CN105688959A - 高水热稳定性钴基费托合成催化剂及制法和应用 - Google Patents
高水热稳定性钴基费托合成催化剂及制法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 16
- 239000010941 cobalt Substances 0.000 title claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 92
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 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 claims description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 14
- 230000002779 inactivation Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UVLYPUPIDJLUCM-UHFFFAOYSA-N indium;hydrate Chemical compound O.[In] UVLYPUPIDJLUCM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DSLAWOVIUYGFOS-UHFFFAOYSA-H N.C([O-])([O-])=O.[Al+3].C([O-])([O-])=O.C([O-])([O-])=O.[Al+3] Chemical compound N.C([O-])([O-])=O.[Al+3].C([O-])([O-])=O.C([O-])([O-])=O.[Al+3] DSLAWOVIUYGFOS-UHFFFAOYSA-H 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- APLQTTYBCHJFIJ-UHFFFAOYSA-N [Ba].[N+](=O)(O)[O-] Chemical compound [Ba].[N+](=O)(O)[O-] APLQTTYBCHJFIJ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
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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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
一种高水热稳定性钴基费托合成催化剂及制法和应用由四氧化三钴、磷酸铝和氧化铝组成,其摩尔组成为四氧化三钴:金属助剂氧化物:磷酸铝:氧化铝=0.1-0.3:0.02-0.1:0.01-0.1:1。本发明具有适用于浆态床或固定床反应器,高稳定性的优点。
Description
技术领域
本发明涉及一种催化剂及制备方法和应用,具体地说是一种高水热稳定性钴基费托合成催化剂及制法和应用。
背景技术
费托合成反应是CO催化加氢生成烃类化合物的过程,其产物环境友好,不含芳烃、硫化物以及氮化合物等,受到了日益广泛的关注。用于费托合成反应的钴基催化剂具有较高的链增长能力,对水煤气变换反应不敏感,在反应过程中稳定、不易积炭和中毒、产物中含氧化合物少,CO转化可接近理论转化率。
沉淀法制备的活性氧化铝由于比表面积大、孔容大、孔分布集中、活性中心多,可以满足催化剂高选择性和高反应活性的要求,被广泛用作钴基催化剂载体。然而氧化铝的水热稳定性差,很容易在费托合成反应的水热条件下进行水合反应,促使氧化铝颗粒间Al-O-Al桥键不断形成,生成拟薄水铝石、碳酸铝氨或者氢氧化铝,同时形貌发生改变,造成氧化铝比表面积大幅下降、孔结构破坏,负载其上的金属容易脱落,最终导致催化剂失活。为了保证氧化铝负载钴催化剂的有效使用,需要采取措施对氧化铝载体进行改性,以改善其作为载体的催化稳定性。
在氧化铝结构中引入某些离子对氧化铝作为载体的水热稳定性和抑制相变具有显著影响,若能有效地去除氧化铝表面的羟基和阴、阳离子空穴就可改善氧化铝的水热稳定性,阻止相变发生并维持其氧化铝固有孔道结构高比表面积。磷在焙烧过程中从-3价变至+5价,能增加氧化铝中的阴离子空位,Al-OH被不易脱除的P-OH取代,从而提高了氧化铝的表面碱性。焙烧后磷在氧化铝表面以无定型态存在,改变了氧化铝表面羟基的数量及性质,抑制了氧化铝的脱羟基烧结和颗粒长大,提高了热稳定性。
发明内容
本发明目的在于提供一种适用于浆态床或固定床反应器,高稳定性的钴基费托合成催化剂及制备方法和应用。
本发明在氧化铝前驱体的制备过程中引入PO4 3-,在前驱体焙烧过程中,引入的PO4 3-与Al2O3之间易形成无定型的磷酸铝AlPO4,覆盖在Al2O3表面,消除了表面阴离子空穴,提高了焙烧后氧化铝水热稳定性,从而提高了负载钴费托合成催化剂的稳定性。
本发明催化剂由四氧化三钴、磷酸铝和氧化铝组成,其摩尔组成为四氧化三钴:金属助剂氧化物:磷酸铝:氧化铝=(0.1-0.3):(0.02-0.1):(0.01-0.1):1。
如上所述的金属助剂氧化物为氧化铈、氧化铟、氧化锶或氧化钡中的一种。
本发明催化剂的制备方法如下:
(1)按最终催化剂组成,称取硝酸和磷源溶于水配制成溶液A,再称取偏铝酸钠溶于水配制成与A等体积的溶液B,其中,硝酸的物质的量:(偏铝酸钠的物质的量+磷源的物质的量)=(0.95-1.05):1;
(2)将溶液A和溶液B在水浴50-85℃下进行并流共沉淀,体积流量相同,沉淀完毕后在70-85℃下老化2-24h;
