,同时大部分钴催化剂保留在溶剂相中以循环到加氢甲酰化反应中。通过用与水不相混溶的溶剂再萃取,将至少部分在萃取后残留于水相中的催化剂回收并循环到加氢甲酰化反应中。然后将3-羟基丙醛在含水溶液中氢化得到所需的1,3-丙二醇。
Description
本发明涉及1,3-丙二醇的制备。一方面,本发明涉及以高产率生产1,3-丙二醇的钴催化方法,该方法不使用钴催化剂的膦配体。具体地讲,本发明涉及在该方法中改进钴催化剂的回收和循环程度。
1,3-丙二醇(PDO)是纤维和胶片所用聚酯生产过程中的中间体。已知可用两步法制备PDO,所述方法包括(1)将环氧乙烷进行钴催化的加氢甲酰化反应(与合成气即H2/CO反应)生成中间体3-羟基丙醛(HPA),和(2)将HPA氢化生成PDO。起始的加氢甲酰化步骤可以在高于100℃的温度和高合成气压力下进行以达到实用的反应速率。但是,得到的产物混合物对HPA的选择性很差。
在另一种加氢甲酰化方法中,将钴催化剂与膦配体联合使用以便在较低的温度和压力下高选择性地制备HPA。但是,使用膦配体增加了催化剂的成本并且增加了催化剂循环的复杂性。
因此需要以低温、选择性的方法制备HPA,在该方法中,钴催化剂的回收廉价但基本完全。
因此,本发明的目的是提供制备1,3-丙二醇的方法,该方法在制备HPA中间体时无需使用膦配位的催化剂,能够基本完全回收和循环钴催化剂。
根据本发明,制备1,3-丙二醇的方法包括如下步骤:
(a)将环氧乙烷与一氧化碳和氢气在基本上与水不相混溶的溶剂中、在有效量非膦配位的钴催化剂和有效量助催化剂存在下、在能够有效生成含有低于15%(重量)3-羟基丙醛的中间体产物混合物的反应条件下接触;
(b)向所述中间体产物混合物中加入含水液体并将大部分3-羟基丙醛萃取到所述含水液体中,从而得到所含3-羟基丙醛的浓度大于所述中间体产物混合物中3-羟基丙醛浓度的水相,以及含有大部分钴催化剂或其含钴衍生物的有机相;
(c)将水相与有机相分离;
(d)向所述水相中加入新鲜的与水不相混溶的溶剂并将所述水相中所含的钴催化剂或其含钴衍生物的至少一部分萃取到所述新鲜溶剂中,以得到含有3-羟基丙醛的第二水相和含有钴催化剂或其含钴衍生物的第二有机相;
(e)将第二水相与第二有机相分离;
(f)将第一有机相和第二有机相转移到步骤(a)的反应中;
(g)将含有3-羟基丙醛的第二水相与氢气在氢化催化剂存在下于氢化条件下接触,生成含有1,3-丙二醇的氢化产物混合物;然后
(h)从所述氢化产物混合物中回收1,3-丙二醇。
该方法能够以高产率选择性地生成1,3-丙二醇,在加氢甲酰化步骤中无需使用膦配位的钴催化剂并且提高了钴催化剂的回收和循环。
图1是钴回收率提高了的本发明1,3-丙二醇制备方法的一个实施方案的流程图。
可以参照图1方便地对本发明的1,3-丙二醇制备方法进行描述。将单独的或混合的环氧乙烷1、一氧化碳和氢气流2加入到加氢甲酰化容器3内,该容器可以是压力反应器如泡罩塔或搅拌槽,并且以分批或连续的方式操作。将原料流在非膦配位的钴催化剂、即未与膦配体预反应的羰基钴组合物存在下接触。通常以1∶2至8∶1,优选1.5∶1至5∶1的摩尔比将氢气和一氧化碳通入反应容器。
反应在能够有效生成含有大部分3-羟基丙醛(HPA)和少部分乙醛和1,3-丙二醇的加氢甲酰化反应产物混合物的条件下进行,同时保持反应混合物中3-羟基丙醛的含量低于15%(重量),优选在5-10%(重量)的范围内。(为了保证溶剂具有不同的密度,反应混合物中HPA的所需浓度用摩尔浓度表示时应低于1.5M,优选在0.5-1M的范围内)。
通常,加氢甲酰化反应在低于100℃的升温下进行,优选60-90℃,最优选75-85℃,反应压力在3.4-34.5MPa(500-5000磅/平方英寸)的范围内,优选(为了方法的经济性)6.9-24.1MPa(1000-3500磅/平方英寸),为了能有较高的选择性,优选较高的压力。可以通过调节反应条件如环氧乙烷的浓度、催化剂的浓度、反应温度以及停留时间来控制中间体产物混合物中3-羟基丙醛的浓度。通常,优选相对低的反应温度(低于90℃)和相对短的停留时间(20分钟至1小时)。在本发明方法的实践中,HPA的收率可以超过80%(以环氧乙烷的转化率为基准计),以超过30h-1的速率形成高于7%(重量)的HPA。(催化速率在本文中以术语“周转频率”或“TOF”表述,用每小时每摩尔钴的摩尔数或h-1的单位来表示)。文献中报道的速率基于下列观察结果:在大部分E0被转化之前,反应体系中环氧乙烷的浓度基本上为零数量级并且与钴浓度成正比。
