CN107684919B - 负载型Ni3P催化剂及其制备方法和应用 - Google Patents
负载型Ni3P催化剂及其制备方法和应用 Download PDFInfo
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- CN107684919B CN107684919B CN201710655419.4A CN201710655419A CN107684919B CN 107684919 B CN107684919 B CN 107684919B CN 201710655419 A CN201710655419 A CN 201710655419A CN 107684919 B CN107684919 B CN 107684919B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229940027987 antiseptic and disinfectant phenol and derivative Drugs 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 10
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 20
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
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- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003635 deoxygenating effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
- 229910018104 Ni-P Inorganic materials 0.000 description 26
- 229910018536 Ni—P Inorganic materials 0.000 description 26
- 239000003921 oil Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 p-cresol decalin Chemical compound 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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Abstract
负载型Ni3P催化剂及其制备方法和应用。本发明属于生物质油加工技术领域,其中所述的催化剂采用化学镀法制备。所述制备方法是将催化剂载体置于化学镀液中,然后升温至75‑95℃,反应0.5‑4h制得催化剂前体;在化学气氛下将催化剂前体升温至200‑600℃,热处理0.5‑5h后降温,制得负载型Ni3P催化剂。其催化的加氢脱氧反应以含氧的苯酚及其衍生物的水溶液或油溶液为反应原料,在连续流动的固定床反应器中进行。本发明中,采用化学镀法制备的负载型Ni3P催化剂较之体相Ni3P,具有更高的催化苯酚及其衍生物加氢脱氧活性,对生物质油的脱氧提质具有很好的效果。
Description
技术领域
本发明属于多相负载型催化剂制备技术领域,涉及一类在催化剂载体表面化学镀镍磷合金层以制备负载型Ni3P催化剂的方法,以及该催化体系在生物质油加氢脱氧反应中的应用。
背景技术
近年来,能源消耗与环境污染日益加剧,以生物质油为代表的可再生能源的开发利用受到关注。生物质油具有可再生性、二氧化碳零排放、硫和氮含量较低、资源分布广、转化方式多等优点,但其中氧和水的含量较高。生物质油中大量的含氧化合物会导致一些严重的问题,如油品热值低、化学稳定性差、粘度大、腐蚀设备等,严重阻碍其作为汽柴油替代燃料的广泛使用,必须对其进行脱氧精制。在加氢脱氧(HDO) 催化剂中,研究较多的是炼油工业用的Ni(Co)MoS/γ-Al2O3加氢脱硫(HDS)催化剂。然而,在HDO反应过程中,硫化物催化剂会因硫原子被氧原子同晶取代或者被水氧化成相应的硫酸盐而导致失活,故而需要开发耐水的、高活性及稳定性的加氢脱氧催化剂。以Ni2P、MoP、WP、Co2P以及CoP为代表的一系列过渡金属磷化物以其高活性和稳定性在加氢精制(包括加氢脱氧)领域有广阔的应用前景。在前期的研究中发现,Ni3P具有较高的催化苯酚水相及油相加氢脱氧活性及稳定性。