(3)老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于90-120℃干燥10-24h得到含磷铝前驱体,将得到的前驱体于400-650℃焙烧4-10h,得到含磷氧化铝载体;
(4)按最终催化剂组成,称取可溶性钴盐和助剂金属盐配制水溶液,等体积浸渍于上述含磷氧化铝载体,90-120℃下干燥10-24h,300-400℃焙烧4-10h,制得最终催化剂。
如上所述的硝酸为浓硝酸、发烟硝酸的一种。
如上所述的磷源为磷酸、磷酸二氢钠、磷酸氢二钠、磷酸钠或次亚磷酸钠的一种。
如上所述的钴盐为硝酸钴、醋酸钴等的一种。
如上所述的可溶性助剂金属盐为硝酸铈、硝酸铟、硝酸锶或硝酸钡的一种。
如上所述的费托合成钴基催化剂,可以在固定床反应器中进行还原、反应;还原条件为:350-450℃,0.3-1.5MPa,体积空速GHSV=500-1000h-1,恒温12-24h,采用氮中氢还原气,H2含量为15%-85%(v/v);反应条件为:170-230℃,2.0-3.0MPa,体积空速GHSV=700-2500h-1,H2/CO(v/v)=2.0-2.5。
如上所述的费托合成钴基催化剂,可以在浆态床反应器中进行还原、反应;还原条件为:270-320℃,0.2-1.2MPa,体积空速GHSV=500-800h-1,恒温12-36h,采用氮中氢还原气,H2含量为15%-85%(v/v),转速为400-800rpm;反应条件为:170-230℃,2.0-3.0MPa,体积空速GHSV=700-2000h-1,H2/CO(v/v)=2.0-3.0,转速为400-800rpm。
本发明掺磷氧化铝负载钴催化剂与现有费托合成钴基催化剂相比,在水热反应条件下,焙烧后氧化铝能维持固有孔道结构和高比表面积,提高了水热稳定性,阻止了氧化铝相变,从而提高了负载钴催化剂费托合成稳定性。
具体实施方式
下面实施例将对本发明做进一步说明,本发明的保护范围并不受这些实施例的限制。
实施例1:
按照最终催化剂组成,称取1894.7g,浓度为66.5wt%的浓硝酸和14.2g磷酸氢二钠溶于水配制成20L溶液A,再称取1648.2g偏铝酸钠溶于水配制成20L溶液B;将溶液A和溶液B在水浴50℃下进行并流共沉淀,体积流量相同,沉淀完毕后在70℃下老化6h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于120℃干燥10h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于600℃焙烧6h,得到含磷氧化铝;按最终催化剂组成,称取2619g六水合硝酸钴和42.3g无水硝酸锶配制水溶液,等体积浸渍于上述载体,65℃下干燥24h,300℃焙烧10h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化锶:磷酸铝:氧化铝=0.3:0.02:0.01:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:350℃,0.3MPa,恒温10h,1000h-1(v/v),采用氮中氢,H2含量为15%(v/v)。反应条件为:230℃,3.0MPa,2500h-1(v/v),H2/CO(mol)=2.2。评价结果:CO转化率75.5%,CH4选择性为8.3%,720h内失活率为0.10%。
取上述催化剂20ml于1L浆态床反应器进行评价,还原条件为,350℃,0.2MPa,500h-1(v/v),采用氮中氢,H2含量为15%(v/v),恒温36h,600rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为230℃,2.0MPa,2000h-1(v/v),H2/CO(v/v)=2.2,600rpm。评价结果:CO转化率46.1%,CH4选择性为15.2%,720h内失活率为0.13%。
实施例2:
按照最终催化剂组成,称取128.6g浓度为98wt%的发烟硝酸和2.4g磷酸二氢钠溶于水配制成8L溶液A,再称取165.6g偏铝酸钠溶于水配制成8L溶液B;将溶液A和溶液B在水浴60℃下进行并流共沉淀,体积流量相同,沉淀完毕后在80℃下老化3h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于110℃干燥8h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于500℃焙烧6h,得到含磷氧化铝;按最终催化剂组成,称取218.3g六水合硝酸钴和7.8g硝酸钡配制水溶液,等体积浸渍于上述载体,75℃下干燥18h,305℃焙烧6h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化钡:磷酸铝:氧化铝=0.25:0.03:0.02:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:450℃,0.4MPa,恒温12h,600h-1(v/v),采用氮中氢,H2含量为80%(v/v),。反应条件为:220℃,2.0MPa,2000h-1(v/v),H2/CO(mol)=2.0。评价结果:CO转化率39.6%,CH4选择性为11.8%,720h内失活率为0.12%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,330℃,0.4MPa,800h-1(v/v),采用氮中氢,H2含量为80%(v/v),恒温24h,750rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为200℃,2.2MPa,1200h-1(v/v),H2/CO(v/v)=2.2,700rpm。评价结果:CO转化率70.5%,CH4选择性为4.9%,720h内失活率为0.02%。
