CN113578345B - 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 - Google Patents
二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 Download PDFInfo
- Publication number
- CN113578345B CN113578345B CN202110861234.5A CN202110861234A CN113578345B CN 113578345 B CN113578345 B CN 113578345B CN 202110861234 A CN202110861234 A CN 202110861234A CN 113578345 B CN113578345 B CN 113578345B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- propane
- carbon dioxide
- auxiliary agent
- load capacity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001294 propane Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000002131 composite material Substances 0.000 title abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- QHCZOWRGLNMSKI-UHFFFAOYSA-N carbon dioxide;propane Chemical compound CCC.O=C=O QHCZOWRGLNMSKI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 description 36
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- 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
Abstract
本发明公开了一种二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法，该催化剂的载体是SiO2或Al2O3，活性组分为Pt和Sn，第一助剂为CeO2，第二助剂为Fe、Co、Ni、Pd、Ru等任意一种或多种；以催化剂的质量为100％计，Pt的负载量为0.1％～1.0％，Sn的负载量为0.5％～5.0％，第一助剂中Ce元素的负载量为1.0％～5.0％，第二助剂的负载量为0.01％～0.5％；该催化剂采用浸渍法制备而成，制备流程简单，经济环保。本发明催化剂对二氧化碳氧化丙烷临氢脱氢具有较高的丙烷和二氧化碳转化率以及丙烯收率，同时富产合成气，具有良好的工业化应用前景。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种用于二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气的铂基复合催化剂，及采用该催化剂催化二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气的方法。
背景技术
丙烯作为石油化工生产中重要的的有机原料之一，一般用于生产聚丙烯、异丙醇、丙三醇、丙烯腈、环氧丙烷、丙酮、苯酚等衍生产品。近年来，随着我国经济的快速发展，丙烯需求一直在稳步增长。目前，丙烯主要来自与石脑油等清油的蒸气热裂解和催化热裂解等，但是存在丙烯产率低，能耗大以及化石资源匮乏等问题。而考虑到持续增加的丙烯需求量和廉价易得的丙烷的高效利用等因素，目前丙烷直接脱氢(PDH)被看做是一条重要的生产丙烯的工艺。
对于丙烷直接脱氢而言，热力学分析结果表明，在反应体系中引入氢气，提高了反应产物的浓度，不利于PDH反应向正向进行，进而抑制丙烯的生成，降低生产效率。但动力学研究结果表明，在丙烷脱氢反应中引入氢气，也就是丙烷临氢脱氢能够有效抑制催化剂上的积炭反应，提高催化剂稳定性的同时，明显降低了碳损失，显著提高了丙烯的收率，因此被应用于实际工业生产之中。
此外，二氧化碳氧化丙烷脱氢(CO2-ODP)一方面能够克服PDH能耗高和原料处理能力较低等问题，同时实现温室气体CO2的资源化利用；另一方面，与分子氧氧化丙烷脱氢相比，不存在丙烷过度氧化的问题，有望成为一条节能且环境友好的绿色合成工艺，但现有催化剂普遍存在活性偏低、失活迅速等难题。
发明内容
本发明在综合上述PDH和CO2-ODP各自优缺点的基础上，提出在丙烷直接脱氢反应体系中同时引入H2和CO2，一方面利用反应体系中引入的CO2弱氧化剂来缓解丙烷直接脱氢的热力学平衡限制，提高丙烷的转化率，同时在反应体系中引入H2抑制积炭，提高催化剂的寿命和丙烯收率；另一方面，利用丙烷和二氧化碳重整反应(CRP)、逆水煤气变换反应(RWGS)及二者的耦合效应，达到同时制取丙烯和合成气的目的。
本发明同时提供具有催化PDH、CRP以及RWGS功能的铂基复合催化剂，以满足用于二氧化碳氧化丙烷临氢脱氢同时高效制丙烯和合成气的需求。
针对上述目的，本发明所采用的铂基复合催化剂的载体是SiO2或Al2O3，活性组分为Pt和Sn，第一助剂为CeO2，第二助剂为Fe、Co、Ni、Pd、Ru中任意一种或多种；以催化剂的质量为100％计，Pt的负载量为0.1％～1.0％，Sn的负载量为0.5％～5.0％，第一助剂中Ce元素的负载量为1.0％～5.0％，第二助剂的负载量为0.01％～0.5％；该催化剂通过下述方法制备得到：
采用浸渍法，按照催化剂的组成，将活性组分的前驱体、第一助剂的前驱体和第二助剂的前驱体溶于无水乙醇中，然后将所得溶液与载体粉末混合，于室温下静置6～12h，然后在60～110℃干燥4～10h，500～650℃焙烧3～6h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂。
上述铂基复合催化剂中，以催化剂的质量为100％计，优选Pt的负载量为0.3％～0.6％，Sn的负载量为0.5％～2.5％，第一助剂中Ce元素的负载量为1.0％～3.0％，第二助剂的负载量为0.02％～0.3％。
