CN1201861C - 一种二氧化碳选择性氧化丙烷制取丙烯的催化剂及其制法 - Google Patents
一种二氧化碳选择性氧化丙烷制取丙烯的催化剂及其制法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001294 propane Substances 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims description 8
- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
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- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Chemical group 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052742 iron Chemical group 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910018663 Mn O Inorganic materials 0.000 description 4
- 229910003176 Mn-O Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 230000000505 pernicious effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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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Abstract
一种用于二氧化碳选择氧化丙烷制取丙烯的催化剂,它是以比表面积为200~500m2/g的超细二氧化硅为载体担载有5%的铬和0.2~0.4%钾。采用本发明的催化剂,丙烷与CO2反应可高选择性的转化为丙烯,丙烷单程转化率为30%,丙烯的选择性可达90%。并且转化温度可以大大降低。本发明公开了催化剂的制法。
Description
一、技术领域
本发明涉及一种用二氧化碳选择性氧化丙烷制取丙烯的催化剂及其制备方法。
二、背景技术
在天然气、石油液化气及炼厂气中存在大量的低碳烷烃,随着生产的发展,将其转化为烯烃等重要化工原料将会产生显著的经济效益和社会效益。对于低碳烷烃脱氢制烯烃过程,二十世纪30年代开始实现工业化生产,在70年代又开发出采用Cr2O3/Al2O3或Pt-Sn/Al2O3催化剂进行丙烷、丁烷生产丙烯和丁烯新的工艺路线。但由烷烃如丙烷直接脱氢制备丙烯,受热力学平衡限制,丙烷转化率不高,并且需要高温,反应的能耗较大。而由空气氧化丙烷脱氢的方法,则因为深度氧化和氧分子***等副反应,尚未能取得其催化活性和丙烯选择性都令人满意的结果。以二氧化碳作为一种选择性氧化剂催化转化丙烷制取丙烯,一方面可以提供重要的工业原料丙烯,同时又可以消除导致温室效应的二氧化碳,这是一个具有工业化应用前景的催化反应。伊藤伸一(1,日本化学会志,8(1999)553)使用V2O5-Rh/SiO2催化剂,表明在CO2气氛中对丙烷脱氢有一定催化活性,但丙烯的选择性不太理想。Takahara(2,Catal.Today,45(1998)55)的结果是5wt%Cr2O3/SiO2催化剂,在550℃的CO2气氛中,丙烯选择性和收率由Ar气氛中的90.4%和6.5%分别提高到94.0%和9.1%。Krylov O V等人(3,Ind.Eng.Chem.Res.,34(1995)474)采用1.5%K-5.5%Cr-17%Mn-O/SiO2,在830℃、3600hr-1和CO2/C3H8=1.5的条件下,丙烷的转化率为96%,烯烃的总收率为73%,但丙烯的定向选择性不够高。此外徐龙伢等(4,CN 1181993A;CN1152566A)在11%K-5%Cr-14%Mn-O/SiO2催化剂上,在740℃、0.6Mpa、800hr-1和CO2/C3H8=1的条件下,得到了丙烷转化率84.2%、丙烯选择性42.4%和乙烯选择性30.2%的结果。
三、发明内容
本发明的目的是提供一种用于二氧化碳选择氧化丙烷制取丙烯的催化剂及其制备方法。
本发明的技术方案如下:
一种用于二氧化碳选择氧化丙烷制取丙烯的催化剂,它是以比表面积为200~500m2/g的超细二氧化硅为载体担载质量比为5%的铬和0.2~0.4%钾。
上述的催化剂优选的钾的担载量是0.4%。
上述的催化剂中钾可以由镁、钙、钡、镍、镧或铁替代。
上述的催化剂中镁、钙、钡、镍、镧或铁的担载量为0.4%。
一种上述催化剂的制法,它由以下步骤组成:
步骤一、将计量的硝酸铬和硝酸钾溶于水,配成溶液,加入比表面积为200~500m2/g的超细二氧化硅浸渍,蒸干。
步骤二、将步骤一所得的浸渍有硝酸铬和硝酸钾的二氧化硅在650~800℃空气气氛下焙烧4~10小时,即得本发明的催化剂。
上述的催化剂制法中硝酸钾可以由硝酸镁、硝酸钙、硝酸钡、硝酸镍、硝酸镧或硝酸铁替代。
采用本发明的催化剂,丙烷与CO2反应可高选择性的转化为丙烯,丙烷单程转化率为30%,丙烯的选择性可达90%。并且转化温度可以大大降低。
四、具体实施方式
实施例一
将18.24克硝酸铬(Cr(NO3)3·9H2O)和0.49克硝酸钾(KNO3)加水50毫升溶解,加入50克比表面积为200m2/g的超细二氧化硅浸渍,边加热边搅拌蒸发至干,然后于800℃空气气氛下焙烧4小时,制得本发明的催化剂(组成为5%Cr-0.4%K/SiO2)。丙烷与CO2的催化转化反应在连续进料固定床石英反应器(内径6毫米)中进行,催化剂在650℃分别用氧气和氮气依次吹扫0.5小时,然后切换成反应气(物质的量之比:CO2/C3H8=1/3.6,下同)开始反应。反应产物经在线气相色谱分析。结果列于表1。
表1.C3H8和CO2在含有不同含量助催化剂K的5%Cr/SiO2催化剂上的反应结果
转化率(%) 选择性(%)
催化剂
C3H8 C3H6 CH4 C2H4+C2H6
5%Cr/SiO2 27.0 85.0 12.4 2.6
5%Cr-0.1%K/SiO2 24.8 80.0 15.3 4.7
5%Cr-0.2%K/SiO2 22.3 100 - -
5%Cr-0.4%K/SiO2 31.3 91.2 7.7 1.1
5%Cr-0.8%K/SiO2 17.4 89.1 8.6 2.3
5%Cr-1.0%K/SiO2 3.0 70.0 21.6 8.4
*GHSV=2800h-1,大气压,650℃,2小时反应结果。
实施例二
采用比表面积为500m2/g的超细二氧化硅,其它步骤同实施例一,焙烧温度为650℃,焙烧10小时,所制得的本发明的催化剂的催化效果基本同实施例一制得的催化剂。
实施例三
采用比表面积为300m2/g的超细SiO2为载体,采用实施例1所述方法,用K、Mg、Ca、Ba、La、Ni、Fe等的硝酸盐替代硝酸钾,制得本发明的催化剂,并用于丙烷与CO2的催化转化反应,反应结果列于表2。
表2.C3H8和CO2在含不同助催化剂的5%Cr/SiO2催化剂上的反应结果
转化率(%) 选择性(%)
催化剂
C3H8 C3H6 CH4 C2H4+C2H6
5%Cr/SiO2 27.0 85.0 12.4 2.6
5%Cr-0.4%Mg/SiO2 24.8 100 - -
5%Cr-0.4%K/SiO2 31.3 91.2 7.7 1.1
5%Cr-0.4%Ca/SiO2 19.8 100 - -
5%Cr-0.4%Ba/SiO2 14.2 100 - -
5%Cr-1%Ni/SiO2 16.2 100 - -
5%Cr-0.4%La/SiO2 23.4 90.0 10.0 -
5%Cr-0.4%Fe/SiO2 20.5 100 - -
*GHSV=2800h-1,大气压,650℃,2小时反应结果。
实施例四、
与文献结果比较
本发明的催化剂与文献所用的催化剂用于丙烷与CO2的催化转化反应的结果比较示于表3。
表3.本发明催化剂与文献催化剂用于丙烷与CO2的催化转化反应结果
催化剂 C3H8转化率(%) C3H6选择性(%) 反应温度(℃)
aCr-Mg/SiO2 24.8 100 650
aCr-K/SiO2 31.3 91.2 650
b1V-Rh/SiO2 42.4 43.4 650
b2Cr2O3/SiO2 9.6 94.0 550
b3K-Cr-Mn-O/SiO2 96.0 c73 830
b4K-Cr-Mn-O/SiO2 84.2 42.4 740
(a)本发明催化剂,(b)文献所用催化剂,(c)总烯烃选择性
由此可见,采用本发明的催化剂,CO2可将丙烷高选择性的转化为丙烯。并且本发明的催化剂使转化反应的温度大大降低。鉴于CO2是导致大气温室效应的有害气体之一,利用它来选择性氧化低碳烷烃具有重要意义。
Claims (6)
1.一种用于二氧化碳选择氧化丙烷制取丙烯的催化剂,其特征是:它是以比表面积为200~500m2/g的超细二氧化硅为载体担载质量比为5%的铬和0.2~0.4%钾。
2.根据权利要求1所述的催化剂,其特征是:钾的担载量是0.4%。
3.根据权利要求2所述的催化剂,其特征是:钾由镁、钙、钡、镍、镧或铁替代。
4.根据权利要求3所述的催化剂,其特征是:镁、钙、钡、镍、镧或铁的担载量为0.4%。
5.一种权利要求1所述催化剂的制法,其特征是它由以下步骤组成:
步骤一、将计量的硝酸铬和硝酸钾溶于水,配成溶液,加入比表面积为200~500m2/g的超细二氧化硅浸渍,加热蒸干,
步骤二、将步骤一所得的浸渍有硝酸铬和硝酸钾的二氧化硅在650~800℃空气气氛下焙烧4~10小时,即得本发明的催化剂。
6.根据权利要求5所述的催化剂的制法,其特征是:硝酸钾由硝酸镁、硝酸钙、硝酸钡、硝酸镍、硝酸镧或硝酸铁替代。
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CN100428993C (zh) * | 2005-09-29 | 2008-10-29 | 北京化工大学 | 一种二氧化碳氧化丙烷制丙烯的金属载体催化剂及其制备方法 |
EP2143701B1 (en) * | 2008-07-10 | 2011-03-02 | Rohm and Haas Company | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same |
CN112657499A (zh) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | 二氧化碳氧化环己烷的催化剂及其制法与应用 |
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