以苯酚为代表的酚类化合物加氢脱氧通常分为两条反应路径:一是直接脱氧(DDO)形成芳烃;二是通过预加氢(HYD)路径形成环醇,在酸中心作用下催化脱水形成烯烃,再加氢形成烷烃(Chem.Comm.,2010,46:1038-1040)。故而高活性的加氢脱氧催化剂需要同时具有加氢中心和酸中心。非负载的磷化镍催化剂酸性较弱(J. Phys.Chem.C,2008,112:16584-16592),欲满足催化加氢脱氧需求,需制备酸性载体负载的磷化镍催化剂。传统的负载型磷化镍催化剂多采用浸渍法制备前体,再采用H2程序升温还原制备催化剂。以Al2O3、沸石分子筛等为载体时,在催化剂制备过程中P 与Al发生作用形成尖晶石结构(Catal.Lett.,2012,142:1413-1436),从而限制了磷化镍的形成。采用化学镀法可以在低温下合成无定形Ni-P催化剂前体,避免高温环境下载体与活性组分的反应,有利于Ni-P催化剂的制备。目前,化学镀法制备Ni-P多用于制备防腐和耐磨材料(J.Solid StateElectr.,2014,18:1951-1961;Cryst.Res.Technol., 2014,49:178-189),未有用于制备磷化镍加氢脱氧催化剂方面的报道。
发明内容
本发明的目的在于提供一种由新的制备方法所制得的负载型Ni3P催化剂,并提供其制备方法以及用途。
本发明所述及的新的负载型Ni3P催化剂的制备方法是将催化剂载体置于化学镀液中,然后升温至75-95℃,反应0.5-4h制得催化剂前体;在化学气氛下将催化剂前体升温至200-600℃,热处理0.5-5h后降温,制得负载型Ni3P催化剂。
本发明所述的化学镀的方法可以在较低温度下合成负载型Ni3P催化剂,对应用的载体并不限定,可应用的载体不仅包括SiO2、Al2O3等常用载体,还包括WO3、TiO2、 ZrO2、CeO2等功能性氧化物和HY、HZSM-5、Hβ等沸石分子筛。
而以上述方法所制备出的负载型Ni3P催化剂对于苯酚及其衍生物的加氢脱氧反应,相对于体相Ni3P,也表现出更高的反应活性。该方法制备的催化剂,在固定床反应器中以较温和的反应条件进行连续加氢脱氧反应,对生物质油的脱氧提质具有很好的效果。
基于此,本发明另一方面公开上述本发明的方法制得的负载型Ni3P催化剂,再一方面也提供上述催化剂在生物油中苯酚及其衍生物加氢脱氧反应中的应用,亦即一种生物油中苯酚及其衍生物加氢脱氧的方法,该方法包括加氢脱氧反应,所述反应中使用本发明的方法制得的负载型Ni3P催化剂。
附图说明
本发明附图2幅:
图1是采用化学镀法制备的负载型Ni3P催化剂的XRD谱图,所使用的载体分别是SiO2、Al2O3、TiO2、ZrO2、WO3、CeO2、HZSM-5、Hβ、HY;
图2是催化苯酚水相加氢脱氧反应前后的EP-Ni-P/SiO2和EP-Ni-P/Al2O3催化剂的XRD谱图。
具体实施方式
本发明旨在提供一种新的化学镀的方法制备负载型Ni3P催化剂的方法,并且提供该新的负载型Ni3P催化剂及其应用。本发明所述的负载型Ni3P催化剂的制备方法,是在催化剂载体表面化学镀镍磷合金层,制备负载型Ni3P催化剂的方法:将催化剂载体置于化学镀液中,然后在油浴氛围下升温至75-95℃,反应0.5-4h后,抽滤洗涤干燥得到制得催化剂前体;在化学气氛下将催化剂前体置于管式炉中升温至200-600℃,热处理0.5-5h后降温,制得负载型Ni3P催化剂。
具体的实施方式中,所述的化学镀液为含有下述溶质的水溶液:
(1)主盐:浓度为10-100g/L的NiCl2、NiSO4或Ni(NO3)2,优选NiCl2;
(2)还原剂:浓度为10-100g/L的NaH2PO2或NH4H2PO2,优选NaH2PO2;
(3)络合剂:浓度为10-100g/L的Na3C6H5O7;
(4)表面活性剂:浓度为1-10g/L的十六烷基三甲基溴化铵(CTAB)或十二烷基磺酸钠,优选CTAB。
(5)pH调节剂:NH3·H2O或CO(NH2)2,优选NH3·H2O。
上述本发明的方法中所述的催化剂载体是氧化物或沸石分子筛载体,举例但不限于SiO2、Al2O3、WO3、TiO2、ZrO2、CeO2、HY沸石分子筛、HZSM-5沸石分子筛或 Hβ沸石分子筛。所述催化剂中,金属Ni的负载量为催化剂质量的5-50%。
具体实施方式中,所述的催化剂载体在化学镀液中的反应,即化学镀,是90±2℃条件下反应1-3小时。
另一具体实施方式中,所述的热处理是400±5℃条件下处理1-3h。热处理所使用的化学气氛选自空气、氮气、氩气或氢气。优选氮气。
