CN1073464C - 低碳烷烃脱氢催化剂及其制法 - Google Patents
低碳烷烃脱氢催化剂及其制法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 11
- 239000012188 paraffin wax Substances 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 title abstract 2
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 28
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012974 tin catalyst Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 229910002847 PtSn Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006298 dechlorination reaction Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 235000014121 butter Nutrition 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 abstract description 20
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001282 iso-butane Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 12
- 235000013847 iso-butane Nutrition 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen hydrocarbon Chemical class 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种用于低碳烷烃催化脱氢的担载型铂-锡催化剂PtSn/MgAl(O),其载体为MgAl(O)复合氧化物,Mg与Al的摩尔比为2∶1~15∶1,Rt为载体MgAl(O)重量的0.2至1.2%,Rt与Sn的摩尔比为0.5∶1-1.5∶1,并提供了该催化剂的制法。它对于异丁烷脱氢反应有较高的异丁烯选择性(97-98%),有较强的抗失活能力。
Description
本发明涉及低碳烷烃催化脱氢的催化剂。
液化石油气(主要成分:丙烷、丁烷、异丁烷等)的转化对有效利用石油资源具有十分重要的意义,尤其是异丁烷催化脱氢的产物异丁烯是生产甲基叔丁基醚的主要原料。甲基叔丁基醚是生产高辛烷值无铅汽油的添加剂,近年来国内外市场需求日益扩大。有关低碳烷烃(C34)催化脱氢的研究已有大量的报道,[见U.S.Pat 5,220,091(1993);4,393,259(1983);4,381,418(1983);J.Catal.,158,1-12(1996);燃料化学学报,22(5),22-26(1993)]。低碳烷烃的催化脱氢反应一般使用担载型铂-锡催化剂,反应温度在550-670℃范围内,催化剂载体可以是Al2O3、ZnAl2O4、CaAl2O4等。然而,使用前述载体的担载型铂-锡催化剂用于低碳烷烃(C3-4)催化脱氢反应,烯烃的选择性较差、催化剂的寿命较短。
本发明的目的在于提供一种用于低碳烷烃(C3-4)的催化脱氢反应,有较好的目标烯烃选择性和催化剂寿命较长的担载型铂-锡催化剂。
本发明的技术方案是:
一种用于低碳烷烃脱氢的担载型铂-锡催化剂,其载体为MgAl(O)复合氧化物,Mg与Al的摩尔比为2∶1至15∶1,Pt为载体MgAl(O)重量的0.2至1.2%,Pt与Sn的摩尔比为0.5∶1至1.5∶1的担载型铂-锡催化剂PtSn/MgAl(O)。
本发明的担载型铂-锡催化剂的制法,是在含有计量的硝酸镁和硝酸铝的溶液中加入氨和碳酸铵的混和溶液,得到沉淀,沉淀经洗涤除去硝酸根离子后,烘干,650至1000℃焙烧,得到MgAl(O)复合氧化物;用等量浸渍法将计量的锡负载到上述MgAl(O)载体上,烘干,在450至550℃水蒸气脱氯,在650至1000℃焙烧得到Sn/MgAl(O),再用等量浸渍法将计量的铂负载到Sn/MgAl(O)上,烘干,450至550℃水蒸气脱氯,在650至1000℃焙烧,即得到担载型铂-锡催化剂PtSn/MgAlO。
上述的催化剂制法,在计量的硝酸镁和硝酸铝溶液中,金属离子总浓度为1至2摩尔/升,Mg与Al的摩尔比为2∶1至15∶1。
上述的催化剂制法,氨和碳酸铵混和溶液中氨的用量按下式计算:n氨水=1.1×(2n硝酸镁+3n硝酸铝),
碳酸铵的用量为:n碳酸铵=0.5n硝酸铝,其中,n为摩尔数。将计量的氨水和碳酸铵配成与硝酸镁和硝酸铝混合溶液等体积的溶液。
上述的催化剂制法,用等量浸渍法将计量的锡负载到MgAl(O)载体上,所用的锡化合物是四氯化锡溶液。
上述的催化剂制法,用等量浸渍法将计量的铂负载到Sn/MgAl(O)上。所用的铂化合物是H2PtCl6或Pt(NH3)2Cl4溶液。
用本发明的担载型铂-锡催化剂进行低碳烷烃(C4烷烃)的脱氢反应,其异丁烯的选择性达97-98%,并且催化剂的寿命较长。
以下通过实施例进一步说明本发明。
实施例:称取1.5摩尔硝酸镁和0.5摩尔硝酸铝,溶于2升水中,得硝酸镁和硝酸铝的混合溶液,将含5摩尔氨和0.25摩尔碳酸铵的2升水溶液加入上述硝酸镁和硝酸铝的混合溶液中沉淀出水滑石,洗涤除去硝酸根离子,120℃烘干,700℃焙烧,即得到MgAl(O)载体60克。采用等量浸渍法将0.3克SnCl4负载到上述MgAl(O)载体上,经100℃烘干,480℃下水蒸气脱氯,700℃焙烧得到Sn/MgAl(O),再用等量浸渍法将0.47克H2PtCl6负载到Sn/MgAl(O)上,经100℃烘干,480℃下水蒸气脱氯,然后在700℃焙烧,筛取20-40目的颗粒状PtSn/MgAl(O)催化剂,该催化剂的Pt/Mg/Al(O)重量比为0.375%,Pt∶Sn摩尔比为1∶1。用该催化剂进行异丁烷脱氢的活性测定。
异丁烷脱氢的活性测定:反应的温度:610℃(反应前催化剂在480℃还原1小时);反应物:混合C4烷烃(异丁烷81.4%,正丁烷18.6%);烷烃空速:1800 h-1;常压脱氢,氢烃体积比为1∶1。反应结果见表1。表1中催化剂1为上述本发明的催化剂PtSn/MgAl(O),催化剂2为参比的催化剂PtSn/Al2O3,其Pt/Al2O3的重量比为0.375%,Pt∶Sn的摩尔比为0.2∶1。所有预处理和反应条件均同上。表1异丁烷催化脱氢反应催化剂性能的比较
反应时间(小时) | 0 | 1 | 2 | 3 | 4 | 5 | |
催化剂1 | 异丁烯的选择性(mol%)异丁烷的转化率(mol%)异丁烯的收率(mol%) | 97.3758.9957.44 | 98.0455.2854.19 | 97.5251.4750.19 | 97.9951.0650.04 | 98.0148.9748.00 | 97.9346.5245.56 |
催化剂2 | 异丁烯的选择性(mol%)异丁烷的转化率(mol%)异丁烯的收率(mol%) | 94.8068.1664.62 | 95.3061.1458.27 | 95.3655.1952.63 | 95.0151.6649.09 | 95.1243.2041.10 | 94.0239.2936.95 |
从表中可以看出,催化剂1异丁烯的选择性达97-98%,高于参比催化剂2的异丁烯选择性(94-95%);反应5小时后,催化剂1以异丁烷转化率和异丁烯收率计的活性明显高于参比催化剂2,说明本发明的催化剂有较强的抗失活能力。
Claims (6)
1.一种用于低碳烷烃催化脱氢的担载型铂-锡催化剂,其特征是载体为MgAl(O)复合氧化物,Mg与Al的摩尔比为2∶1至15∶1,Pt为载体MgAl(O)重量的0.2至1.2%,Pt与Sn的摩尔比为0.5∶1至1.5∶1的担载型铂-锡催化剂PtSn/MgAl(O)。
2.根据权利要求1所述的担载型铂-锡催化剂的制法,其特征是在含有计量的硝酸镁和硝酸铝的溶液中加入氨和碳酸铵的混和溶液,得到沉淀,沉淀经洗涤除去硝酸根离子后,烘干,650至1000℃焙烧,得到MgAl(O)复合氧化物;用等量浸渍法将计量的锡负载到上述MgAl(O)载体上,烘干,在450至550℃水蒸气脱氯,在650至1000℃焙烧得到Sn/MgAl(O),再用等量浸渍法将计量的铂负载到Sn/MgAl(O)上,烘干,450至550℃水蒸气脱氯,在650至1000℃焙烧,即得到担载型铂-锡催化剂PtSn/MgAlO。
3.根据权利要求2所述的催化剂制法,其特征是在硝酸镁和硝酸铝溶液中,Mg与Al的摩尔比为2∶1至15∶1。
4.根据权利要求2所述的催化剂制法,其特征是在氨和碳酸铵混和溶液中氨的用量按下式计算:n氨水=1.1×(2n硝酸镁+3n硝酸铝),碳酸铵的用量为:n碳酸铵=0.5n硝酸铝,其中,n为摩尔数。
5.根据权利要求2所述的催化剂制法,其特征是用四氯化锡溶液将锡负载到MgAl(O)载体上。
6.根据权利要求2所述的催化剂制法,其特征是用H2PtCl6或Pt(NH3)2Cl4将铂负载到Sn/MgAl(O)上。
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CN102211972B (zh) * | 2010-04-06 | 2014-12-10 | 中国石油化工股份有限公司 | 水滑石负载型催化剂在异丁烷脱氢制备异丁烯中的用途 |
CN102441444B (zh) * | 2010-10-13 | 2016-03-30 | 中国石油化工股份有限公司 | 一种脱氢催化剂的制备方法 |
CN103055951A (zh) * | 2011-10-21 | 2013-04-24 | 中国科学院大连化学物理研究所 | 一种c10-c13长链正构烷烃脱氢催化剂载体的制备方法 |
CN104107718B (zh) * | 2013-04-16 | 2016-08-03 | 中国石油化工股份有限公司 | 用于低碳烷烃脱氢制烯烃的催化剂及其制备方法 |
CN105582925A (zh) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂 |
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CN1103010A (zh) * | 1993-11-26 | 1995-05-31 | 中国科学技术大学 | 含铜、镧氧化物和铂、铑的三效催化剂及其制法 |
WO1996013475A1 (en) * | 1994-10-27 | 1996-05-09 | Regents Of The University Of Minnesota | Catalytic oxidative dehydrogenation process |
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Patent Citations (7)
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US4931419A (en) * | 1987-10-21 | 1990-06-05 | Pro-Catalyse | Catalyst for the conversion of vehicular exhaust gases and process for preparing the catalyst |
CN1033949A (zh) * | 1987-12-17 | 1989-07-19 | 环球油品公司 | 层状的脱氢催化剂颗粒 |
EP0332289A2 (en) * | 1988-03-08 | 1989-09-13 | The British Petroleum Company P.L.C. | A process for the production of mono-olefins by the catalytic oxidative dehydrogenation of gaseous paraffinic hydrocarbons having two or more carbon atoms |
CN1055303A (zh) * | 1990-02-07 | 1991-10-16 | 斯南普罗吉蒂联合股票公司 | 碳原子数为2-5的链烷烃脱氢的催化组合物 |
CN1069493A (zh) * | 1991-08-09 | 1993-03-03 | 廖自基 | 从“十大功劳”提取精制黄连素工艺 |
CN1103010A (zh) * | 1993-11-26 | 1995-05-31 | 中国科学技术大学 | 含铜、镧氧化物和铂、铑的三效催化剂及其制法 |
WO1996013475A1 (en) * | 1994-10-27 | 1996-05-09 | Regents Of The University Of Minnesota | Catalytic oxidative dehydrogenation process |
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