CN1032678C - 饱和烃类脱氢用催化剂 - Google Patents
饱和烃类脱氢用催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 229930195734 saturated hydrocarbon Natural products 0.000 title claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 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 abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000011324 bead Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002803 maceration Methods 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000005673 monoalkenes Chemical class 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 241001455226 Sauria Species 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000007654 immersion Methods 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 35
- 239000011135 tin Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 20
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000012752 auxiliary agent Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229960002668 sodium chloride Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical group [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
- C07C5/324—Catalytic processes with metals
- C07C5/325—Catalytic processes with metals of the platinum group
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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Abstract
饱和烃类脱氢用催化剂由铂、锡、钠/r-Al2O3组成。其载体为大孔径r-Al2O3孔径在1000-1000A的孔至少占总孔体积的40%。铂、锡、钠采用共浸的方法浸渍到载体上，经干燥，焙烧，水蒸汽处理和氢还原制得高稳定性脱氢催化剂。
Description
本发明是一种用于饱和烃类脱氢反应，特别适用于C6-C16直链烷烃脱氢反应制取直链单稀烃的催化剂及其制备方法。
烃类脱氢反应是工业上的重要转化过程，工业上通过烃类脱氢反应，如脂肪烃、环烷烃的脱氢反应制造洗涤剂原料，医药产品，塑料和合成橡胶等各种化学品。这类脱氢反应所用的催化剂主要是以铂为活性组份，以锡、砷、钴、铅、锗、铊、铟等金属为第二或第三组份，并加有碱金属锂、钾或碱土金属钙等作助剂。如美国专利US3531543，US3725304，US3851003，US3909451，US4070413描述的脱氢催化剂为铂、锡、锂/r-AL2O3催化剂，适用于C2-C30直链(正构)烷烃脱氢反应过程。
美国专利US3998900，US4430517，US4608360，US4677237揭示的催化剂是以铂为活性组份，锡或铟为第二组份，并加有锂或钾为助剂。US3998900催化剂的组成为铂、锡、锂或钾/r-AL2O3，催化剂的制备采用先浸渍铂、锡，焙烧处理后再浸渍锂，使用前还必须以H2S和H2气混合气进行硫化。催化剂的载体采用US2620314所述的方法制备的中等孔径r-AL2O3小球，其载体的孔径分布集中在300A左右。该文献报导，当含有锂或钾时，催化剂能获得最好的结果。