另一方面,本发明提供由上述化学镀的方法所制备得到的负载型Ni3P催化剂。该催化剂在苯酚及其衍生物加氢脱氧反应中具有异常优异的表现。基于此,本发明进一步公开其应用方法,即一种生物油中苯酚及其衍生物加氢脱氧的方法,该方法亦即使用本发明的负载型Ni3P催化剂作为加氢脱氧反应的催化剂。
上述苯酚及其衍生物加氢脱氧的方法中,所述的苯酚及其衍生物包括苯酚及取代苯酚,所述的取代苯酚由下述基团任意取代:甲基(-CH3)或羟基(-OH)。本发明中,当述及“任意取代”时,表示在满足一般化学原理的前提下,对取代基的个数以及取代位置均无特定的限制。上述取代苯酚则包括由任意数量的甲基(-CH3)或羟基(-OH)在苯酚的苯环或酚羟基上任意位置的取代。取代所获得的化合物可以举例但不限于:苯酚、苯甲醚、邻甲酚、间甲酚和对甲酚。
所述苯酚及其衍生物加氢脱氧的方法中,包含以苯酚及其衍生物为反应底物的加氢脱氧反应,所述的加氢脱氧反应可以采用固定床反应器连续进料反应。该所述加氢脱氧反应的反应温度为100-400℃;反应压力为1.0-5.0MPa。
更为具体地考虑,所述的加氢脱氧反应可以在水相或油相的反应介质中进行,分别为水相反应或油相反应,其中:水相反应的反应介质为去离子水,反应底物的质量分数为1-10%,产物用二氯甲烷萃取后以无水硫酸镁干燥;油相反应的反应介质为十氢萘,反应底物的质量分数为0.1-5%,反应后产物可以直接应用。
以下结合技术方案和附图详细叙述本发明的具体实施方式。
实施例1
采用化学镀法制备负载型Ni3P催化剂。
分别称取4.5g NiCl2·6H2O、6.0g NaH2PO2、3.75g Na3C6H5O7、7.5g NH4Cl、0.27 gCTAB共溶于150毫升去离子水中制成溶液A,再加入10毫升NH3·H2O调节pH=10- 11,在不断搅拌下加入3g载体(分别以SiO2、Al2O3、TiO2、ZrO2、WO3、CeO2、HZSM- 5、Hβ、HY为载体),油浴中升温至90℃后反应2h后抽滤洗涤干燥制得催化剂前体 B。将B置于管式反应器中,于化学气氛下升温至400℃再保持2h后降温,制得催化剂,记为EP-Ni-P/载体。通过将这些催化剂的XRD谱图与Ni3P和Ni的标准谱图对比(图1)可以看出,采用该方法成功制备出负载型Ni-P催化剂,主要晶型为Ni3P和 Ni的混合相。
实施例2
苯酚在EP-Ni-P/SiO2和EP-Ni-P/Al2O3上300℃下水相加氢脱氧反应性能。
反应在内径10毫米的高压固定床管式反应器中进行。按实施例1在反应器中制得相应的催化剂后,将反应器温度调至反应温度(300℃),总压增至4MPa,用高压恒流泵打入反应原料(质量浓度为5%的苯酚水溶液),重时空速30h-1,氢/油体积比 1000,脱氧率以烃类收率计算。反应稳定后取液体样品,用二氯甲烷萃取有机相产物,再用无水MgSO4脱除残留的微量水,在Aglient 6890N型气相色谱分析,色谱柱为市售INNO-WAX毛细管柱,氢火焰检测器,反应结果列于表1(苯酚在EP-Ni-P/SiO2和 EP-Ni-P/Al2O3上300℃下水相加氢脱氧反应性能)。由表1可以看出,在EP-Ni-P/SiO2和EP-Ni-P/Al2O3上苯酚的转化率分别高达98.2%和98.4%,而脱氧率分别为21.7%和 38.1%,说明制备的催化剂具有较高的催化苯酚水相加氢脱氧性能,其中在脱氧率方面 EP-Ni-P/Al2O3(38.1%)略优于EP-Ni-P/SiO2(21.7%)。对比反应前后催化剂的XRD 谱图(图2),催化剂的晶型在反应前后保持不变,具有较好的稳定性。
表1
催化剂 | 苯酚转化率(%) | 脱氧率(%) |
EP-Ni-P/SiO<sub>2</sub> | 98.2 | 21.7 |
EP-Ni-P/Al<sub>2</sub>O<sub>3</sub> | 98.4 | 38.1 |
实施例3
苯甲醚、邻甲酚、间甲酚和对甲酚在EP-Ni-P/SiO2上300℃下油相加氢脱氧反应。
反应在内径10毫米的高压固定床管式反应器中进行。按实施例1在反应器中制得相应的催化剂后,将反应器温度调至反应温度(300℃),总压增至4MPa,用高压恒流泵打入反应原料(质量浓度为1%的苯甲醚、邻甲酚、间甲酚或对甲酚十氢萘溶液),重时空速106.8h-1,氢/油体积比1000,脱氧率以相应的烃收率计算。反应稳定后取液体样品,在Aglient 6890N型气相色谱分析,色谱柱为市售INNO-WAX毛细管柱,氢火焰检测器,反应结果列于表2(苯甲醚、邻甲酚、间甲酚和对甲酚在EP-Ni- P/SiO2上300℃下油相加氢脱氧反应性能)。可以看出,对于苯酚取代物,EP-Ni-P/SiO2具有较高的催化加氢脱氧活性,活性依次降低为:对甲酚(99.8%)≈间甲酚(99.4%) ≈邻甲酚(99.3%)>苯甲醚(92.8%)。
