CN1073893A - 丙烷氧化脱氢制丙烯催化剂 - Google Patents
丙烷氧化脱氢制丙烯催化剂 Download PDFInfo
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- CN1073893A CN1073893A CN92111518A CN92111518A CN1073893A CN 1073893 A CN1073893 A CN 1073893A CN 92111518 A CN92111518 A CN 92111518A CN 92111518 A CN92111518 A CN 92111518A CN 1073893 A CN1073893 A CN 1073893A
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- fluorochemical
- catalyzer
- propane
- rare earth
- metal
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- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001294 propane Substances 0.000 title claims abstract description 18
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- -1 metal oxide compound Chemical class 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910004573 CdF 2 Inorganic materials 0.000 claims 1
- 229910017768 LaF 3 Inorganic materials 0.000 claims 1
- 229910001512 metal fluoride Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 229910052714 tellurium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000012495 reaction gas Substances 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- 229910052713 technetium Inorganic materials 0.000 abstract 1
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明是开发一种以稀土和过渡金属氧化物、氟
化物为主的丙烷氧化脱氢制丙烯的新型催化制。它
含有稀土金属特别是Ce、La、Sm、Nd、Y、Th等的氧
化物或/和其它金属特别是Bi、Sn、Cr、Cd、Pb、Tc
的氧化物；还含有氟化物，可以是稀土金属特别是
Cc、La、Sm的氟化物，也可以是Bi、Cd的氟化物。
本发明的催化剂用于丙烷氧化脱氟制丙烯，在反应气
配比为C3H8∶O2∶N2为8∶6∶86，空速为
6000/h，反应温度在450—550℃之间，丙烯收率在
12—36％之间。
Description
本发明涉及一种催化剂。
丙烷广泛存在于天然气和石油气中，是液化石油气的主要成份。由于副产丙烯的乙烯生产路线将要面临变革的推动，丙烷氧化脱氢制丙烯或直接一步选择（氨）氧化制丙烯醛（腈）的研究近几年来不断为许多著名的催化学者所倡导和重视（如御圆生诚等，“催化技术的进展”，载《石油化工译丛》，1992年第2期，PP.21），有关的研究和技术开发也十分活跃。如：H.H.Kung等报道V-Mg-O体系在催化丙烷氧化脱氢中的作用〔J.Catal.，1987，105∶483〕，在540℃，原料比为C3H8∶O2＝2∶1时，丙烯收率达15.2%。N.Gior-dano等报道用CdX2（X＝F、Cl）参杂的Mo-Te-O/SiO2或Al2O3催化剂研究丙烷的氧化〔Oxidn.Commun.1984，7∶99〕，在500℃时，丙烷转化率为20-30%，生成丙烯和丙烯醛的总选择性约为40%。US，Pat.，4607129（1986）公布的V2O5/SiO2催化剂用于石油重整，也可用于丙烷和异丁烷脱氢。以上文献报道的结果各有其特点，但收率普遍较低。
本发明的目的在于开发一种以稀土和其它金属氧化物、氟化物为主的丙烷氧化脱氢制丙烯的新型催化剂。
本发明的催化剂是一种丙烷氧化脱氢制丙烯的催化剂。所说的催化剂含有一种金属的氧化物。所说的金属可以是稀土金属，特别是Ce、La、Sm、Y、Nd、Th等，也可以是其它金属，如Bi、Sn、Cr、Pb、Te、Cd等。本发明的特征是所说的催化剂还含有一种或二种氟化物。所说的氟化物可以是稀土金属，特别是Ce、La、Sm、Y、Nd、Th等的氟化物，也可以是Bi、Cr、Pb、Cd等的氟化物。氧化物和氟化物的摩尔比范围为5∶1至1∶5。其中以氧化物和氟化物的摩尔比为2∶1至1∶2为较好，以2∶1时为最好。
氟化物可以用稀土元素或其它金属的可溶盐以NH4F或HF的水溶液沉淀相应的可溶盐制备，也可以直接用市售的氟化物。
所说的催化剂是把计量的氟化物和计量的氧化物或可以分解为氧化物的盐类混合碾磨均匀，再用蒸馏水调匀成糊状，于100℃下烘干2小时。高温焙烧3至8小时，焙烧温度范围为750-900℃，最好是在800-900℃。然后再制成所需要的粒度，一般为0.22至0.40mm。
催化剂评价是在国定床反应器中进行，常压，反应气配比为C3H8∶O2∶N2为8∶6∶86，空速为6000/h，反应温度一般为450-550℃之间，丙烯收率在12-36%之间。
本发明的催化剂制作简单，机械强度好，催化性能稳定，可在较低温度下用于丙烷氧化脱氢制丙烯，丙烯收率较高。
下面以实施例对本发明作进一步说明。
实施例1：
把3.44克CeO2加入1.97克CeF3中，混合均匀，加入蒸馏水调匀，在100℃下烘干3小时，850℃下焙烧3小时，制成0.22至0.40mm粒度。所制备的催化剂用于丙烷氧化脱氢制丙烯的反应。反应条件为：反应气配比∶C3H8∶O2∶N2＝8∶6∶86，反应温度500℃，催化剂用量0.5ml，空速为6000/h。分析反应尾气可知丙烷转化率为53.4%，生成丙烯选择性为67.5%，丙烯收率为36.0%。
实施例2：
把0.86克CeO2加入1.97克CeF3中，按上述方法制备出催化剂，在同样反应条件下丙烷转化率为41.3%，丙烯选择性为81.1%，丙烯收率为33.5%。连续反应84小时，烯收率仍达到31.7%。
实施例3：
1.2克Bi2O3加入1.97克CeF3中，加入蒸馏水研磨均匀，在100℃下烘干2小时，再在850℃下焙烧3小时，制成0.22至0.40mm的粒度，在同例1的反应条件下评价催化剂的活性。丙烷转化率为45.6%，丙烯选择性为76.4%，丙烯收率为34.8%。
Claims (4)
1、一种丙烷氧化脱氢制丙烯的催化剂，所说的催化剂含有一种金属的氧化物，所说的金属可以是稀土金属，特别是Ce、La、Sm、Y、Nd、Th等，也可以是其它金属，如Bi、Sn、Cr、Pb、Te等，本发明的特征是所说的催化剂还含有一种或二种氟化物，所说的氟化物可以是稀土金属，特别是Ce、La、Sm、Y、Nd、Th等的氟化物，也可以是Bi、Cr、Pb、Cd等的氟化物，催化剂中氧化物和氟化物的摩尔比范围为5∶1至1∶5；所说的催化剂是将计量的氟化物加入计量的氧化物中，混合研磨至粉末，以蒸馏水调匀，于100℃烘干2小时，在750-950℃之间焙烧2至8小时，最好是在800℃至900℃焙烧3至5小时制成。