上述铂基复合催化剂中，优选第二助剂为Fe、Ni、Fe-Ni、Co-Ni、Pd-Ni或Ru。
上述活性成分Pt的前驱体为H2PtCl6·6H2O，活性成分Sn的前驱体为SnCl2·2H2O，Ce、Fe、Co、Ni的前驱体为其硝酸盐，分别是Ce(NO3)3·6H2O、Fe(NO3)3·9H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O)；Pd和Ru的前驱体为其氯化物，分别是PdCl2·2H2O和RuCl3·3H2O。
本发明催化剂催化二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法为：将40～60目催化剂装填入微型固定床反应器的石英管中，向反应器中通入氢气和氩气，从室温升温到250～550℃，还原0.5～3h后，切换为氩气，继续升温至500～650℃，然后切换为反应气，所述反应气是二氧化碳气体、氢气、丙烷的体积比为0.5～5.0:0.5～3.0:1.0的混合气，在压力为0.05～0.15MPa下进行反应。
上述催化二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法中，优选将40～60目催化剂装填入微型固定床反应器的石英管中，向反应器中通入氢气和氩气，从室温升温到400～500℃，还原1～2h后，切换为氩气，继续升温至580～630℃，然后切换为反应气，在压力为0.1～0.15MPa下进行反应。
上述反应气优选二氧化碳气体、氢气与丙烷体积比为1～2:1～1.5:1的混合气。
本发明的有益效果如下：
1、本发明将采用常规浸渍法制备的铂基复合催化剂用于二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气反应中，其中Pt-Sn为高效丙烷脱氢的活性组分，而金属氧化物助剂CeO2具有丰富的氧空位和优良的氧化还原性能，不仅能够改善活性物种分散度，提高丙烷转化率，而且能够促进CO2的有效活化。在此基础上，通过控制添加金属助剂Fe、Co、Ni、Pd、Ru的含量及其之间的比例，影响PDH、CRP、RWGS反应过程以及三者的耦合效应，进而达到同时高效生产丙烯和合成气的目的。
具体实施方式
下面结合对比例和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
对比例1
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％，将13.4mg H2PtCl6·6H2O和11.5mg SnCl2·2H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置6h，然后在80℃鼓风烘箱中干燥6h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn/Al2O3。
对比例2
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％，将13.8mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O和96.9mg Ce(NO3)3·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置6h，然后在60℃鼓风烘箱中干燥8h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce/Al2O3。
实施例1
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Ni的负载量为0.1％，将13.9mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O和5.2mg Ni(NO3)2·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置8h，然后在80℃鼓风烘箱中干燥6h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.1％Ni/Al2O3。
实施例2
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Co的负载量为0.1％，将13.9mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O和5.2mg Co(NO3)2·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置8h，然后在80℃鼓风烘箱中干燥6h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.1％Co/Al2O3。
实施例3
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Fe的负载量为0.2％，将13.9mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.1mg Ce(NO3)3·6H2O和15.1mg Fe(NO3)3·9H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置8h，然后在80℃鼓风烘箱中干燥6h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.2％Fe/Al2O3。
实施例4
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Pd的负载量为0.05％，将13.8mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O和1.0mg PdCl2·2H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置12h，然后在60℃鼓风烘箱中干燥8h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.05％Pd/Al2O3。