表2
反应底物 | 转化率(%) | 脱氧率(%) |
苯甲醚 | 92.8 | 47.4 |
邻甲酚 | 99.3 | 92.9 |
间甲酚 | 99.4 | 93.5 |
对甲酚 | 99.8 | 92.1 |
对比例1
苯酚在体相Ni3P上300℃下水相加氢脱氧反应。
反应条件与实施例2类似,不同之处是催化剂为体相Ni3P,反应结果列于表3(苯酚在Ni3P上300℃下水相加氢脱氧反应性能)。对比表1和表3可以看出,苯酚的转化率在EP-Ni-P/SiO2(98.2%)和EP-Ni-P/Al2O3(98.4%)上高于体相Ni3P(85.0%),脱氧率在EP-Ni-P/SiO2(21.7%)上略低于体相Ni3P(24.2%),而在EP-Ni-P/Al2O3 (38.1%)上较高。
表3
催化剂 | 苯酚转化率(%) | 脱氧率(%) |
Ni<sub>3</sub>P | 85.0 | 24.2 |
对比例2
苯甲醚、邻甲酚、间甲酚和对甲酚在Ni3P上300℃下油相加氢脱氧反应。
反应条件与实施例3类似,不同之处是催化剂为体相Ni3P,重时空速降低为26.7 h-1,反应结果列于表4(苯甲醚、邻甲酚、间甲酚和对甲酚在Ni3P上300℃下油相加氢脱氧反应)。同样可以看出,在4倍重时空速的条件下,反应底物在EP-Ni-P/SiO2上的转化率(苯甲醚、邻甲酚、间甲酚和对甲酚分别为92.8%、99.3%、99.4%和99.8%) 均略高于体相Ni3P上(74.8%、93.4%、99.3%和99.7%),说明制备的EP-Ni-P/SiO2催化剂具有更高的催化苯酚取代物油相加氢脱氧性能。
表4
反应底物 | 转化率(%) | 脱氧率(%) |
苯甲醚 | 74.8 | 72.7 |
邻甲酚 | 93.4 | 93.1 |
间甲酚 | 99.3 | 98.8 |
对甲酚 | 99.7 | 92.4 |
本发明经过上述的描述,已清楚地公开了本发明催化剂组成和制备条件。但是,本领域内的技术人员十分清楚,对本发明可以进行一些修改和改进。所以,只要不离开本发明的精神,对本发明所进行的任何修改和改进都应在本发明的范围内。本发明的范围在附属的权利要求书中提出。
Claims (9)
1.负载型Ni3P催化剂的制备方法,其特征在于,是将催化剂载体置于化学镀液中,然后升温至75-95℃,反应0.5-4小时制得催化剂前体;在化学气氛下将催化剂前体升温至200-600℃,热处理0.5-5小时后降温,制得负载型Ni3P催化剂,其中,
所述的化学镀液为含有下述溶质的水溶液:
(1)浓度为10-100g/L的NiCl2、NiSO4或Ni(NO3)2;
(2)浓度为10-100g/L的NaH2PO2或NH4H2PO2;
(3)浓度为10-100g/L的Na3C6H5O7;
(4)浓度为1-10g/L的十六烷基三甲基溴化铵或十二烷基磺酸钠;
(5)NH3·H2O或CO(NH2)2,调整体系pH为10-11;
所述的化学气氛选自空气、氮气、氩气或氢气。
2.根据权利要求1所述的制备方法,其特征在于,所述的催化剂载体选自SiO2、Al2O3、WO3、TiO2、ZrO2、CeO2、HY沸石分子筛、HZSM-5沸石分子筛或Hβ沸石分子筛。
3.根据权利要求1所述的制备方法,其特征在于,所述的催化剂载体在化学镀液中的反应是90±2℃条件下反应1-3小时。
4.根据权利要求1所述的制备方法,其特征在于,所述的热处理是400±5℃条件下处理1-3小时。
5.权利要求1所述的方法制备的负载型Ni3P催化剂。
6.生物油中苯酚及其衍生物加氢脱氧的方法,包括加氢脱氧反应,其特征在于,反应中使用权利要求5所述的负载型Ni3P催化剂。
7.根据权利要求6所述的方法,其特征在于,所述的苯酚及其衍生物包括苯酚及取代苯酚,所述的取代苯酚由下述基团任意取代:甲基、羟基或甲氧基。
8.根据权利要求7所述的方法,其特征在于,所述的苯酚及其衍生物包括苯酚、苯甲醚、邻甲酚、间甲酚和对甲酚。
9.根据权利要求6所述的方法,其特征在于,所述的加氢脱氧反应温度为100-400℃,反应压力为1.0-5.0MPa。
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