2、根据权利要求1所述的催化剂，其特征是所说的稀土金属氟化物是CeF3、LaF3、SmF3。
3、根据权利要求1所述的催化剂，其特征是所说的其它金属氟化物包括BiF3、CdF2。
4、根据权利要求1所述的催化剂，其特征是氧化物与氟化物的摩尔比为1∶1和2∶1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111518A CN1029915C (zh) | 1992-10-19 | 1992-10-19 | 丙烷氧化脱氢制丙烯催化剂 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111518A CN1029915C (zh) | 1992-10-19 | 1992-10-19 | 丙烷氧化脱氢制丙烯催化剂 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1073893A true CN1073893A (zh) | 1993-07-07 |
| CN1029915C CN1029915C (zh) | 1995-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92111518A Expired - Fee Related CN1029915C (zh) | 1992-10-19 | 1992-10-19 | 丙烷氧化脱氢制丙烯催化剂 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1029915C (zh) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044787C (zh) * | 1993-12-29 | 1999-08-25 | 厦门大学 | 异丁烷氧化脱氢制异丁烯催化剂及其制造方法 |
| US6239325B1 (en) | 1998-05-18 | 2001-05-29 | Nippon Shokubai Co Ltd | Lower alkane oxidative dehydrogenation catalysts and a process for producing olefins |
| US6635794B2 (en) * | 2000-10-26 | 2003-10-21 | Nippon Shokubai Co Ltd | Catalysts for oxidative dehydrogenation of alkanes and a process for producing olefins |
| US6756517B2 (en) | 1998-05-18 | 2004-06-29 | Nippon Shokubai Co., Ltd. | Lower alkane oxidative dehydrogenation catalysts and a process for producing olefins |
| US7321058B2 (en) | 2000-06-14 | 2008-01-22 | Basf Aktiengesellschaft | Method for producing acrolein and/or acrylic acid |
| DE102007006647A1 (de) | 2007-02-06 | 2008-08-07 | Basf Se | Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts |
| CN101543781B (zh) * | 2009-05-04 | 2013-06-05 | 厦门大学 | 丙烷氧化脱氢制丙烯催化剂及其制备方法 |
| US8530717B2 (en) | 2008-07-21 | 2013-09-10 | Basf Se | Process for the industrial isolation of propene |
| CN114220979A (zh) * | 2021-11-13 | 2022-03-22 | 深圳信息职业技术学院 | 催化剂载体及其制备方法、催化剂、燃料电池 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434407C (zh) * | 2006-01-19 | 2008-11-19 | 中国石油化工股份有限公司 | 一种丙烷脱氢制丙烯的方法 |
-
1992
- 1992-10-19 CN CN92111518A patent/CN1029915C/zh not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044787C (zh) * | 1993-12-29 | 1999-08-25 | 厦门大学 | 异丁烷氧化脱氢制异丁烯催化剂及其制造方法 |
| US6239325B1 (en) | 1998-05-18 | 2001-05-29 | Nippon Shokubai Co Ltd | Lower alkane oxidative dehydrogenation catalysts and a process for producing olefins |
| US6756517B2 (en) | 1998-05-18 | 2004-06-29 | Nippon Shokubai Co., Ltd. | Lower alkane oxidative dehydrogenation catalysts and a process for producing olefins |
| US7321058B2 (en) | 2000-06-14 | 2008-01-22 | Basf Aktiengesellschaft | Method for producing acrolein and/or acrylic acid |
| US6635794B2 (en) * | 2000-10-26 | 2003-10-21 | Nippon Shokubai Co Ltd | Catalysts for oxidative dehydrogenation of alkanes and a process for producing olefins |
| DE102007006647A1 (de) | 2007-02-06 | 2008-08-07 | Basf Se | Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts |
| US8530717B2 (en) | 2008-07-21 | 2013-09-10 | Basf Se | Process for the industrial isolation of propene |
| CN101543781B (zh) * | 2009-05-04 | 2013-06-05 | 厦门大学 | 丙烷氧化脱氢制丙烯催化剂及其制备方法 |
| CN114220979A (zh) * | 2021-11-13 | 2022-03-22 | 深圳信息职业技术学院 | 催化剂载体及其制备方法、催化剂、燃料电池 |
| CN114220979B (zh) * | 2021-11-13 | 2024-04-16 | 深圳信息职业技术学院 | 催化剂载体及其制备方法、催化剂、燃料电池 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1029915C (zh) | 1995-10-04 |
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