加氢甲酰化反应在对反应试剂呈惰性的液体溶剂中进行。“惰性”是指该溶剂在反应过程中不被消耗。通常,用于该无膦配体方法的理想溶剂能够溶解一氧化碳、基本上与水不相混溶并且具有低至中等的极性,从而可以使3-羟基丙醛中间产物在加氢甲酰化条件下可以溶解到至少5%(重量)的所需浓度,并且在用水萃取后仍有大量溶剂以分离的相的形式保留下来。“基本上与水不相混溶”是指25℃时,该溶剂在水中的溶解度低于25%(重量),从而在用水从加氢甲酰化反应混合物中萃取HPA后可以形成分离的、富含烃的相。优选该溶解度低于10%,最优选低于5%(重量)。用奥斯特瓦尔德系数表示,一氧化碳在选定溶剂中的溶解通常大于0.15v/v(1atm,25℃),优选大于0.25v/v。
优选的溶剂类型是醇和醚,可将其用如下结构式表示,
R2-O-R1 (1)
其中R1是氢或C1-8烃基,R3、R4和R5彼此独立地选自C1-8烃基、烷氧基和氧化烯。所述醚包括,例如甲基叔丁基醚、乙基叔丁基醚、二乙醚、苯基异丁基醚、乙氧基乙基醚、二苯醚和二异丙醚。也可以使用溶剂的混合物如四氢呋喃/甲苯、四氢呋喃/庚烷以及叔丁醇/己烷来达到所需的溶剂性质。目前优选的溶剂是甲基叔丁基醚,其原因在于可以在适中的反应条件下得到高产率的HPA。
催化剂为非膦配位的羰基钴化合物。尽管膦配位的催化剂在加氢甲酰化反应中是有活性的,但本发明方法能够不使用配体而得到良好的收率和选择性。可将钴催化剂以任何形式加入到加氢甲酰化反应器中,包括例如金属、载体上的金属、阮内钴、氢氧化物、氧化物、碳酸盐、硫酸盐、乙酰基丙酮化物、羧酸盐或钴盐水溶液。可直接以羰基钴如八羰基合二钴或氢羰基钴的形式加入。如果不是以后一种形式加入,则可改变操作条件,从而可以通过与H2和CO反应就地生成羰基钴,参见J.Falbe,“有机合成中的一氧化碳”,Springer-Verlag,NY(1970)。通常,催化剂的形成条件包括温度至少为50℃,一氧化碳的分压至少为0.7MPa(100磅/平方英寸)。为了使反应更加迅速地完成,可采用120-200℃的温度,CO的压力至少为3.4MPa(500磅/平方英寸)。加入高表面积的活性炭或沸石、特别是那些含有或载有铂或钯金属的种类,可以促进从无羰基的前体生成羰基钴。生成的催化剂保持在一氧化碳的稳定气体氛围下,一氧化碳还可以防止与氧气接触。最经济和优选的催化剂活化和循环催化剂的再活化方法包括,在少量羰基钴晶种存在下,在H2/CO气氛下从氢氧化钴预形成羰基钴。Co+2向所需羰基钴的转变在75-200℃、优选100-140℃的温度范围内和6.9-34.5MPa(1000-5000磅/平方英寸)的压力下进行,反应时间优选少于3小时。预形成步骤可以在加压预形成反应器中进行或在加氢甲酰化反应器中就地进行。
反应混合物中钴的含量取决于其它反应条件,但通常在0.01-1%(重量)、优选0.05-0.3(重量)的范围内,以反应混合物的重量为基准计。
加氢甲酰化反应混合物优选含有助催化剂以加快反应速率。适宜的助催化剂包括可以提供一价和多价弱碱金属阳离子的物质,如碱金属、碱土金属和稀土金属的羧酸盐。其它适宜的助催化剂是亲脂性助催化剂例如亲脂性磷盐和亲脂性胺,它们可以加快加氢甲酰化反应速率而不会使活性催化剂具有亲水性(水溶性)。本文使用的“亲脂性”是指用水萃取HPA后,助催化剂倾向于保留在有机相中。助催化剂的含量通常为0.01-0.6摩尔/摩尔钴。适宜的金属盐包括钠、钾和铯的乙酸盐、丙酸盐和辛酸盐;碳酸钙和乙酸镧。目前优选的金属盐是乙酸钠,其原因在于易得并且已证实可以促进环氧乙烷的加氢甲酰化反应。目前优选的亲脂性助催化剂是二甲基十二烷基胺和四丁基乙酸磷。
通常优选控制加氢甲酰化反应混合物中水的浓度,因为过量的水会使(HPA+PDO)的选择性降低到可接受的水平以下,并且会导致形成第二个液相。在低浓度下,水有助于促进所需的羰基钴催化剂的形成。可接受的水的含量取决于所用的溶剂,更具极性的溶剂通常能够接受更高的水浓度。例如,据信在用甲基叔丁基醚溶剂进行的加氢甲酰化反应中,最佳水含量为1-2.5%(重量)。
加氢甲酰化反应后,将含有3-羟基丙醛、反应溶剂、1,3-丙二醇、钴催化剂和少量反应副产物的加氢甲酰化反应产物混合物4冷却并转移到萃取容器5中,通过6向其中加入含水液体以萃取并浓缩HPA以用于随后的氢化步骤,所述含水液体通常是水和视具体情况存在的可混溶溶剂。可通过任何适宜的方法例如混合澄清槽、填料或塔板萃取柱、或转盘式抽提器完成液体萃取。如需要,萃取可分多级进行。也可以视具体情况而定将含水加氢甲酰化反应产物混合物转移到澄清槽(未示出)内以使混合物分成水相和有机相。通常,加入到加氢甲酰化反应产物混合物中的水量应能够提供1∶1至1∶20、优选1∶5至1∶15范围内的水∶混合物比。在该反应阶段加入水的另一优点是可以抑制不利的重尾馏份的形成。用相对少量的水进行萃取可以得到超过20%(重量)HPA、优选超过35%(重量)HPA的水相,从而可以经济地将HPA氢化成PDO并回收PDO产物。优选在25℃至55℃的温度下进行水萃取,同时避免使温度进一步升高从而最大限度地抑制缩合产物(重尾馏份)的形成和催化剂歧化形成无活性的、水溶性钴化合物。为了最大限度的回收催化剂,优选在0.3-1.4MPa(50-200磅/平方英寸)一氧化碳下于25-55℃进行水萃取。
可通过7将含有反应溶剂和大部分钴催化剂的有机相从萃取容器循环到加氢甲酰化反应中。根据本发明,将含水萃取液8转移到第二萃取容器9中,在该容器中,通过10加入一定量新鲜的加氢甲酰化反应所用的与水不相混溶的溶剂如甲基叔丁基醚,以萃取残留在水相中的羰基钴或其含钴衍生物。为了方法的经济性,优选将这些钴催化剂尽可能多地回收和循环到加氢甲酰化步骤中。已发现,将第二次萃取步骤与蒸馏或其它浓缩被循环到加氢甲酰化反应中的物流中的钴的方法结合使用时,通常可以回收30%(重量)以上、最佳可回收75%(重量)以上的钴,否则这些钴将流失到水萃取后的含水3-羟基丙醛相中。该方法有助于实现回收和循环存在于加氢甲酰化反应过程中的至少99.6%(重量)钴的总目标。
第二次萃取步骤所用的溶剂可以是上述用于加氢甲酰化反应步骤的任何溶剂;但是,优选该溶剂与加氢甲酰化步骤所选的溶剂相同,首选甲基叔丁基醚。所述溶剂可以是新补充的溶剂,也可以是从后续蒸馏过程回收的溶剂。
第二阶段的萃取首选在25-55℃的温度下进行,优选且视具体情况而定的一氧化碳的压力为0.3-1.3MPa(50-200磅/平方英寸)。该过程可以在与水萃取步骤相同或不同的容器中,通过将溶剂在搅拌下加入到水相中然后使有机相和水相分层来完成。在该过程中,以待处理液相的量计,溶剂的用量可以是3-300%(重量),这取决于循环催化剂和反应溶剂过程所选用的方法。或者,可将含钴的水相在上述条件下与加入的溶剂在多级容器中逆流接触。将含有回收钴的第二级萃取的溶剂相通过11循环到加氢甲酰化反应中,通过蒸馏或其它方法控制钴的浓度。
将脱钴的含水产物混合物12转移到氢化容器13中,并在氢化催化剂存在下与氢气14反应,生成含有1,3-丙二醇的氢化产物混合物15。氢化步骤还可以使一些重尾馏份复原成PDO。可通过在柱16中蒸馏来回收溶剂和萃取剂水17,在通过进一步蒸馏(未示出)分离并除去轻馏份后将其重新用于水萃取步骤。可将含有PDO的产物流18转移到蒸馏柱19中,以便从重尾馏份21中回收PDO 20。
将HPA转变成PDO的氢化反应可以在含水溶液中,在升高的温度及至少0.7MPa(100磅/平方英寸)、通常为1.4-13.8MPa(200-2000磅/平方英寸)的氢气压力下进行,所述温度在氢化步骤的至少部分时间内为40℃,一般在50-175℃的范围内。反应在固定床氢化催化剂的存在下进行,所述催化剂是例如任何基于Ⅷ族金属,包括镍、钴、钌、铂和钯,以及铜、锌和铬以及它们的混合物和合金的催化剂。优选的催化剂是含镍组合物颗粒。氢化反应优选在三个连续的温度阶段进行:第一阶段在50-70℃;第二阶段在70-100℃;第三阶段、即高温阶段在120℃以上,以将重尾馏份转变成1,3-丙二醇。在略显酸性的反应条件下可以得到最高的收率。
实施例1
进行该实验用来检测是否可以从3-羟基丙醛水溶液中脱除残余的羰基钴加氢甲酰化催化剂,所述3-羟基丙醛水溶液是通过用水从羰基钴催化的环氧乙烷加氢甲酰化反应的反应产物混合物中萃取3-羟基丙醛而得到的。
室温及4.1MPa(600磅/平方英寸)1∶1(CO∶H2)合成气下,向一份3-羟基丙醛水溶液中边搅拌边加入两份新鲜的甲基叔丁基醚。使两相分离。取出“新”的水相,将两相均通过钴特异性的钴比色法进行分析。最初水相中的60%的钴得到回收。
实施例2
进行一系列实验,其中的含水中间体产物直接从3.81(1加仑)环氧乙烷加氢甲酰化反应液中取样,随后在反应器中于25-45℃及3.4-9.0MPa(500-1300磅/平方英寸)1∶1合成气下用水萃取。将含水产物转移到氮气密封的盛有用氮气喷入的甲基叔丁基醚的瓶中。使用合成气可以在瓶的上方形成合成气层。振摇瓶以使水相与MTBE充分接触,然后使各相分离。用酸分解后,通过比色法测定各相中钴的含量。结果如表1所示。根据所采用的条件,溶剂再萃取的钴回收率为5-80%。
表1用MTBE再萃取含水产物回收钴
序号 | Co初始浓度UL(ppm) | Co初始浓度LL(ppm) | 再萃取MTBE/LL比MTBE/LL | Co再萃取液LL(ppm) | Co再萃取液MTBE(ppm) | 回收率% |
1 | 2211 | 168 | 0.34 | 33 | 400 | 80 |
2 | 2266 | 132 | 1.45 | 52 | 28 | 44 |
3 | 236 2 | 225 | 3.33 | 110 | 52 | 54 |
4 | 2325 | 208 | 6.33 | 142 | 34 | 39 |
5 | 2421 | 257 | 3.06 | 226 | 54 | 17 |
6 | 2581 | 187 | 2.06 | 185 | 64 | 5 |
7 | 2156 | 181 | 0.17 | 129 | 407 | 29 |
8 | 2102 | 92 | 0.17 | 64 | 361 | 31 |
9 | 2287 | 136 | 0.10 | 115 | 238 | 16 |
10 | 2156 | 130 | 0.14 | 62 | 339 | 57 |
%回收率=可通过再萃取回收的原始LL中的钴%UL=上层LL=下层 |
实施例3
在用塑料环填充的高76.2cm(30英寸)、内径2.54cm(1英寸)的萃取器内,将来自连续中试装置PDO制备方法第一萃取阶段的含水产物(含25%(重量)3-羟基丙醛中间体和67ppm钴)以7.08g/分钟的流速用逆流的新鲜MTBE以0.67g/分钟的流量萃取。萃取在40℃和9.7MPa(1400磅/平方英寸)3∶1 H2/CO下进行。第二萃取器的含水流出液中钴的含量为43ppm,使初始物料中35%的钴得到回收。MTBE溶剂由塔顶排出,含254ppm钴。MTBE的流速与补充经含水产物从加氢甲酰化系统中流失的MTBE所需的量相匹配。为了得到更高的萃取效率,可以增加MTBE流速,同时将催化剂和MTBE分离以循环浓度更高的钴/MTBE物料流,并保持加氢甲酰化系统中MTBE溶剂的总量。
Claims (10)
1.制备1,3-丙二醇的方法,该方法包括如下步骤:
(a)将环氧乙烷与一氧化碳和氢气在基本上与水不相混溶的溶剂中、在有效量非膦配位的钴催化剂和有效量助催化剂存在下、在能够有效生成含有低于15%(重量)3-羟基丙醛的中间体产物混合物的反应条件下接触;
(b)向所述中间体产物混合物中加入含水液体并将大部分3-羟基丙醛萃取到所述含水液体中,从而得到所含3-羟基丙醛的浓度大于所述中间体产物混合物中3-羟基丙醛浓度的第一水相,以及含有大部分羰基钴催化剂或其含钴衍生物的第一有机相;
(c)将第一水相与第一有机相分离;
(d)向所述第一水相中加入新鲜的与水不相混溶的溶剂并将所述水相中所含的钴催化剂或其含钴衍生物的至少一部分萃取到所述溶剂中,以得到含有3-羟基丙醛的第二水相和含有钴催化剂或其含钴衍生物的第二有机相;
(e)将第二水相与第二有机相分离;
(f)将第一有机相和第二有机相转移到步骤(a)的反应中;
(g)将含有3-羟基丙醛的第二水相与氢气在氢化催化剂存在下于氢化条件下接触,生成含有1,3-丙二醇的氢化产物混合物;然后
(h)从氢化产物混合物中回收1,3-丙二醇。
2.权利要求1的方法,其中步骤(a)中水的含量为1-2.5%(重量)。
3.权利要求1或2的方法,其中步骤(a)中一氧化碳和氢气的比为H2/CO=1.5∶1-5∶1,并且步骤(a)在60-90℃的温度和6.9-24.1MPa的压力下进行。
4.权利要求1-3中任一项的方法,其中步骤(b)在25-55℃的温度下进行。
5.权利要求1-4中任一项的方法,其中步骤(b)和(d)在一氧化碳下进行。
6.权利要求1-5中任一项的方法,其中步骤(a)和(d)中与水不相混溶的溶剂包括醚。
7.权利要求6的方法,其中步骤(a)和(d)中与水不相混溶的溶剂是甲基叔丁基醚。
8.权利要求1-7中任一项的方法,其中步骤(d)通过将新鲜溶剂与第一水相分级逆流接触来完成。
9.权利要求1-8中任一项的方法,其中步骤(d)中溶剂的加入量为3-300%(重量),以水相的重量为基准计。
10.权利要求1-9中任一项的方法,其中步骤(d)在25-55℃的温度和0.3-1.4MPa的一氧化碳压力下进行。
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US08/615,544 US5770776A (en) | 1994-09-30 | 1996-03-11 | Process for preparing 1,3-propanediol |
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US (1) | US5770776A (zh) |
EP (1) | EP0888266B1 (zh) |
KR (1) | KR100515874B1 (zh) |
CN (1) | CN1089330C (zh) |
AU (1) | AU711691B2 (zh) |
DE (1) | DE69705209T2 (zh) |
NO (1) | NO309897B1 (zh) |
WO (1) | WO1997033851A1 (zh) |
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CN111377808A (zh) * | 2018-12-27 | 2020-07-07 | 上海华谊能源化工有限公司 | 一种处理含有钴基催化剂的3-羟基丙醛混合溶液的方法 |
CN111377808B (zh) * | 2018-12-27 | 2022-10-04 | 上海华谊能源化工有限公司 | 一种处理含有钴基催化剂的3-羟基丙醛混合溶液的方法 |
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DE69705209D1 (de) | 2001-07-19 |
AU711691B2 (en) | 1999-10-21 |
AU2153997A (en) | 1997-10-01 |
KR19990087591A (ko) | 1999-12-27 |
WO1997033851A1 (en) | 1997-09-18 |
DE69705209T2 (de) | 2001-11-15 |
EP0888266A1 (en) | 1999-01-07 |
KR100515874B1 (ko) | 2006-01-12 |
NO984111D0 (no) | 1998-09-07 |
CN1089330C (zh) | 2002-08-21 |
US5770776A (en) | 1998-06-23 |
NO309897B1 (no) | 2001-04-17 |
NO984111L (no) | 1998-11-06 |
EP0888266B1 (en) | 2001-06-13 |
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