美国专利US4672146所报导的催化剂为铂、锡、锂(或钾)/r-AL2O3催化剂，含有氨和硫，锡是在制备r-AL2O3载体时加入的。该催化剂适用于C2-C30烷烃脱氢反应过程。
美国专利US4762960所涉及的催化剂以铂为活性组份，第二组份选自锡、锗、铼。锂或钾为助剂，活性组份铂采用表面浸渍的方法浸到载体上。其表面100nm外壳的铂平钧浓度为200nm心处浓度的两倍。催化剂含有氯。该催化剂用于烃类脱氢反应。
美国专利US4886928叙述的催化剂以铂为活性组份，第二组份选自钪、钇、锕，第三组份选自锡、铅、锗，并选择锂或钾为助剂。该催化剂用于烃类脱氢反应。
中国专利CN87101513A的催化剂是铂、锡、锂、硫/r-AL2O3催化剂。以铂为活性组份，锡为第二组份，锂为助剂，含有硫。该催化剂的载体平均孔径大于200A。催化剂以硫化物为硫化剂湿法硫化，使用前需用氢气还原，还原后的催化剂用于C3-C30饱和烃类脱氢反应。本发明是该专利的继续和发展。
综合上述文献所述的催化剂都不含有钠，均以锂或钾、钙为助剂，以改善脱氢催化剂的催化性能。而且文献《载体进展和水溶液中表面电荷的控制》【《催化杂志》101，186—194(1986)】也报导了钠会影响负载型催化剂的活性。
至今为止，所报导的烃类脱氢催化剂，均认为，在以铂为活性组份，锡等为第二组份或第三组份时，加入锂或钾、钙为助剂的催化剂能获得最佳的效果。
然而，上述的这类催化剂，在使用前必须硫化而且随着脱氢工艺支术的发展，其稳定性已不能满足高转化率脱氢新工艺的要求。
本发明的目的是提供一种用于饱和烃类脱氢，特别是适用于C6-C16直链烷烃脱氢制取直链单烯烃的高稳定性，适用于高温低压的苛刻操作条件的催化剂，并革除通常脱氢催化剂使用前须经硫化处理步骤。
本发明以铂为活性组份，锡为第二组份，载体为大孔径r-Al2O3，加入钠作助剂的催化剂，能获得比加入锂作助剂的催化剂更理想的效果。
本发明是一种用于饱和烃类脱氢反应的负载型铂、锡、纳/r-Al2O3催化剂。催化剂的载体采用CN87101513A的方法制备，制得的小球经水蒸汽处理，制得大孔径的r-Al2O3载体。该载体的孔径在1000-10000A的孔至少占总孔体积的40％。催化剂的制备采用铂、锡、钠共浸技术，将铂、锡、钠金属组份负载到大孔径的r-AL2O3小球载体上。其催化剂组成的重百分数为：铂0.01-2.Owt％，锡0.01-5.Owt％，钠0.01-5.Owt％，其余为r-AL2O3载体。
本发明的催化剂载体的制备过程是将2—10wt％浓度的三氯化铝水溶液，在60—80℃的温度下，用1—10wt％浓度的氨水中和至PH＝7.5-8.5，生成的氢氧化铝溶胶经过滤，水洗至中性(PH＝7)，然后用硝酸酸化至PH＝3—6。酸化后的浆液按CN87101513A方法在油氨柱中加压成球。湿球经水洗，干燥后在600—800℃焙烧1—10小时，焙烧后的小球在以体积比为10—100％的水蒸汽—空气存在下于600—800℃处理1—20小时，处理后的r-AL2O3小球载体用压汞法测试其孔径。其载体孔径在1000—10000的孔至少占总孔体积的40％。载体的孔径分布曲线见图1.所示。
本发明的催化剂的制备过程是将氨铂酸、氯化亚锡、氯化钠、乙醇盐酸和水均匀混合制成浸渍液。浸渍在大孔径r-AL2O3小球载体上。浸渍时的液/固的体积比为0.5—2。浸渍液中乙醇的含量为40—60％(体积百分数)，盐酸的含量为3—8％(体积百分数)。浸渍后的催化剂经干燥，在400—600℃的温度下焙烧1—10小时和用含水蒸汽的空气处理1—10小时。水蒸汽处理时，空气中水蒸汽含量为10—50％(体积百分数)。经上述处理后的催化剂再以含水量小于与20ppm的氢气在400—600℃温度下还原5—20小时。还原后的催化剂为本发明的催化剂，用于饱和烃类脱氢反应过程。
本发明的催化剂最佳组成的重量百分数为铂0.2—1.0wt％，锡0.2—1.5wt％，钠0.1—1.5wt％，载体为大孔径r-AL2O3小球，其中孔径为1000—10000的孔至少占总孔体积的40％。
本发明的催化剂，在高温低压苛刻条件下具有高稳定性。该催化剂适用于苛刻反应条件下的饱和烃类脱氢反应，特别适用于C6-C16直链烷烃脱氢制取直链单烯烃的反应过程。并革除了通常脱氢催化剂使用前须经硫化处理的步骤。
附图说明
图1.为本发明催化剂载体r-AL2O3小球孔径分布曲线。
实施例1.
载体r-AL2O3小球的制备：
将浓度为4wt％的三氯化铝水溶液，在65±5℃的温度下，用6wt％的氨水中和至PH＝7—8，生成的氢氧化铝溶液经过滤，水洗至中性(PH＝7)然后用硝酸酸化至PH＝4—5，酸化后的浆液按CN87101513A专利方法成球，湿球经水洗，干燥后于700℃焙烧4小时，再在700℃用体积比为50％的水蒸汽—空气处理15小时。水蒸汽处理后的载体r-AL2O3小球用压汞法测试其孔径。孔径在1000—10000的孔至少占总孔体积的40％。载体的孔径分布曲线见图-1所示。
实施例2
催化剂的制备：
取含铂12.5毫克/毫升的氯铂酸水溶液328毫升，含锡40毫克/毫升的氯化亚锡水溶液187毫升，含钠25毫克/毫升的氯化钠水溶液220毫升，15wt％(重量百分数)的盐酸水溶液146.5毫升，无水乙醇1240毫升均匀混合制成浸渍液，同时取实施取例1.制得的载体r-AL2O3小球1000克，将浸渍液浸渍到载体上。待浸渍均匀后干燥，然后在温度450—500℃下焙烧4小时，焙烧时空气的气时空速1500小时-1。再在450—500℃的温度下，以体积比为30％的水蒸汽—空气处理4小时，然后以空气干燥降温，再以含水小于20PPm的氢气还原12小时。还原时氢气的气时空速为1000小时-1，温度为450—500℃。制得本发明催化剂(I)，其催化剂的组成的重量百分数为：铂0.41wt％，锡0.748wt％，钠0.55wt％。
实施例3
评价试验：
将实施例2.制得的催化剂(I)进行评价试验，试验中以含硫小于1PPm的C10-C13直链烷烃为原料，反应条件为表压0.1mpa，入口温度为480℃，液时空速20小时-1，氢烃比(摩尔比)为5∶1。催化剂(I)烷烃转化成单烯烃的反应中选择性为90％，平均转化率为18.6％，详见表-1催化剂(I)的转化率表。
表1. 催化剂(I)的转化率表
| 时间(小时) 8 16 24 32 40 48 56 64 72 86转化率(％)催化剂(I) 22.4 21.1 19.8 19.5 19.1 18.1 17.6 17.2 16.4 14.8 |
实施例4
对比试验1
本发明的催化剂(I)含铂0.41wt％，锡0.748wt％，钠0.55wt％。催化剂(II)含铂0.41wt％，锡0.62wt％，钠0.35％wt％，载体为实施例1.制得r-AL2O3小球。催化剂(III)含铂0.41wt％，锡0.50wt％，钠0.35wt％，载体为实施例1.制得r-AL2O3小球，以经加氢精制的含硫小于1ppm的C10-C13直链烷烃为原料。所用反应条件为表压0.1mpa，入口温度480℃，液时空速20小时-1，氢烃比(摩尔比)为5∶1.试验周期为90小时，试验期间的平均转化率催化剂(I)为18.6％，催化剂(II)和(III)18％，选择性均为90％。由实施例4.可见，本发明的催化剂当催化剂中锡、钠含量有变化时，其催化剂的稳定性不变。实施例5对比实验2
本发明的催化剂(I)，含铂0.41wt％，锡0.748wt％，钠0.55wt％。催化剂(A)(中国专利CN87101513A)含铂0.375wt％，锡0.68wt％，锂0.48wt％，经湿法硫化。将催化剂(I)和催化剂(A)作对比试验。试验中以加氢精制含硫小于1ppm的C10-C13直链烷烃为原料，反应条件为表压0.1mpa，入口温度为480℃，液时空速20小时-1，氢烃比(摩尔比)为5∶1。催化剂(I)和催化剂(A)烷烃转化成单烯烃的反应中选择性均为90％，催化剂(I)的平均转化率为18.6％，而催化剂(A)的平均转化率为16.9％，详见表-2两种催化剂的转化率比较表。
表-2 两种催化剂的转化率比较表
| 时间(小时) 8 16 24 32 40 48 56 64 72 86转化率(％)催化剂(I) 22.4 22.1 19.8 19.5 19.1 18.1 17.8 17.2 16.4 14.8 |
| 催化剂(A) 21.1 19.6 19.4 18.4 17.6 17.0 15.5 14.4 14.2 11.8 |
两种催化剂(I)和(A)的性能对比试验结果表明：在选择性均为90％时，本发明的催化剂(I)的转化率高于催化剂(A)(中国专利CN87101513A)。
实施例6
对比试验3
本发明的催化剂(I)含铂0.41wt％，锡0.748wt％，钠0.55wt％，催化剂(B)含铂0.41wt％，锡0.748wt％，钠0.55wt％，载体为US3998900专利的方法(US2620314)成型的r-AL2O3小球(孔径<1000占90％以上)，把催化剂(I)和催化剂(B)作对比试验。试验中以加氢精制含硫小于1ppm的C10-C13直链烷烃为原料，反应条件为表压0.1mpa，入口温度480℃，液时空速20小时-1，氢烃比(摩尔比)为5∶1。催化剂(I)和催化剂(B)的烷烃转化成单烯烃的选择性均为90％，催化剂(I)的平均转化率为18.6％，催化剂(B)的平均转化率为15.7％。由对比试验结果可见，两种催化剂(I)和(B)其组成和含量相同，只是本发明的催化剂(I)载体为大孔径r-AL2O3小球。而催化剂(B)载体r-AL2O3小球是孔径<1000占90％以上的中等孔径载体，催化剂(I)平均转化率明显高于催化剂(B)的平均转化率。
实施例7
对比试验4
本发明的催化剂(I)含铂0.41wt％，锡0.748wt％，钠0.55wt％。催化剂(C)含铂0.41wt％，锡0.748wt％，锂0.60wt％，载体为实施例1.制得的大孔r-AL2O3小球。将催化剂(I)和催化剂(C)作性能对比试验。以经加氢精制含硫小于1ppm的C10-C13直链烷烃为原料，反应条件为表压0.1mpa，入口温度480℃，液时空速20小时-1，氢烃比(摩尔比)为5∶1。催化剂(I)的烷烃转化成单烯的选择性为90％，催化剂(I)的平均转化率为18.8％，而催化剂(C)的烷烃转化成单烯的选择性为89％，平均转化率为17.2％，由对比试验结果可见，两种催化剂的载体相同，只是加入助剂不同，催化剂(I)为铂、锡、钠/r-AL2O3体系。而催化剂(C)为铂、锡、锂/r-AL2O3体系。催化剂(I)平均转化率明显高于催化剂(C)的平均转化率。
实施例8
对比试验5
本发明催化剂(I)含铂0.41wt％，锡0.748wt％，钠0.55wt％，催化剂(A)(中国专利CN87101513A)含铂0.375wt％，锡0.68wt％，锂0.48wt％，经湿法硫化。催化剂(D)(美国专利US3909451)含铂0.370wt％，锡0.45wt％，锂0.48wt％，其余为r-AL2O3载体。催化剂(E)(美国专利(US4608360)含铂0.40wt％，锡0.45wt％，铟0.31wt％，锂0.45wt％，其余为r-AL2O3载体。将催化剂(I)、(A)、(D)、(E)进行对比试验。以经加氢精制含硫小于1ppm的C10-C13直链烷烃为原料，反应条件为表压0.14mpa，入口温度482℃，液时空速20小时-1，氢烃比(摩尔比)为6∶1。试验周期500小时，催化剂(I)、(A)、(D)、(E)的烷烃转化成单烯烃的选择性均为85％，催化剂(I)的平均转化率为18.2％，催化剂(D)为11.3％，催化剂(E)为13.3％，催化剂(A)为13.4％，详见表-3四种催化剂对比试验结果表。
由对比试验结果可见，在选择性相同时本发明的催化剂(I)平均转化率为最高。
表-3 四种催化剂对比试验结果表
| 对比试验结果催化剂(专利号) | 选择性(％) | 转化率(％) |
| 催化剂(I)(本发明) | 85％ | 18.2％ |
| 催化剂(A)(CN87101513A) | 85％ | 13.4％ |
| 催化剂(D)(US3909451) | 85％ | 11.3％ |
| 催化剂(E)(US4608360) | 85％ | 13.3％ |
Claims (8)
1.一种用于饱和烃类脱氢反应的高稳定性负载型铂、锡、钠/r-Al2O3催化剂，其特征在于催化剂的组成的重量百分数为：铂0.01-2.0wt％，锡0.01-5.0wt％，钠0.01-5.0wt％，其余为双孔型分布的大孔径的r-Al2O3载体，在该载体中，孔径在1000-10000的孔的体积至少占总孔体积的40％。
2.根据权利要求1所述的催化剂，其特征在于催化剂的组成的重量百分数为：铂0.2-1.0wt，锡0.2-1.5wt％，钠0.1-1.5wt％。
3.权利要求1所述的催化剂的制备方法，其特征在于它由下述步骤组成：
(1).将三氯化铝溶液和氨水中和生成的氢氧化铝溶胶用硝酸酸化后在油氨柱中加压滴球成型，制得的小球在600-800℃焙烧1-10小时；
(2).焙烧后的r-Al2O3小球用含水蒸汽10-100％(体积百分数)的空气于600-800℃处理1-20小时；
(3).将氯铂酸、氯化亚锡、氯化钠、盐酸、乙醇和水混合均匀制成浸渍液；
(4)将(3)制得的浸渍液浸渍经(2)处理后的r-Al2O3小球，干燥后于400-600℃焙烧1-10小时；
(5).用水蒸气含量为10-50％(体积百分数)的空气-水蒸气混合气体于400-600℃处理1-10小时；
(6).用含水量小于20PPM的氢气于400-600℃还原5-20小时。
4.根据权利要求2所述的催化剂的制备方法，其特征在于(4)所述的浸渍时的液/固的体积比为0.5-2。
5.根据权利要求2所述的催化剂的制备方法，其特征在于(3)所述的乙醇在浸渍液中的含量为40-60％(体积百分数)。
6.根据权利要求2所述的催化剂的制备方法，其特征在于(3)所述的盐酸在浸渍液中的含量为3-8％(体积百分数)。
7权利要求1所述的催化剂用于饱和烃类脱氢反应制取直链单烯烃的过程。
8.根据权利要求7所述的催化剂，用于C6-C16直链(正构)烷烃脱氢反应制取直链单烯烃的过程。
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| CN112892612B (zh) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | 一种用于烃类转化反应的催化剂 |
