CN111229302A - 一种钴基催化剂及其用途 - Google Patents
一种钴基催化剂及其用途 Download PDFInfo
- Publication number
- CN111229302A CN111229302A CN202010114607.8A CN202010114607A CN111229302A CN 111229302 A CN111229302 A CN 111229302A CN 202010114607 A CN202010114607 A CN 202010114607A CN 111229302 A CN111229302 A CN 111229302A
- Authority
- CN
- China
- Prior art keywords
- beta
- catalyst
- carrier
- cobalt
- molecular sieve
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 16
- 239000010941 cobalt Substances 0.000 title claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000001294 propane Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C07C5/3335—Catalytic processes with metals
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种钴基催化剂及其用途,该催化剂包括活性组分金属Co和载体,载体为纯硅片状ZSM‑5或经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛。本发明催化剂具有较高的脱氢活性和稳定性,制备工艺简单,成本较低,对环境友好,具有很好的工业应用前景。
Description
技术领域
本发明涉及催化剂和用途,特别涉及一种钴基催化剂及其用途。
背景技术
以丙烯为代表的低碳烯烃应用极为广泛,是工业上多种化工产品进一步生产的基础原料。目前我国对丙烯的需求量的增长速度已经远超过乙烯。丙烯是生产聚丙烯的主要原料,另外丙烯还可用于生产丙烯酸及其脂类、异丙醇、苯酚和丙酮、丁醇和辛醇等,丙烯制成品其良好的性能,在现代石油和化学工业中占据着重要的地位。目前,丙烯主要来源于石脑油裂解和石油催化裂化。随着石油资源的日益枯竭,丙烯的生产途径也从化石燃料裂化向低碳烷烃转化转变。由于我国天然气的开发,使得获得廉价丙烷成为可能,因此近年来我国已有多套丙烷脱氢装置在建以满足市场逐年递增的丙烯的需求。
丙烷催化脱氢反应受限于热力学平衡,须在高温、低压的苛刻反应条件下进行。同时丙烷脱氢过程中还伴随发生脱氢、裂化、氢解和积碳等复杂过程。当前,丙烷脱氢制丙烯主要采用UOP公司的Oleflex、Lummus Technology公司的Catofin工艺以及其他生产丙烯的方法。上述丙烷脱氢的工艺主要区别在于催化剂的制备方法,反应器的设计和催化剂的再生方法。UOP公司的Oleflex工艺采用Pt-Al2O3为催化剂,Lummus Technology公司的Catofin工艺采用Cr-Al2O3为催化剂。由于Cr会对环境造成污染,限制了工业使用。Pt基催化剂是被广泛应用的丙烷脱氢制丙烯催化剂。虽然在550℃常压条件下负载Pt基催化剂经过15min具有46%的丙烷转化率和93%的丙烯选择性,但由于高温条件下积碳比较严重,10h后催化剂已失活,稳定性较差,使用寿命较短。另外贵金属催化剂成本也较高。为了改善丙烷脱氢催化剂的反应性能,研究人员做了很多工作,例如周钰明等考察了Pt催化剂上的丙烷脱氢反应,其使用了多类载体,包括常规氧化铝、ZSM-5、SBA-15、介孔氧化铝等,发现分子筛具有最高的稳定性。采用分子筛替代传统的γ-Al2O3载体,有利于活性组分在载体表面充分分散,降低活性组分在催化剂表面的团聚,提高催化效果;其次,分子筛较短的孔道和众多的窗口,不利于积碳在催化剂表面上的沉积,从而抑制催化剂的快速失活;相比于硅铝分子筛,纯硅的分子筛具有较低的载体表面酸性,抑制裂解等优点,因此开发工艺简单且成本经济的合成方法,制备具有多级孔结构的分子筛具有重要意义。
中国专利201510833517.3研发了一种以三氧化二铝为载体,Pt为活性中心,Sn为第一助剂,在载体前驱体制备过程中引入La、Ce组分,制成改性的载体,然后再使用初湿浸渍的方法,将Pt、Sn浸渍到改性的载体上,干燥焙烧后再浸渍K、Na碱性金属。该专利公开的催化剂在丙烷脱氢中有较好的选择性,但转化率仍有待改善。