实施例3:
按照最终催化剂组成,称取940.3g浓度为67wt%的浓硝酸和24.6g磷酸钠溶于水配制成20L溶液A,再称取832.3g偏铝酸钠溶于水配制成20L溶液B;将溶液A和溶液B在水浴65℃下进行并流共沉淀,体积流量相同,沉淀完毕后在70℃下老化3h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于110℃干燥9h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于450℃焙烧5h,得到含磷氧化铝;按最终催化剂组成,称取627g四水合醋酸钴和127.52g水合硝酸铟配制水溶液,等体积浸渍于上述载体,85℃下干燥12h,325℃焙烧6h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化铟:磷酸铝:氧化铝=0.22:0.04:0.03:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:360℃,0.5MPa,恒温4h,800h-1(v/v),采用氮中氢,H2含量为20%(v/v),。反应条件为:225℃,2.5MPa,1800h-1(v/v),H2/CO(mol)=2.5。评价结果:CO转化率45.3%,CH4选择性为7.7%,720h内失活率为0.07%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,340℃,0.5MPa,900h-1(v/v),采用氮中氢,H2含量为70%(v/v),恒温18h,720rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为185℃,2.8MPa,1100h-1(v/v),H2/CO(v/v)=2.5,800rpm。评价结果:CO转化率59.2%,CH4选择性为3.9%,720h内失活率为0.09%。
实施例4:
按照最终催化剂组成,称取128.6g浓度为98wt%的发烟硝酸和4.9g磷酸溶于水配制成4L溶液A,再称取168.1g偏铝酸钠溶于水配制成4L溶液B;将溶液A和溶液B在水浴70℃下进行并流共沉淀,体积流量相同,沉淀完毕后在85℃下老化2h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于100℃干燥8h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于650℃焙烧2h,得到含磷氧化铝;按最终催化剂组成,称取174.6g四水合醋酸钴和21.7g六水合硝酸铈配制水溶液,等体积浸渍于上述载体,95℃下干燥10h,350℃焙烧4h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化铈:磷酸铝:氧化铝=0.2:0.05:0.05:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:390℃,0.6MPa,恒温12h,500h-1(v/v),采用氮中氢,H2含量为30%(v/v),。反应条件为:215℃,2.5MPa,1500h-1(v/v),H2/CO(mol)=2.5。评价结果:CO转化率67.5%,CH4选择性为6.8%,720h内失活率为0.08%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,320℃,0.1MPa,1000h-1(v/v),采用氮中氢,H2含量为60%(v/v),恒温36h,600rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为190℃,2.5MPa,1300h-1(v/v),H2/CO(v/v)=2.0,700rpm。评价结果:CO转化率69.7%,CH4选择性为4.2%,720h内失活率为0.01%。
实施例5:
按照最终催化剂组成,称取193.8g浓度为65wt%的浓硝酸和7.4g次亚磷酸钠溶于水配制成10L溶液A,再称取169.7g偏铝酸钠溶于水配制成10L溶液B;将溶液A和溶液B在水浴80℃下进行并流共沉淀,体积流量相同,沉淀完毕后在90℃下老化1h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于80℃干燥12h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于550℃焙烧10h,得到含磷氧化铝;按最终催化剂组成,称取157.1g六水合硝酸钴和37.5g水合硝酸铟配制水溶液,等体积浸渍于上述载体,120℃下干燥10h,370℃焙烧6h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化铟:磷酸铝:氧化铝=0.18:0.06:0.07:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:450℃,0.3MPa,恒温6h,800h-1(v/v),采用氮中氢,H2含量为15%(v/v),。反应条件为:220℃,2.0MPa,2500h-1(v/v),H2/CO(mol)=2.2。评价结果:CO转化率85.1%,CH4选择性为4.5%,720h内失活率为0.02%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,320℃,0.3MPa,700h-1(v/v),采用氮中氢,H2含量为100%(v/v),恒温36h,700rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为195℃,1.5MPa,2000h-1(v/v),H2/CO(v/v)=2.1,650rpm。评价结果:CO转化率48.9%,CH4选择性为9.7%,720h内失活率为0.13%。