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|---|---|---|---|---|
| NL76445C (zh) * | 1950-03-08 | |||
| US3531534A (en) * | 1969-02-10 | 1970-09-29 | Us Navy | Bisfluorodinitro ethers and their preparation |
| US3725304A (en) * | 1970-12-28 | 1973-04-03 | F Wilhelm | Hydrocarbon conversion catalyst |
| US3851003A (en) * | 1970-12-28 | 1974-11-26 | Universal Oil Prod Co | Dehydrogenation method and multicomponent catalytic composite for use therein |
| US3998900A (en) * | 1973-03-05 | 1976-12-21 | Universal Oil Products Company | Dehydrogenation of hydrocarbons with a multimetallic catalytic composite |
| US3909451A (en) * | 1973-03-05 | 1975-09-30 | Universal Oil Prod Co | Dehydrogenation catalyst |
| US4070413A (en) * | 1976-10-28 | 1978-01-24 | Uop Inc. | Dehydrogenation of saturated hydrocarbons |
| US4430517A (en) * | 1981-12-02 | 1984-02-07 | Uop Inc. | Dehydrogenation process using a catalytic composition |
| US4677237A (en) * | 1984-11-29 | 1987-06-30 | Uop Inc. | Dehydrogenation catalyst compositions |
| US4608360A (en) * | 1985-07-02 | 1986-08-26 | Uop Inc. | Dehydrogenation catalyst compositions and method of preparing same |
| US4672146A (en) * | 1985-07-02 | 1987-06-09 | Uop Inc. | Dehydrogenation catalyst compositions and its use in dehydrogenation |
| US4717779A (en) * | 1985-09-11 | 1988-01-05 | Uop Inc. | Dehydrogenation of dehydrogenatable hydrocarbons |
| US4762960A (en) * | 1987-02-25 | 1988-08-09 | Uop Inc. | Dehydrogenation catalyst composition and paraffin dehydrogenation |
| CN1013361B (zh) * | 1987-03-13 | 1991-07-31 | 中国科学院大连化学物理研究所 | 饱和烃类脱氢用铂、锡、锂、硫催化剂 |
| US4886928A (en) * | 1988-09-26 | 1989-12-12 | Uop | Hydrocarbon dehydrogenation process |
| US5258567A (en) * | 1992-08-26 | 1993-11-02 | Exxon Research And Engineering Company | Dehydrogenation of hydrocarbons |
-
1992
- 1992-12-21 CN CN92114525A patent/CN1032678C/zh not_active Expired - Lifetime
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1993
- 1993-11-19 US US08/155,400 patent/US5358920A/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1088482A (zh) | 1994-06-29 |
| US5358920A (en) | 1994-10-25 |
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