实施例5
以SiO2为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Ru的负载量为0.05％，将13.8mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O和1.3mg RuCl3·3H2O溶于1.2mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置12h，然后在60℃鼓风烘箱中干燥8h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.05％Ru/SiO2。
实施例6
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Co的负载量为0.05％、Ni的负载量为0.05％，将14.0mg H2PtCl6·6H2O、12.0mg SnCl2·2H2O、97.9mg Ce(NO3)3·6H2O、2.6mg Co(NO3)2·6H2O和2.6mg Ni(NO3)2·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置8h，然后在80℃鼓风烘箱中干燥6h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.05％Co-0.05％Ni/Al2O3。
实施例7
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Pd的负载量为0.02％、Ni的负载量为0.05％，将13.9mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O、0.4mg PdCl2·2H2O和2.6mg Ni(NO3)2·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置12h，然后在60℃鼓风烘箱中干燥8h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.02％Pd-0.05％Ni/Al2O3。
实施例8
以Al2O3为载体，Pt负载量为0.5％、Sn负载量为0.6％、CeO2中Ce元素负载量为3％、Fe的负载量为0.1％、Ni的负载量为0.03％，将13.9mg H2PtCl6·6H2O、11.9mg SnCl2·2H2O、97.0mg Ce(NO3)3·6H2O、7.6mg Fe(NO3)3·9H2O和1.6mg Ni(NO3)2·6H2O溶于1mL无水乙醇中，将所得溶液与1.0g Al2O3粉末混合，于室温下静置6h，然后在100℃鼓风烘箱中干燥4h，马弗炉中550℃下焙烧4h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂，记为0.5％Pt-0.6％Sn-3％Ce-0.1％Fe-0.03％Ni/Al2O3。
为了证明本发明的有益效果，发明人将对比例1和2和实施例1～8制备的催化剂用于催化二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气反应，具体方法如下：
常压条件下，将500mg 40～60目催化剂置于固定床反应器的恒温区内中，向反应器中通入H2与Ar体积比为1:9的混合气，流量为50mL·min-1，以5℃·min-1的升温速率从室温升至500℃，待温度稳定后，继续还原1h。随后关闭混合气，切换为Ar，以5℃·min-1的升温速率升温至600℃，待温度稳定后，切换为反应气，并以N2作为内标气，所述反应气是CO2、C3H8、H2的体积比为1:1:1的混合气，CO2、C3H8、H2和N2的流量分别为16、16、16和2mL·min-1，反应气体的总流量为50mL·min-1，在P＝0.1MPa条件下反应。反应器流出的产物在常州盘诺仪器有限公司生产的PANNAA91 Plus型气相色谱仪上进行分析(反应产物进入分析色谱前，采用无水氯化钙干燥，防止水分进入色谱，从而影响分析结果)。反应的主要产物有CO2、CO、CH4、C2H6、C2H4、C3H8、C3H6、H2。用Ar当作色谱柱载气，TCD用于分析CO2、CO、H2的含量，FID则分析CH4、C2H4、C2H6、C3H6、C3H8的含量。反应5min后，进行产物的定性和定量分析。实验结果见表1，其中H2转化率为负值时说明在反应过程中产氢，为正值时则相反。
表1
| 催化剂 | <![CDATA[C<sub>3</sub>H<sub>8</sub>转化率]]> | <![CDATA[CO<sub>2</sub>转化率]]> | <![CDATA[H<sub>2</sub>转化率]]> | <![CDATA[C<sub>3</sub>H<sub>6</sub>选择性]]> | <![CDATA[C<sub>3</sub>H<sub>6</sub>收率]]> |
| 对比例1 | 38.5％ | 36.3％ | -2.7％ | 91.3％ | 35.2％ |
| 对比例2 | 52.1％ | 47.2％ | -10.7％ | 81.1％ | 42.3％ |
| 实施例1 | 55.5％ | 54.3％ | -15.7％ | 80.4％ | 44.6％ |
| 实施例2 | 54.1％ | 49.5％ | -13.2％ | 81.0％ | 43.8％ |
| 实施例3 | 57.5％ | 55.3％ | -18.7％ | 78.1％ | 44.9％ |
| 实施例4 | 58.0％ | 57.1％ | -20.7％ | 76.0％ | 44.1％ |
| 实施例5 | 57.4％ | 54.3％ | -16.7％ | 85.3％ | 49.0％ |
| 实施例6 | 57.5％ | 53.5％ | -16.7％ | 83.1％ | 47.8％ |
| 实施例7 | 55.4％ | 49.7％ | -20.4％ | 83.5％ | 46.3％ |
| 实施例8 | 57.6％ | 52.7％ | -18.3％ | 86.4％ | 49.8％ |