中国专利CN201110283358公开了一种用于丙烷脱氢的负载型Pt基催化剂,该催化剂的载体为介孔MCM-41分子筛,活性组分为Pt,负载量为0.1-1.0%,助剂为Sn、Sn-Ce或Sn-Ce-Ca。该催化剂具有较高的催化活性,反应2h后转化率下降10%。专利USP5192728报道了以ZSM或硼硅酸盐为载体,通过负载Pt、Sn、Mg,用于低碳烷烃脱氢的反应。专利101066532公开了一种以骨架含Sn的ZSM-5分子筛为载体的丙烷脱氢的催化剂,骨架中Sn的含量为0.1~6wt%,主要活性组分为Pt、Pd、Ir、Rh等中的至少一种,含量为0.01~2wt%,碱性金属助剂为IA或IIA族金属,含量为0.01~5wt%。Sn也可以负载在ZSM-5分子筛上,Sn的含量为0.01~10wt%。该催化剂具有较高的催化活性和抗积碳的能力。Pt系催化剂对丙烷脱氢制丙烯有显著地催化作用,能够显著地提高丙烷的转化率,提高丙烯的选择性,但是催化剂中以Pt为活性中心,有时还需要加入其它的一些助催化剂和碱金属,使得催化剂的制备流程长,催化剂的成本较高。上述催化脱氢的催化剂很难同时满足高活性、高选择性和高稳定性。因此需要提供一种同时满足达到“三高”的催化剂。
现有技术中的丙烷脱氢催化剂通常以Pt、Cr为主要金属活性组分,以γ-Al2O3为载体,活性组分分散程度、催化活性及稳定性仍需提升。本发明的目的是克服催化剂丙烷转化率和丙烯选择性不高且易于失活等缺陷,提供一种丙烷脱氢催化剂及其制备方法以及丙烷脱氢制丙烯的方法。
发明内容
发明目的:本发明目的是提供一种钴基催化剂。
本发明的另一目的是提供所述钴基催化剂的用途。
技术方案:本发明提供一种钴基催化剂,包括活性组分金属Co和载体,载体为纯硅片状ZSM-5或经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛。
进一步地,当载体为纯硅片状ZSM-5时,催化剂中Co的百分含量为0.5~1.5%。
进一步地,当载体为纯硅片状ZSM-5时,催化剂的制备方法,包括如下步骤:
(1)将TPAOH水溶液加入到去离子水中,加入尿素,搅拌1~2h;
(2)将TEOS及Co(NO3)2·6H2O的水溶液分别加入到上述溶液中,室温下搅拌24~48h,得到凝胶,再在180℃下晶化24~48h;
(3)将上述得到的产物过滤、洗涤、干燥、焙烧,去除模板剂,研磨即可。
进一步地,所述步骤(1)中TPAOH、去离子水与尿素的用量比为6~8:10~15:1~3;所述步骤(2)中TEOS及Co(NO3)2·6H2O的水溶液的用量为6~10g、2~15g。
进一步地,当载体为经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛时,催化剂的制备方法包括如下步骤:采用真空浸渍的方法将Co负载于高硅Beta分子筛上,
(1)载体的预处理:向硝酸中加入Beta分子筛进行脱铝处理,冷却后过滤洗涤至中性,干燥,记作DeAl~Beta;
(2)催化剂的制备:取所得DeAl-Beta于容器中,在搅拌下用真空泵持续抽真空,将Co(NO3)2·6H2O水溶液注入容器中,继续在搅拌下抽真空,最后将所得物质干燥、煅烧,即可。
进一步地,所述步骤(1)中Beta分子筛的SiO2/Al2O3=10~60。
一种钴基催化剂的用途,用于丙烷催化脱氢制丙烯。
有益效果:本发明的Co-ZSM-5、Co-Beta催化剂用于丙烷脱氢制丙烯具有较高的脱氢活性和稳定性,而且制备催化剂的工艺简单,成本较低,对环境友好,具有很好的工业应用前景。本发明分别以纯硅的ZSM-5分子筛、Beta分子筛为载体,以Co为活性组分的催化剂。合成的Co-ZSM-5催化剂,Co的含量在1%左右,在丙烷脱氢中,丙烯的选择性在94%左右,在反应50h的过程中,转化率达36%;合成的Co-Beta催化剂,Co的负载量仅约为0.5%,但在丙烷脱氢反应中的转化率达23%。
附图说明
图1为Co-ZSM-5催化剂的XRD图;
图2为Co-ZSM-5催化剂的BET图;
图3为Co-ZSM-5催化剂的SEM图和TEM图;
图4为Co-ZSM-5催化剂催化丙烷脱氢的活性图;
图5为Co-Beta催化剂的XRD图;
图6为Co-Beta催化剂催化丙烷脱氢的活性图。
具体实施方式
实施例1
本实施例的催化剂包括以纯硅片状ZSM-5作为载体,以金属Co为活性组分,采用水热的方法制备Co-ZSM-5催化剂,催化剂中Co的百分含量为1%,步骤如下:
(1)将8g浓度为2M的TPAOH水溶液加入到15g的去离子水中,然后加入3g分析纯的尿素,在磁力搅拌器下搅拌2h;
(2)将10g试剂纯的TEOS加入到上述溶液中,在搅拌下滴入10g的浓度为0.7mol/L的Co(NO3)2·6H2O的水溶液在室温下搅拌48h,得到凝胶,将溶液转移到50mL的水热釜中,在180℃下晶化48h;
(3)将上述得到的产物过滤、用去离子水洗涤3次,然后在80℃的烘箱中干燥12h,最后在600℃空气下焙烧3h,升温速率为3℃/min,用研钵研磨后即可得到片状的Co的含量为1%的Co-ZSM-5催化剂。
此产品的XRD谱图示于图1,可以看到,XRD谱图上在2θ为23.0°、23.9°、24.4°处分别有3个衍射峰,为ZSM-5分子筛的特征衍射峰。此产品的BET图示于图2,该产品有较大的比表面积434m2/g。此产品的SEM和TEM电镜图示于图3,可以看出晶化较好的尺寸在1.2μm左右。此产品的催化丙烷脱氢的催化性能图示于图4,丙烯的选择性在94%左右,在反应50h的过程中,转化率从38%降至36%左右,该催化剂具有高活性、高选择性和高稳定性的特点。
实施例2
本实施例的催化剂包括以纯硅片状ZSM-5作为载体,以金属Co为活性组分,采用水热的方法制备Co-ZSM-5催化剂,催化剂中Co的百分含量为0.5%,步骤如下:
(1)将6g浓度为2M的TPAOH水溶液加入到10g的去离子水中,然后加入1g分析纯的尿素,在磁力搅拌器下搅拌1h;
(2)将6g试剂纯的TEOS加入到上述溶液中,在搅拌下滴入2g的浓度为0.5mol/L的Co(NO3)2·6H2O的水溶液在室温下搅拌24h,得到凝胶,将溶液转移到50mL的水热釜中,在180℃下晶化48h;
(3)将上述得到的产物过滤,用去离子水洗涤3次,然后在80℃的烘箱中干燥12h,最后在600℃空气下焙烧3h,升温速率为3℃/min,用研钵研磨后即可得到片状的Co的含量为0.8%的Co-ZSM-5催化剂。
实施例3
本实施例的催化剂包括以纯硅片状ZSM-5作为载体,以金属Co为活性组分,采用水热的方法制备Co-ZSM-5催化剂,催化剂中Co的百分含量为1.5%,步骤如下:
(1)将7g浓度为2M的TPAOH水溶液加入到12g的去离子水中,然后加入2g分析纯的尿素,在磁力搅拌器下搅拌1-2h;
(2)将8g试剂纯的TEOS加入到上述溶液中,在搅拌下滴入15g的浓度为0.6mol/L的Co(NO3)2·6H2O的水溶液在室温下搅拌33h,得到凝胶,将溶液转移到50mL的水热釜中,在180℃下晶化48h;
(3)将上述得到的产物过滤、用去离子水洗涤3次,然后在80℃的烘箱中干燥12h,最后在600℃空气下焙烧3h,升温速率为3℃/min,用研钵研磨后即可得到片状的Co的含量为0.9%的Co-ZSM-5催化剂。
实施例4
本实施例的催化剂包括包括活性组分和载体。活性组分为Co,在催化剂中所占的质量百分比为0.55%;载体为经过脱铝处理商用Beta(SiO2/Al2O3=30)分子筛得到的高硅Beta分子筛。采用真空浸渍的方法将Co负载于Beta分子筛上,具体步骤如下:
(1)载体的预处理:取20mL 10~15M的HNO3于50mL圆底烧瓶中,在搅拌条件下加入1g商用Beta(SiO2/Al2O3=30)分子筛,于100℃下进行12h脱铝处理。冷却后,过滤洗涤至中性、100℃干燥20h,命名为DeAl-Beta;
(2)催化剂的制备:取500mg DeAl-Beta于三口烧瓶中,在搅拌下用真空泵持续抽真空5h;取0.3mL,浓度为0.4mol/L的Co(NO3)2·6H2O水溶液注入三口烧瓶中的DeAl-Beta中,继续在搅拌下抽真空5h;将上述所得物质于80℃干燥3h、在马弗炉中以3℃/min的升温速率升温至550℃,保持3h,即为Co-beta催化剂。
此产品的XRD谱图示于图5,可以看到,XRD谱图上在2θ为7.9°、13.6°、14.7°、21.7°、22.6°、25.5°、27.2°、28.6°、29.8°处的衍射峰,为Beta分子筛的特征衍射峰,表明脱铝处理并没有破坏Beta分子筛的骨架结构。此产品的催化丙烷脱氢的催化性能图示于图6,丙烯的选择性在89%左右,在反应12h的过程中,转化率从23%将至21%左右,该催化剂具有高活性和较好的稳定性的特点。
实施例5
本实施例的催化剂包括包括活性组分和载体。活性组分为Co,在催化剂中所占的质量百分比为0.4%;载体为经过脱铝处理的商用Beta(SiO2/Al2O3=10)分子筛。采用真空浸渍的方法将Co负载于Beta分子筛上,具体步骤如下:
(1)载体的预处理:取20mL 10M的HNO3于50mL圆底烧瓶中,在搅拌条件下加入1g商用Beta(SiO2/Al2O3=20)分子筛,于80℃下进行12h脱铝处理。冷却后,过滤洗涤至中性、100℃干燥10h,命名为DeAl-Beta;
(2)催化剂的制备:取500mg DeAl-Beta于三口烧瓶中,在搅拌下用真空泵持续抽真空5h;取0.3mL,浓度为0.3mol/L的Co(NO3)2·6H2O水溶液注入三口烧瓶中的DeAl-Beta中,继续在搅拌下抽真空5h;将上述所得物质于80℃干燥3h、在马弗炉中以3℃/min的升温速率升温至550℃,保持3h,即为Co-beta催化剂。
实施例6
本实施例的催化剂包括包括活性组分和载体。活性组分为Co,在催化剂中所占的质量百分比为0.8%;载体为经过脱铝处理的商用Beta(SiO2/Al2O3=60)分子筛。采用真空浸渍的方法将Co负载于Beta分子筛上,具体步骤如下:
(1)载体的预处理:取20mL 13M的HNO3于50mL圆底烧瓶中,在搅拌条件下加入1g商用Beta(SiO2/Al2O3=26)分子筛,于90℃下进行12h脱铝处理。冷却后,过滤洗涤至中性,100℃干燥10~20h,命名为DeAl-Beta;
(2)催化剂的制备:取500mg DeAl-Beta于三口烧瓶中,在搅拌下用真空泵持续抽真空5h;取0.3mL,浓度为0.35mol/L的Co(NO3)2·6H2O水溶液注入三口烧瓶中的DeAl-Beta中,继续在搅拌下抽真空5h;将上述所得物质于80℃干燥3h,在马弗炉中以3℃/min的升温速率升温至550℃,保持3h,即为Co-beta催化剂。
Claims (8)
1.一种钴基催化剂,其特征在于:包括活性组分金属Co和载体,载体为纯硅片状ZSM-5或经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛。
2.根据权利要求1所述的钴基催化剂,其特征在于:当载体为纯硅片状ZSM-5时,催化剂中Co的百分含量为0.5~1.5%。
3.根据权利要求1所述的钴基催化剂,其特征在于:当载体为纯硅片状ZSM-5时,催化剂的制备方法,包括如下步骤:
(1)将TPAOH水溶液加入到去离子水中,加入尿素,搅拌1~2h;
(2)将TEOS及Co(NO3)2·6H2O的水溶液分别加入到上述溶液中,室温下搅拌24~48h,得到凝胶,再在180℃下晶化24~48h;
(3)将上述得到的产物过滤、洗涤、干燥、焙烧,去除模板剂,研磨即可。
4.根据权利要求3所述的钴基催化剂,其特征在于:所述步骤(1)中TPAOH、去离子水与尿素的用量比为6~8:10~15:1~3;所述步骤(2)中TEOS及Co(NO3)2·6H2O的水溶液的用量为6~10g、2~15g。
5.根据权利要求1所述的钴基催化剂,其特征在于:当载体为经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛时,催化剂中Co的百分含量为0.40~0.80%。
6.根据权利要求1所述的钴基催化剂,其特征在于:当载体为经过脱铝处理Beta(SiO2/Al2O3=10~60)分子筛得到的高硅Beta分子筛时,催化剂的制备方法包括如下步骤:采用真空浸渍的方法将Co负载于高硅Beta分子筛上,
(1)载体的预处理:向硝酸中加入Beta分子筛进行脱铝处理,冷却后过滤洗涤至中性,干燥,记作DeAl~Beta;
(2)催化剂的制备:取所得DeAl-Beta于容器中,在搅拌下用真空泵持续抽真空,将Co(NO3)2·6H2O水溶液注入容器中,继续在搅拌下抽真空,最后将所得物质干燥、煅烧,即可。
7.根据权利要求6所述的钴基催化剂,其特征在于:所述步骤(1)中Beta分子筛的SiO2/Al2O3=10~60。
8.一种钴基催化剂的用途,其特征在于:用于丙烷催化脱氢制丙烯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010114607.8A CN111229302A (zh) | 2020-02-25 | 2020-02-25 | 一种钴基催化剂及其用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010114607.8A CN111229302A (zh) | 2020-02-25 | 2020-02-25 | 一种钴基催化剂及其用途 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111229302A true CN111229302A (zh) | 2020-06-05 |
Family
ID=70871467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010114607.8A Pending CN111229302A (zh) | 2020-02-25 | 2020-02-25 | 一种钴基催化剂及其用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111229302A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115722260A (zh) * | 2022-12-07 | 2023-03-03 | 昆明理工大学 | 镍基Beta沸石催化剂在甲烷干重整制备合成气中的应用 |
CN115920947A (zh) * | 2022-12-27 | 2023-04-07 | 中触媒新材料股份有限公司 | 一种Co@Silicalite-1低碳烷烃脱氢催化剂及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103030501A (zh) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | 生产丙烯的方法 |
CN109675548A (zh) * | 2019-01-21 | 2019-04-26 | 福州大学 | 一种用于丙烷脱氢制丙烯的分子筛催化剂及其制备方法 |
-
2020
- 2020-02-25 CN CN202010114607.8A patent/CN111229302A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103030501A (zh) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | 生产丙烯的方法 |
CN109675548A (zh) * | 2019-01-21 | 2019-04-26 | 福州大学 | 一种用于丙烷脱氢制丙烯的分子筛催化剂及其制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115722260A (zh) * | 2022-12-07 | 2023-03-03 | 昆明理工大学 | 镍基Beta沸石催化剂在甲烷干重整制备合成气中的应用 |
CN115920947A (zh) * | 2022-12-27 | 2023-04-07 | 中触媒新材料股份有限公司 | 一种Co@Silicalite-1低碳烷烃脱氢催化剂及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106512994B (zh) | 一种抗积碳铂基丙烷脱氢制丙烯催化剂及其制备方法 | |
CN105478107B (zh) | 铂催化剂在丙烷制备丙烯中的应用 | |
CN110975938A (zh) | 一种用于二氧化碳加氢制甲醇的催化剂及其制备方法 | |
CN111068648A (zh) | 以l酸氧化铝为载体的抗积碳制丙烯催化剂、制备及应用 | |
CN111229302A (zh) | 一种钴基催化剂及其用途 | |
CN114602495A (zh) | 一种丙烷脱氢Pt催化剂的制备方法 | |
CN102233282B (zh) | 一种以氧化硅-氧化铝为载体的费托合成催化剂及其应用 | |
CN117225400B (zh) | 一种改性氧化铝载体、制备方法和应用 | |
CN110496618B (zh) | 异丁烷脱氢催化剂及其制备方法以及异丁烷脱氢制异丁烯的方法 | |
CN111097485A (zh) | 一种催化柴油加氢转化催化剂及其制备方法和应用 | |
CN110026235B (zh) | 一种用于丙烷脱氢制备丙烯的催化剂及其制备方法 | |
CN111437813B (zh) | 一种异丁烷脱氢催化剂及其制备方法和应用 | |
CN110170333B (zh) | 一种用于二氧化碳气氛下乙烷制乙烯催化剂及其制备方法 | |
CN110329992B (zh) | 甲醇低温水汽重整制氢催化剂及其制备方法 | |
CN116116453B (zh) | 一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用 | |
CN114029064B (zh) | 一种超疏水型多孔铜铟催化剂的制备方法及应用 | |
CN114054023B (zh) | 一种合金单原子催化剂的制备方法和应用 | |
CN114054079B (zh) | 一种乙醇脱氢制备乙醛催化剂的制备方法与应用 | |
CN113289671A (zh) | 一种锌基分子筛催化剂及其制备方法和应用 | |
CN108568310B (zh) | 嵌入式微孔-介孔复合分子筛甲烷化催化剂及应用 | |
CN112536040A (zh) | 一种稠环芳烃加氢催化剂及其制备方法 | |
CN102373069A (zh) | 用于碳六烷烃裂解的方法 | |
CN110496635B (zh) | 异丁烷脱氢催化剂及其制备方法以及异丁烷脱氢制异丁烯的方法 | |
CN113213506B (zh) | 一种金属改性的sapo-34分子筛的制备方法及应用 | |
CN107224980B (zh) | 无需还原活化的二氧化碳甲烷化催化剂的制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |