CN105381817A - 一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 - Google Patents
一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 Download PDFInfo
- Publication number
- CN105381817A CN105381817A CN201510691282.9A CN201510691282A CN105381817A CN 105381817 A CN105381817 A CN 105381817A CN 201510691282 A CN201510691282 A CN 201510691282A CN 105381817 A CN105381817 A CN 105381817A
- Authority
- CN
- China
- Prior art keywords
- sapo
- preparation
- molecular sieve
- microspherical catalyst
- slurry
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 60
- 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 60
- 239000002002 slurry Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000010009 beating Methods 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 4
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0054—Drying of aerosols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法和应用。该制备方法,包括如下步骤:1)将SAPO-18分子筛、SAPO-34分子筛和基质粘结剂于去离子水中混合搅拌,得到浆料;2)将步骤1)中的浆料进行胶磨或打浆,得到胶磨或打浆后的浆料;3)对步骤2)中的胶磨或打浆后的浆料进行干燥,得到微球催化剂。本发明制备微球催化剂的制备方法简单,利于大规模工业化生产。该微球催化剂可用于甲醇或/和二甲醚制取低碳烯烃反应,可以通过SAPO-18与SAPO-34分子筛的加入比例有效调节产物乙烯和丙烯的比例,同时可以提高乙烯和丙烯选择性。
Description
技术领域
本发明属于化学化工领域,具体涉及一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法和应用。
背景技术
乙烯、丙烯是现代化工的基本原料,工业上乙烯和丙烯主要是以石油炼制而得的轻质油(石脑油和轻柴油)为原料进行生产,完全依赖于石油资源。随着社会经济的发展,烯烃需求日益增大,研究开发烯烃生产新技术一直是重要的研究方向,其中煤经甲醇制取低碳烯烃(MTO)是最具有应用前景的非石油路线生产乙烯、丙烯的新途径。
几十年来,国内外研究机构均投入了大量人力和物力进行研究开发。早期甲醇制烯烃过程主要以改性HZSM-5分子筛为催化剂(USP3,911,041、USP4,049,573、USP4,100,219、USP4,542,252、USP5,367,100、USP5,573,990、JP60-126233、JP61-97231、JP62-70324),其最佳结果为USP5,367,100和5,573,990中公开的大连化学物理研究所甲醇或二甲醚制取低碳烯烃技术,在磷和镧改性的HZSM-5分子筛催化剂上,其气相产物中乙烯和丙烯总选择性仅为65wt%左右,乙烯、丙烯和丁烯总选择性大于85wt%。在上世纪80年代初,美国联合碳化物公司(UCC)开发了新型磷酸硅铝系列分子筛(SAPO-n)(USP4,440,871),SAPO分子筛是一类结晶硅铝磷酸盐,由PO4 +、AlO4 -、及SiO4的四面体构成三维骨架结构。随着磷酸硅铝系列分子筛的问世,人们开始将这种小孔且酸性适中的分子筛用于MTO反应,如SAPO-17,SAPO-34,SAPO-35,SAPO-44等(USP4,499,327),它们的孔径大约为0.43nm,是一类较好的择形催化剂。其中SAPO-34分子筛由于具有适宜的酸性和孔道结构在MTO反应中呈现出优异的催化性能,成为了取代ZSM-5沸石分子筛的新一代MTO催化剂的活性组分。
SAPO-18分子筛是1994年Chen,J.S.等报道的一种新型磷酸硅铝分子筛(CatalysisLetters,28,241-248,1994),晶体骨架拓扑结构为AEI型,与具有CHA结构的SAPO-34拓扑结构极为相似,二者均具有相同的由双六元环组成的周期结构单元,再由周期结构单元连接成八元环孔道结构,由于其连接方式的不同分别形成了CHA和AEI两种拓扑结构。由此可见,SAPO-34和SAPO-18分子筛均具有相同的初级结构单元和类似的孔道结构,其孔口直径均为0.43nm。同时对SAPO-18分子筛的酸性测试表明,其Bronsted酸位点均少于SAPO-34分子筛,因此SAPO-18分子筛在MTO反应中也呈现出优异的催化性,不仅有利于提高产物丙烯选择性并可以延缓积炭的生成。
中国申请专利CN102372291公开了一种SAPO-18/SAPO-34共生分子筛的制备方法,其特征在于共生分子筛中至少含有SAPO-18和SAPO-34两种共生物相,其中共生分子筛中以重量百分比计SAPO-34分子筛的含量为40%~98%。CN103418431公开了一种用于制备有机含氧化合物制低碳烯烃的催化剂的复合分子筛及其制备方法,所述复合分子筛的结构是以SAPO-18分子筛为核、以SAPO-34分子筛为壳。CN103878018公开了一种小晶粒SAPO-18/SAPO-34共晶分子筛的合成方法,该方法主要特点是采用单模板剂或双模板剂,在合成过程中加入晶体生长阻止剂,通过调整合成参数,在高速搅拌下进行晶化,所得共晶分子筛中AEI/CHA之比约为50/50~70/30。CN103833047公开了一种复合分子筛,由SAPO-5分子筛、SAPO-18分子筛和SAPO-34分子筛共生而成,通过调节模板剂三乙胺或N,N-二异丙基乙基胺模板剂和SiO2用量,调整SAPO-5分子筛、SAPO-18分子筛和SAPO-34分子筛在复合分子筛中的相对含量,进而调整所述复合分子筛的孔道结构分布和酸性,但是上述SAPO-18/SAPO-34共生或复合分子筛均是在合成体系中改变各种条件参数,实际生产中操作较复杂。
发明内容
本发明的目的是提供一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法。
本发明所提供的制备方法,包括如下步骤:
1)将SAPO-18分子筛、SAPO-34分子筛和基质粘结剂于去离子水中混合搅拌,得到浆料;
2)将步骤1)中的浆料进行胶磨或打浆,得到胶磨或打浆后的浆料;
3)对步骤2)中的胶磨或打浆后的浆料进行干燥,得到微球催化剂。
上述制备方法中,步骤1)中,所述SAPO-18分子筛、SAPO-34分子筛和基质粘结剂的质量比为(2-5):(2-5):13。
所述基质粘结剂选自硅溶胶或硅的氧化物、铝溶胶或铝的氧化物、无定型硅铝氧化物、高岭土和粘土中的至少一种。
当所述基质粘结剂选自高岭土、铝溶胶和硅溶胶时,所述SAPO-18分子筛、所述SAPO-34分子筛、所述高岭土、所述铝溶胶和所述硅溶胶的质量比为(2-5):(2-5):(7-8):(3-4):2,具体可为5:2:8:3:2或2:5:7:4:2。
进一步的,所述高岭土中高岭石的质量分数为50%-90%,进一步可为70%-90%,具体可为85.5%;
所述硅溶胶或硅的氧化物中SiO2的质量分数为10-80%;
所述铝溶胶或铝的氧化物中Al2O3的质量分数为10-80%。
所述浆料的质量固含量为30-40%。
上述制备方法中,步骤2)中,所述胶磨是通过胶体磨进行,所述打浆是通过高速剪切机进行。
上述制备方法中,步骤3)中,所述干燥是通过喷雾干燥的方式进行。
进一步的,所述喷雾干燥的条件如下:采用离心式或压力式喷雾干燥设备,保持喷雾干燥设备的入口温度为300-500℃,出口温度为100-300℃。同时,可进一步通过对离心式喷雾干燥设备中雾化器的转速和压力式喷雾干燥设备中喷嘴的压力进行调变,得到一定粒度分布微球催化剂。
所述微球催化剂中SAPO-18分子筛和SAPO-34分子筛的质量分数为10-50%。
上述制备方法中,步骤3)中,还包括对所述微球催化剂于400-700℃(具体可在空气中)下焙烧3-6h的步骤。
本发明所制备得到的微球催化剂也属于本发明的保护范围。
此外,本发明所制备得到的微球催化剂在催化甲醇或/和二甲醚制取低碳烯烃中的应用亦属于本发明的保护范围。
本发明以SAPO-18和SAPO-34分子筛作为双活性组份,将不同比例SAPO-18和SAPO-34分子筛与基质粘结剂组分混合,然后加水配制成浆料,再经胶体磨胶磨或高速剪切机打浆后进行喷雾干燥,得到成型微球分子筛催化剂。该方法制备催化剂活性组份SAPO-18与SAPO-34分子筛比例调节方便,利于大规模工业化生产。
与现有技术相比,本发明具有如下有益效果:
1)制备的微球催化剂用于甲醇或/和二甲醚制取低碳烯烃反应,可以通过SAPO-18与SAPO-34分子筛的加入比例有效调节产物乙烯和丙烯的比例,同时可以提高乙烯和丙烯选择性。
2)本发明制备微球催化剂的制备方法简单,利于大规模工业化生产。
具体实施方式
下面通过具体实施例对本发明的方法进行说明,但本发明并不局限于此。
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
下述实施例中所用SAPO-34分子筛为市售SAPO-34分子筛即可,具体的制备方法如下:向1m3合成釜中加入390kg去离子水,开启搅拌,然后加入75.2kg活性氧化铝(含Al2O367.8wt%),搅拌下继续加入115.3kg磷酸(含H3PO485wt%),之后再缓慢加入24.0kg硅溶胶(含SiO225.0wt%),继续搅拌不少于30min,最后加入151.5kg三乙胺,继续搅拌直至成为均一相。合成釜升温至200℃及自生压力下晶化24h,降温后物料离心分离,固体产物用去离子水洗涤至中性,在120℃下空气中干燥12h得到SAPO-34分子筛原粉,其XRD分析结果如表1所示:
表1、SAPO-34分子筛的XRD分析结果
下述实施例中所用SAPO-18分子筛为市售SAPO-18分子筛即可,具体的制备方法如下:向1m3合成釜中加入400kg去离子水,开启搅拌,然后加入75.2kg活性氧化铝(含Al2O367.8wt%),搅拌下继续加入109.5kg磷酸(含H3PO485wt%),之后再缓慢加入24.0kg硅溶胶(含SiO225.0wt%),继续搅拌不少于30min,最后加入104.0kgN,N-二异丙基乙胺,继续搅拌直至成为均一相。合成釜升温至170℃及自生压力下晶化12h,降温后物料离心分离,固体产物用去离子水洗涤至中性,在120℃下空气中干燥12h得到SAPO-18分子筛原粉,其XRD分析结果如表2所示:
表2、SAPO-18分子筛的XRD分析结果
实施例1、制取由甲醇或/和二甲醚制取低碳烯烃的微球催化剂:
将上述制备的SAPO-34分子筛、上述制备的SAPO-18分子筛、高岭土(高岭土中高岭石的质量含量为85.5%)、铝溶胶(固含量24.5wt%)和硅溶胶(固含量32.0%)按质量比为5:2:8:3:2计量后依次加入到一定量的去离子水中,搅拌30min,得到质量固含量为35%的浆料;再将浆料通过高速剪切机打浆15min;最后,浆料室温静置2h,采用离心式喷雾干燥设备进行喷雾干燥,离心式雾化器的转速为35Hz,入口温度为380℃,出口温度不低于120℃。得到的喷雾干燥产品在空气气氛下600℃焙烧4h即得到微球催化剂,命名为WQC-01。
实施例2、制取由甲醇或/和二甲醚制取低碳烯烃的微球催化剂:
将上述制备的SAPO-34分子筛、上述制备的SAPO-18分子筛、高岭土(高岭土中高岭石的质量含量为85.5%)、铝溶胶(固含量24.5wt%)和硅溶胶(固含量32.0%)按质量比为2:5:7:4:2计量后依次加入到一定量的去离子水中,搅拌30min,得到固含量为40%的浆料;再将浆料通过高速剪切机打浆15min。浆料室温静置2h,采用离心式喷雾干燥设备进行喷雾干燥,离心式雾化器的转速为33Hz,入口温度400℃,出口温度不低于120℃。得到的喷雾干燥产品在空气气氛下600℃焙烧4h即得到微球催化剂,命名为WQC-02。
实施例3、利用微球催化剂将甲醇转化成低碳烯烃:
将实施例1中得到的微球催化剂进行甲醇转化成低碳烯烃(MethanoltoOlefins,MTO)反应。采用固定流化床反应器,将实施例1中得到的微球催化剂的装填量为10g,首先催化剂在30ml/min的氦气气氛下升至550℃活化1h,然后降温至反应温度500℃,关闭氦气,用微量计量泵将80wt%甲醇水溶液泵入温度为300℃汽化器中,气化后物料进入500℃反应器进行反应,甲醇质量空速WHSV为2.0h-1,反应产物由在线气相色谱进行分析,分析结果如表3所示:
表3、反应产物的气相色谱分析结果
*wt%,产物质量分布。
实施例4、利用微球催化剂将甲醇转化成低碳烯烃:
将实施例2中得到的微球催化剂进行甲醇转化成低碳烯烃(MTO)反应。采用固定流化床反应器,微球催化剂的装填量为10g,首先催化剂在30ml/min的氦气气氛下升至550℃活化1h,然后降温至反应温度450℃,关闭氦气,用质量流量计控制将二甲醚通入温度为300℃汽化器中,之后气化后物料进入450℃反应器进行反应,二甲醚质量空速WHSV为1.0h-1,反应产物由在线气相色谱进行分析,结果如表4所示。
表4、反应产物的气相色谱分析结果
*wt%,产物质量分布。
Claims (10)
1.一种微球催化剂的制备方法,包括如下步骤:
1)将SAPO-18分子筛、SAPO-34分子筛和基质粘结剂于去离子水中混合搅拌,得到浆料;
2)将步骤1)中的浆料进行胶磨或打浆,得到胶磨或打浆后的浆料;
3)对步骤2)中的胶磨或打浆后的浆料进行干燥,得到微球催化剂。
2.如权利要求1所述的制备方法,其特征在于:步骤1)中,所述SAPO-18分子筛、SAPO-34分子筛和基质粘结剂的质量比为(2-5):(2-5):13;
所述基质粘结剂选自硅溶胶或硅的氧化物、铝溶胶或铝的氧化物、无定型硅铝氧化物、高岭土和粘土中的至少一种;
所述浆料的质量固含量为30-40%。
3.如权利要求2所述的制备方法,其特征在于:所述高岭土中高岭石的质量分数为50%-90%;
所述硅溶胶或硅的氧化物中SiO2的质量分数为10-80%;
所述铝溶胶或铝的氧化物中Al2O3的质量分数为10-80%。
4.如权利要求1-3中任一项所述的制备方法,其特征在于:所述基质粘结剂选自高岭土、铝溶胶和硅溶胶时,所述SAPO-18分子筛、所述SAPO-34分子筛、所述高岭土、所述铝溶胶和所述硅溶胶的质量比为(2-5):(2-5):(7-8):(3-4):2。
5.如权利要求1-4中任一项所述的制备方法,其特征在于:步骤2)中,所述胶磨是通过胶体磨进行;
所述打浆是通过高速剪切机进行。
6.如权利要求1-5中任一项所述的制备方法,其特征在于:步骤3)中,所述干燥是通过喷雾干燥的方式进行;
所述微球催化剂中SAPO-18分子筛和SAPO-34分子筛的质量分数为10-50%。
7.如权利要求6所述的制备方法,其特征在于:所述喷雾干燥的条件如下:采用离心式或压力式喷雾干燥设备,保持喷雾干燥设备的入口温度为300-500℃,出口温度为100-300℃。
8.如权利要求1-7中任一项所述的制备方法,其特征在于:步骤3)中,还包括对所述微球催化剂于400-700℃下焙烧3-6h的步骤。
9.权利要求1-8中任一项所述的制备方法得到的微球催化剂。
10.权利要求9所述的微球催化剂在催化甲醇或/和二甲醚制取低碳烯烃中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510691282.9A CN105381817A (zh) | 2015-07-01 | 2015-10-22 | 一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2015103793283 | 2015-07-01 | ||
CN201510379328 | 2015-07-01 | ||
CN201510691282.9A CN105381817A (zh) | 2015-07-01 | 2015-10-22 | 一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105381817A true CN105381817A (zh) | 2016-03-09 |
Family
ID=55414969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510691282.9A Pending CN105381817A (zh) | 2015-07-01 | 2015-10-22 | 一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105381817A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110252391A (zh) * | 2019-07-02 | 2019-09-20 | 中国天辰工程有限公司 | 一种催化剂的制备方法及应用 |
CN111111770A (zh) * | 2020-01-17 | 2020-05-08 | 太原理工大学 | 一种合成气转化制低碳烯烃的微球型双功能催化剂的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103418431A (zh) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | 一种用于制备有机含氧化合物制低碳烯烃的催化剂的sapo-34/sapo-18复合分子筛及其制备方法 |
CN103736519A (zh) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | 耐磨分子筛流化床催化剂的制备方法 |
-
2015
- 2015-10-22 CN CN201510691282.9A patent/CN105381817A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103736519A (zh) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | 耐磨分子筛流化床催化剂的制备方法 |
CN103418431A (zh) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | 一种用于制备有机含氧化合物制低碳烯烃的催化剂的sapo-34/sapo-18复合分子筛及其制备方法 |
Non-Patent Citations (1)
Title |
---|
MICHAEL HUNGER ET AL.: "In situ MAS NMR spectroscopic investigation of the conversion of methanol to olefins on silicoaluminophosphates SAPO-34 and SAPO-18 under continuous flow conditions", 《CATALYSIS LETTERS》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110252391A (zh) * | 2019-07-02 | 2019-09-20 | 中国天辰工程有限公司 | 一种催化剂的制备方法及应用 |
CN111111770A (zh) * | 2020-01-17 | 2020-05-08 | 太原理工大学 | 一种合成气转化制低碳烯烃的微球型双功能催化剂的制备方法 |
CN111111770B (zh) * | 2020-01-17 | 2022-04-22 | 太原理工大学 | 一种合成气转化制低碳烯烃的微球型双功能催化剂的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101903085B (zh) | 催化剂颗粒,用于制备烯烃类产物的方法,以及用于制备含氧化合物转化催化剂的方法 | |
CN103418431B (zh) | 一种用于制备有机含氧化合物制低碳烯烃的催化剂的sapo-34/sapo-18复合分子筛及其制备方法 | |
CN102464338B (zh) | 小晶粒sapo-34分子筛的制备方法 | |
CN101868297A (zh) | 用于制备烯烃类产品的方法 | |
CN101121145A (zh) | 一种含氧化合物转化制烯烃微球催化剂及其制备方法 | |
CN109701619A (zh) | Ssz-13/ssz-39复合结构分子筛及其合成方法 | |
CN106890672B (zh) | 一种甲醇转化制轻烯烃催化剂及其制备方法和应用 | |
CN108298550A (zh) | 一种以四氢呋喃与有机胺混合作为模板剂制备多级孔sapo-34分子筛的方法 | |
CN103011188A (zh) | 具有球形或片状形貌的纳米sapo-34分子筛及其合成方法及由其制备的催化剂和应用 | |
CN101503201B (zh) | Sapo-11分子筛及sapo-11分子筛基催化剂的制备方法 | |
CN104108726A (zh) | 高硅铝比cha结构磷酸硅铝分子筛及其合成方法 | |
CN107774303A (zh) | 多孔金属/分子筛复合催化剂、其制备方法及在合成气制备低碳烯烃中的用途 | |
CN102451763A (zh) | 一种钛硅分子筛复合催化剂及其制备方法 | |
CN103263947B (zh) | 一种用于制备有机含氧化合物制低碳烯烃的催化剂的复合分子筛及其制备方法 | |
CN105381817A (zh) | 一种由甲醇或/和二甲醚制取低碳烯烃的微球催化剂及其制备方法 | |
CN102335623A (zh) | 一种流化床催化剂及其制备方法 | |
CN105268475B (zh) | 正丁烯骨架异构制备异丁烯的方法 | |
CN103418425B (zh) | 甲醇转化制丙烯的催化剂及其制备方法 | |
CN103539144B (zh) | Sapo-44分子筛及其制备方法 | |
CN109180409B (zh) | 一种催化甲醇制丙烯的方法 | |
CN104192860A (zh) | 一种薄层状形貌sapo-34分子筛的合成方法 | |
CN103030155B (zh) | Sapo-44分子筛的合成方法 | |
CN101580248B (zh) | 一种硅铝磷酸盐分子筛sapo-34及其制备方法 | |
CN107029783B (zh) | 一种lpg直接转化为乙烯、丙烯的催化剂及其制备方法 | |
CN105233864A (zh) | 一种流化床用微球催化剂及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
AD01 | Patent right deemed abandoned | ||
AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20180727 |