实施例6:
按照最终催化剂组成,称取1852.9g浓度为68wt%的浓硝酸和78.4g磷酸溶于水配制成50L溶液A,再称取1705.6g偏铝酸钠溶于水配制成50L溶液B;将溶液A和溶液B在水浴70℃下进行并流共沉淀,体积流量相同,沉淀完毕后在80℃下老化4h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于90℃干燥18h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于600℃焙烧2h,得到含磷氧化铝;按最终催化剂组成,称取1309.5g六水合硝酸钴和148.1g无水硝酸锶配制水溶液,等体积浸渍于上述载体,60℃下干燥20h,400℃焙烧5h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化锶:磷酸铝:氧化铝=0.15:0.07:0.08:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:400℃,0.7MPa,恒温12h,700h-1(v/v),采用氮中氢,H2含量为50%(v/v),。反应条件为:230℃,2.0MPa,2200h-1(v/v),H2/CO(mol)=2.4。评价结果:CO转化率42.3%,CH4选择性为14.7%,720h内失活率为0.11%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,270℃,1.2MPa,700h-1(v/v),采用氮中氢,H2含量为70%(v/v),恒温16h,700rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为190℃,2.5MPa,1000h-1(v/v),H2/CO(v/v)=2.0,700rpm。评价结果:CO转化率75.6%,CH4选择性为4.9%,720h内失活率为0.03%。
实施例7:
按照最终催化剂组成,称取128.6g浓度为98wt%的发烟硝酸和12.0g磷酸二氢钠溶于水配制成1L溶液A,再称取172.2g偏铝酸钠溶于水配制成1L溶液B;将溶液A和溶液B在水浴70℃下进行并流共沉淀,体积流量相同,沉淀完毕后在90℃下老化2.5h;老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于烘箱于80℃干燥12h得到含磷氧化铝前驱体;将得到的前驱体置于马弗炉中,于630℃焙烧4h,得到含磷氧化铝;按最终催化剂组成,称取87.3g六水合硝酸钴和26.1g无水硝酸钡配制水溶液,等体积浸渍于上述载体,105℃下干燥16h,385℃焙烧5h,制得最终催化剂,其摩尔比组成为四氧化三钴:氧化钡:磷酸铝:氧化铝=0.1:0.1:0.1:1。
取上述催化剂5ml不稀释装填于固定床反应器中(Ф10×500mm),还原条件为:395℃,1.5MPa,恒温10h,900h-1(v/v),采用氮中氢,H2含量为35%(v/v),。反应条件为:210℃,2.4MPa,2000h-1(v/v),H2/CO(mol)=2.5。评价结果:CO转化率66.6%,CH4选择性为12.5%,720h内失活率为0.05%。
取上述催化剂10ml于1L浆态床反应器进行评价,还原条件为,300℃,0.8MPa,1000h-1(v/v),采用氮中氢,H2含量为40%(v/v),恒温16h,800rpm。还原完毕后降至室温切换成合成气进行反应,反应条件为200℃,2.0MPa,800h-1(v/v),H2/CO(v/v)=2.4,700rpm。评价结果:CO转化率92.8%,CH4选择性为1.6%,720h内失活率为0.01%。
Claims (9)
1.一种高水热稳定性钴基费托合成催化剂,其特征在于催化剂由四氧化三钴、磷酸铝和氧化铝组成,其摩尔组成为四氧化三钴:金属助剂氧化物:磷酸铝:氧化铝=0.1-0.3:0.02-0.1:0.01-0.1:1。
2.如权利要求1所述的一种高水热稳定性钴基费托合成催化剂,其特征在于所述的金属助剂氧化物为氧化铈、氧化铟、氧化锶或氧化钡中的一种。
3.如权利要求1或2所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于包括如下步骤:
(1)按最终催化剂组成,称取硝酸和磷源溶于水配制成溶液A,再称取偏铝酸钠溶于水配制成与A等体积的溶液B,其中,硝酸的物质的量:(偏铝酸钠的物质的量+磷源的物质的量)=0.95-1.05:1;
(2)将溶液A和溶液B在水浴50-85℃下进行并流共沉淀,体积流量相同,沉淀完毕后在70-85℃下老化2-24h;
(3)老化结束后,用去离子水洗涤至滤液中钠离子小于1ppm,然后过滤得到滤饼,将滤饼置于90-120℃干燥10-24h得到含磷铝前驱体,将得到的前驱体于400-650℃焙烧4-10h,得到含磷氧化铝载体;
(4)按最终催化剂组成,称取可溶性钴盐和助剂金属盐配制水溶液,等体积浸渍于上述含磷氧化铝载体,90-120℃下干燥10-24h,300-400℃焙烧4-10h,制得最终催化剂。
4.如权利要求3所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于所述的硝酸为浓硝酸、发烟硝酸的一种。
5.如权利要求3所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于所述的磷源为磷酸、磷酸二氢钠、磷酸氢二钠、磷酸钠或次亚磷酸钠的一种。
6.如权利要求3所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于所述的钴盐为硝酸钴、醋酸钴的一种。
7.如权利要求3所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于所述的可溶性助剂金属盐为硝酸铈、硝酸铟、硝酸锶或硝酸钡的一种。
8.如权利要求1或2所述的一种高水热稳定性钴基费托合成催化剂的应用,其特征在于所述的费托合成钴基催化剂在固定床反应器中进行还原、反应;还原条件为:350-450℃,0.3-1.5MPa,体积空速GHSV=500-1000h-1,恒温12-24h,采用氮中氢还原气,H2体积含量为15%-85%;反应条件为:170-230℃,2.0-3.0MPa,体积空速GHSV=700-2500h-1,H2/CO体积比=2.0-2.5。
9.如权利要求1或2所述的一种高水热稳定性钴基费托合成催化剂的制备方法,其特征在于所述的费托合成钴基催化剂在浆态床反应器中进行还原、反应;还原条件为:270-320℃,0.2-1.2MPa,体积空速GHSV=500-800h-1,恒温12-36h,采用氮中氢还原气,H2体积含量为15%-85%,转速为400-800rpm;反应条件为:170-230℃,2.0-3.0MPa,体积空速GHSV=700-2000h-1,H2/CO体积比=2.0-3.0,转速为400-800rpm。
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CN108187708A (zh) * | 2018-02-01 | 2018-06-22 | 中科合成油内蒙古有限公司 | 一种含磷高稳定性重质烃费托合成催化剂及其制备方法和应用 |
CN108654654A (zh) * | 2017-04-01 | 2018-10-16 | 神华集团有限责任公司 | 沉淀铁费托催化剂及其制备方法和应用 |
CN114632530A (zh) * | 2022-04-20 | 2022-06-17 | 刘盛楹 | 一种甲醇重整制氢铜基催化剂及制备方法和应用 |
CN114632522A (zh) * | 2022-03-30 | 2022-06-17 | 刘盛楹 | 一种富氢气体脱除co钴基催化剂及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060096891A1 (en) * | 1999-08-11 | 2006-05-11 | Dennis Stamires | Quasi-crystalline boehmites containing additives |
CN102618093A (zh) * | 2012-01-18 | 2012-08-01 | 常州大学 | 一种粘土复合材料及其制备方法 |
-
2016
- 2016-02-29 CN CN201610110241.0A patent/CN105688959A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060096891A1 (en) * | 1999-08-11 | 2006-05-11 | Dennis Stamires | Quasi-crystalline boehmites containing additives |
CN102618093A (zh) * | 2012-01-18 | 2012-08-01 | 常州大学 | 一种粘土复合材料及其制备方法 |
Non-Patent Citations (2)
Title |
---|
JONG WOOK BAE等: "Enhanced Fischer–Tropsch activity on Co/P–Al2O3 catalyst: Effect of phosphorous content", 《CATALYSIS COMMUNICATIONS》 * |
唐国旗等: "A12 03对AIP04催化剂的结构及其缩醛化反应活性的影响", 《工业催化》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108654654A (zh) * | 2017-04-01 | 2018-10-16 | 神华集团有限责任公司 | 沉淀铁费托催化剂及其制备方法和应用 |
CN108654654B (zh) * | 2017-04-01 | 2021-09-03 | 国家能源投资集团有限责任公司 | 沉淀铁费托催化剂及其制备方法和应用 |
CN108187708A (zh) * | 2018-02-01 | 2018-06-22 | 中科合成油内蒙古有限公司 | 一种含磷高稳定性重质烃费托合成催化剂及其制备方法和应用 |
CN108187708B (zh) * | 2018-02-01 | 2021-05-04 | 中科合成油内蒙古有限公司 | 一种含磷高稳定性重质烃费托合成催化剂及其制备方法和应用 |
CN114632522A (zh) * | 2022-03-30 | 2022-06-17 | 刘盛楹 | 一种富氢气体脱除co钴基催化剂及其制备方法和应用 |
CN114632530A (zh) * | 2022-04-20 | 2022-06-17 | 刘盛楹 | 一种甲醇重整制氢铜基催化剂及制备方法和应用 |
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