由表1可见，与催化剂对比例1和2相比，本发明催化剂对二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气反应，在保持高丙烯收率的同时，具有较高的二氧化碳转化率。更重要的是，通过引入金属助剂，产氢量显著增加，达到了同时高效制丙烯和合成气的目的。
Claims (7)
1.一种二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：将40～60目催化剂装填入微型固定床反应器的石英管中，向反应器中通入氢气和氩气，从室温升温到250～550℃，还原0.5～3 h后，切换为氩气，继续升温至500～650℃，然后切换为反应气，所述反应气是二氧化碳气体、氢气、丙烷的体积比为0.5～5.0:0.5～3.0:1.0的混合气，在压力为0.05～0.15 MPa下进行反应；
所述催化剂的载体是SiO2或Al2O3，活性组分为Pt和Sn，第一助剂为CeO2，第二助剂为Fe、Co、Ni、Pd、Ru中任意一种或多种；以催化剂的质量为100%计，Pt的负载量为0.1%～1.0%，Sn的负载量为0.5%～5.0%，第一助剂中Ce元素的负载量为1.0%～5.0%，第二助剂的负载量为0.01%～0.5%；该催化剂通过下述方法制备得到：
采用浸渍法，按照催化剂的组成，将活性组分的前驱体、第一助剂的前驱体和第二助剂的前驱体溶于无水乙醇中，然后将所得溶液与载体粉末混合，于室温下静置6～12 h，然后在60～110℃干燥4～10 h，500～650℃焙烧3～6 h，自然冷却至室温，压片，造粒，过40～60目筛，得到催化剂。
2.根据权利要求1所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：以催化剂的质量为100%计，Pt的负载量为0.3%～0.6%，Sn的负载量为0.5%～2.5%，第一助剂中Ce元素的负载量为1.0%～3.0%，第二助剂的负载量为0.02%～0.3%。
3.根据权利要求1或2所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：所述第二助剂为Fe、Ni、Fe-Ni、Co-Ni、Pd-Ni或Ru。
4.根据权利要求1所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：活性成分Pt的前驱体为H2PtCl6·6H2O，活性成分Sn的前驱体为SnCl2·2H2O。
5.根据权利要求1所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：Ce、Fe、Co、Ni的前驱体为其硝酸盐；Pd和Ru的前驱体为其氯化物。
6. 根据权利要求1所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：将40～60目催化剂装填入微型固定床反应器的石英管中，向反应器中通入氢气和氩气，从室温升温到400～500℃，还原1～2 h后，切换为氩气，继续升温至580～630℃，然后切换为反应气，在压力为0.1～0.15 MPa下进行反应。
7.根据权利要求5或6所述的二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法，其特征在于：所述反应气为二氧化碳气体、氢气与丙烷体积比为1～2:1～1.5:1的混合气。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110861234.5A CN113578345B (zh) | 2021-07-29 | 2021-07-29 | 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110861234.5A CN113578345B (zh) | 2021-07-29 | 2021-07-29 | 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113578345A CN113578345A (zh) | 2021-11-02 |
| CN113578345B true CN113578345B (zh) | 2023-04-07 |
Family
ID=78251541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110861234.5A Active CN113578345B (zh) | 2021-07-29 | 2021-07-29 | 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113578345B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116237040A (zh) * | 2023-03-28 | 2023-06-09 | 北京石油化工学院 | 一种用于丙烷脱氢制备丙烯反应的铂系脱氢催化剂及其制备方法和应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164690A (zh) * | 2006-10-20 | 2008-04-23 | 中国科学院大连化学物理研究所 | 一种负载型铂基三元催化剂及制法和应用 |
| CN101411978A (zh) * | 2008-11-28 | 2009-04-22 | 南开大学 | 一种丙烷脱氢制丙烯的催化剂及其制备和应用 |
| CN101785993A (zh) * | 2009-01-22 | 2010-07-28 | 复旦大学 | 一种二氧化碳气氛下丙烷脱氢制丙烯催化剂的制备方法 |
| CN104084198A (zh) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | 一种丙烷脱氢制丙烯的铂氧化铝系列催化剂及制备方法 |
| CN106512994A (zh) * | 2016-09-27 | 2017-03-22 | 大连理工大学 | 一种抗积碳铂基丙烷脱氢制丙烯催化剂及其制备方法 |
| CN111085199A (zh) * | 2019-12-26 | 2020-05-01 | 四川润和催化新材料股份有限公司 | 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 |
-
2021
- 2021-07-29 CN CN202110861234.5A patent/CN113578345B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164690A (zh) * | 2006-10-20 | 2008-04-23 | 中国科学院大连化学物理研究所 | 一种负载型铂基三元催化剂及制法和应用 |
| CN101411978A (zh) * | 2008-11-28 | 2009-04-22 | 南开大学 | 一种丙烷脱氢制丙烯的催化剂及其制备和应用 |
| CN101785993A (zh) * | 2009-01-22 | 2010-07-28 | 复旦大学 | 一种二氧化碳气氛下丙烷脱氢制丙烯催化剂的制备方法 |
| CN104084198A (zh) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | 一种丙烷脱氢制丙烯的铂氧化铝系列催化剂及制备方法 |
| CN106512994A (zh) * | 2016-09-27 | 2017-03-22 | 大连理工大学 | 一种抗积碳铂基丙烷脱氢制丙烯催化剂及其制备方法 |
| CN111085199A (zh) * | 2019-12-26 | 2020-05-01 | 四川润和催化新材料股份有限公司 | 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 |
Non-Patent Citations (1)
| Title |
|---|
| Zeeshan Nawaz et al..Parametric Characterization and Influence of Tin on the Performance of Pt-Sn/SAPO-34 Catalyst for Selective Propane Dehydrogenation to Propylene.《Ind. Eng. Chem. Res.》.2009,(第undefined期),第1274-1280页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113578345A (zh) | 2021-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109647399B (zh) | 常温催化氧化芳香类VOCs的单原子催化剂的制备方法 | |
| CN101637726A (zh) | 一种甲烷-二氧化碳重整制备合成气催化剂的制备方法 | |
| CN101940958B (zh) | 负载型铁基合成气制低碳烯烃催化剂的制备方法 | |
| CN101972656B (zh) | 一种乙醇自热重整制取氢气的镍基催化剂及其制备方法 | |
| CN113578345B (zh) | 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法 | |
| Ting et al. | Low activation energy dehydrogenation of aqueous formic acid on platinum–ruthenium–bismuth oxide at near ambient temperature and pressure | |
| CN111151287B (zh) | 一种碱性氧化物改性氮化硼催化剂及其制备方法与应用 | |
| CN107349956B (zh) | 乙醇水蒸气重整制氢催化剂及其制备方法 | |
| CN111790381A (zh) | 一种用于低碳烷烃脱氢的金属催化剂 | |
| CN107537485A (zh) | 异戊烷脱氢制异戊烯的催化剂及其制备方法 | |
| CN108654641B (zh) | 一种二氧化碳甲烷重整催化剂及其制备方法 | |
| CN113578321B (zh) | 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的金属氧化物改性铂基催化剂及方法 | |
| JP2023533579A (ja) | 銅系水素化触媒の調製方法、それで調製された触媒及び使用 | |
| CN113651671B (zh) | 一种二氧化碳氧化丙烷临氢脱氢同时制丙烯和合成气的方法 | |
| CN115055182B (zh) | 一种丙烷氧化脱氢催化剂及其制备方法与应用 | |
| CN114797946B (zh) | 一种丙烷脱氢制丙烯的负载型Pt基催化剂 | |
| CN100488628C (zh) | 甲烷催化部分氧化制合成气的改良催化剂及其制备方法 | |
| CN1275688C (zh) | 一种用于制备苯乙烯的催化剂及其制备方法和应用 | |
| KR100711509B1 (ko) | 자열개질 반응에 의해 물과 에탄올 혼합물로부터 수소를 제조하는데 사용되는 복합 금속 담지 촉매, 그 제조 방법 및 상기 촉매를 이용하여 수소를 제조하는 방법 | |
| CN117623845A (zh) | 稀土金属氧化物改性铂基催化剂催化二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的方法 | |
| CN114054023B (zh) | 一种合金单原子催化剂的制备方法和应用 | |
| US10737250B2 (en) | PdIn alloy catalyst, method for manufacturing PdIn alloy catalyst and application thereof | |
| KR20220069110A (ko) | 이소프로필벤젠 제조를 위한 촉매, 및 그의 제조 방법 및 용도 | |
| CN107790169B (zh) | 异丁烷氧化脱氢催化剂、制备方法及其应用 | |
| CN112570040B (zh) | 一种异丙苯催化剂的活化方法及得到的异丙苯催化剂与其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |