CN104888867B - 一种制备mto催化剂载体的方法 - Google Patents
一种制备mto催化剂载体的方法 Download PDFInfo
- Publication number
- CN104888867B CN104888867B CN201510365260.3A CN201510365260A CN104888867B CN 104888867 B CN104888867 B CN 104888867B CN 201510365260 A CN201510365260 A CN 201510365260A CN 104888867 B CN104888867 B CN 104888867B
- Authority
- CN
- China
- Prior art keywords
- acid
- zsm
- nano modification
- hours
- template
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008187 granular material Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910001923 silver oxide Inorganic materials 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 150000003053 piperidines Chemical class 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J29/44—Noble 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- C07C2529/80—Mixtures of different zeolites
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明的目的是提供一种制备MTO催化剂载体的方法。具体步骤如下：制备纳米改性复合粉体，取铝源、磷源、水、ZSM‑5原粉和纳米改性复合粉体，搅拌混匀后依次加入模板剂、氢氟酸制得分子筛合成凝胶，将分子筛合成凝胶经晶化处理后，回收晶化产物即得ZSM‑5/AlPO4‑34复合分子筛。以该分子筛作为MTO催化剂载体。本发明制备ZSM‑5/AlPO4‑34复合分子筛的方法简单，晶化时间较短，适于大规模生产应用，其经济效益显著。采用本发明方法制得的ZSM‑5/AlPO4‑34复合分子筛应用于MTO反应中能够显著提高反应的选择性和催化效率。
Description
技术领域
本发明涉及一种制备MTO催化剂载体的方法，属于化工合成技术领域。
背景技术
MTO(Methanol To Olefin)是指由甲醇制取低碳烯烃（乙烯和丙烯）的化工工艺技术，为烯烃生产寻找了一条新的原料路线。不用石油而以甲醇为原料生产烯烃，不仅可使烯烃价格摆脱石油产品的影响，还能减少我国对石油资源的过度依赖。
MTO技术的关键是高性能催化剂的研制，早期对于MTO催化剂的研究主要以ZSM-5等中孔分子筛为主，ZSM-5的中大孔结构使其具有低碳少、寿命长等优点，但是由于其酸性太强，同时又具有烯烃收率低副产物多等缺点。1984年，UCC公司发明了SAPO-34分子筛用于MTO反应，其较小的孔径和较大的比表面积加快了MTO反应速率并且提高了反应的选择性，但是具有积碳高、易失活和寿命短等缺点。
鉴于甲醇制烯烃反应中的应用，需要制备一种ZSM-5/磷酸铝复合分子筛，与ZSM-5相比，ZSM-5/磷酸铝复合分子筛表现出了良好的协同作用和优良的催化性能。
发明内容
为了解决上述技术问题，本发明的目的是提供一种制备MTO催化剂载体的方法，具体步骤如下：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）将铝源、磷源加入水中搅拌待溶解完全，再加入ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入模板剂、氢氟酸，待搅拌3～5小时后制得纳米改性分子筛合成凝胶；
（3）将步骤（2）的分子筛合成凝胶在150～190℃下晶化12～24小时后冷却至室温，过滤，洗涤、在60-80℃下干燥，再在350～580℃下焙烧4～8小时即得纳米改性复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
所述铝源、磷源、模板剂、氢氟酸和水的摩尔比为铝源:磷源:模板剂: 氢氟酸：水=1:（1.0～1.5）:（0.5～2）:（0.1～0.2）：（50～300）；
所述的模板剂为吗啉、哌啶或吡啶。
所述的铝源为拟薄水铝石、异丙醇铝、氢氧化铝、氧化铝中的一种或两种任意比例的混合物。
所述的磷源为正磷酸。
步骤（1）中的酸选自盐酸、硝酸、甲酸、乙酸中的一种或几种。
步骤（3）中合成凝胶在160～180℃水热晶化18小时，干燥温度为60～80℃。
所述ZSM-5原粉的质量占分子筛合成凝胶总量的约1/10～1/5。
本发明的有益效果：
本发明制备纳米改性ZSM-5/AlPO4-34复合分子筛的方法简单，晶化时间较短，适于大规模生产应用，其经济效益显著。分子筛中还采用了特定配比的改性纳米复合粉体，经过表面改性的上述纳米复合粉体可有效改善分子筛的附着性、强度、韧性和耐高温性。ZSM-5/AlPO4-34复合分子筛特定组成中各组分的相互协同，在应用于MTO反应中能够显著提高反应的选择性和催化效率。
具体实施方式
实施例1
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（异丙醇铝+氧化铝）:正磷酸:（哌啶+吡啶）:氢氟酸：去离子水=1:1.0:0.5:0.1：50取各组分，将异丙醇铝和氧化铝石分别添加入到去离子水中搅拌6小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入哌啶和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/5，待搅拌3小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在150℃下晶化24小时后冷却至室温，抽滤，洗涤至中性后在80℃下干燥6小时，再在580℃下焙烧4小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
实施例2
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（氢氧化铝+拟薄水铝石）:正磷酸:（吗啉+吡啶）:氢氟酸：去离子水=1: 1.2: 1: 0.15：200取各组分，将氢氧化铝和拟薄水铝石分别添加入到去离子水中搅拌8小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入吗啉和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/7，待搅拌4小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在在180℃下晶化18小时，然后冷却至室温，抽滤，洗涤至中性后在70℃下干燥8小时，再在450℃下焙烧6小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
实施例3
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（异丙醇铝+拟薄水铝石）:正磷酸:（哌啶+吡啶）:氢氟酸：去离子水=1: 1.5: 2: 0.2：300取各组分，将异丙醇铝和拟薄水铝石分别添加入到去离子水中搅拌8小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入哌啶和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/5，待搅拌5小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在在190℃下晶化12小时，然后冷却至室温，抽滤，洗涤至中性后在60℃下干燥10小时，再在350℃下焙烧8小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
Claims (5)
1.一种制备MTO催化剂载体的方法，其特征在于：具体步骤如下：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中硅烷偶联剂KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）将铝源、磷源加入水中搅拌待溶解完全，再加入ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入模板剂、氢氟酸，待搅拌3～5小时后制得纳米改性分子筛合成凝胶；
（3）将步骤（2）的分子筛合成凝胶在160～180℃下晶化18小时后冷却至室温，过滤，洗涤、在70℃下干燥，再在350～580℃下焙烧4～8小时即得纳米改性复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂；
所述铝源、磷源、模板剂、氢氟酸和水的摩尔比为铝源:磷源:模板剂: 氢氟酸：水=1:（1.0～1.5）:（0.5～2）:（0.1～0.2）：（50～300）；
所述的模板剂为吗啉、哌啶或吡啶。
2.根据权利要求1所述的方法，其特征在于：所述的铝源为拟薄水铝石、异丙醇铝、氢氧化铝、氧化铝中的一种或两种任意比例的混合物。
3.根据权利要求1所述的方法，其特征在于：所述的磷源为正磷酸。
4.根据权利要求1所述的方法，其特征在于：步骤（1）中的酸选自盐酸、硝酸、甲酸、乙酸中的一种或几种。
5.根据权利要求1所述的方法，其特征在于：所述ZSM-5原粉的质量占分子筛合成凝胶总量的1/10～1/5。
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711275649.4A CN107715924A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276228.3A CN107899620A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275072.7A CN107971020A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276227.9A CN107971021A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275134.4A CN107899610A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201510365260.3A CN104888867B (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
| CN201711275606.6A CN107930685A (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510365260.3A CN104888867B (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
Related Child Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711275606.6A Division CN107930685A (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
| CN201711275649.4A Division CN107715924A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276228.3A Division CN107899620A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275134.4A Division CN107899610A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276227.9A Division CN107971021A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275072.7A Division CN107971020A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104888867A CN104888867A (zh) | 2015-09-09 |
| CN104888867B true CN104888867B (zh) | 2018-03-23 |
Family
ID=54022070
Family Applications (7)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711276227.9A Pending CN107971021A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276228.3A Pending CN107899620A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275134.4A Pending CN107899610A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275606.6A Pending CN107930685A (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
| CN201510365260.3A Active CN104888867B (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
| CN201711275649.4A Pending CN107715924A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275072.7A Pending CN107971020A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
Family Applications Before (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711276227.9A Pending CN107971021A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711276228.3A Pending CN107899620A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275134.4A Pending CN107899610A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275606.6A Pending CN107930685A (zh) | 2015-06-29 | 2015-06-29 | 一种制备mto催化剂载体的方法 |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711275649.4A Pending CN107715924A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
| CN201711275072.7A Pending CN107971020A (zh) | 2015-06-29 | 2015-06-29 | 一种mto催化剂载体的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (7) | CN107971021A (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239217A (zh) * | 2019-07-17 | 2021-01-19 | 国家能源投资集团有限责任公司 | Sapo-34分子筛及其制备方法与应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112870A (zh) * | 2013-01-31 | 2013-05-22 | 郑州大学 | 一种聚合物体系中制备ZSM-5/AlPO4-5复合分子筛的方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7309679B2 (en) * | 2005-08-08 | 2007-12-18 | Uop Llc | Attrition resistant MTO catalyst |
| CN101491773B (zh) * | 2008-01-25 | 2013-06-12 | 北京石油化工学院 | 含磷铝结构单元的mcm-41分子筛催化剂、制备方法及其应用 |
| CN101555022B (zh) * | 2009-04-22 | 2011-06-08 | 神华集团有限责任公司 | 一种金属改性sapo-34分子筛和含有该分子筛的催化剂的制备方法 |
| CN102092738B (zh) * | 2011-03-30 | 2012-03-21 | 南开大学 | 水热法无氟合成AlPO4-34 |
-
2015
- 2015-06-29 CN CN201711276227.9A patent/CN107971021A/zh active Pending
- 2015-06-29 CN CN201711276228.3A patent/CN107899620A/zh active Pending
- 2015-06-29 CN CN201711275134.4A patent/CN107899610A/zh active Pending
- 2015-06-29 CN CN201711275606.6A patent/CN107930685A/zh active Pending
- 2015-06-29 CN CN201510365260.3A patent/CN104888867B/zh active Active
- 2015-06-29 CN CN201711275649.4A patent/CN107715924A/zh active Pending
- 2015-06-29 CN CN201711275072.7A patent/CN107971020A/zh active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112870A (zh) * | 2013-01-31 | 2013-05-22 | 郑州大学 | 一种聚合物体系中制备ZSM-5/AlPO4-5复合分子筛的方法 |
Non-Patent Citations (2)
| Title |
|---|
| ZSM-5/磷酸铝复合分子筛在甲醇制烯烃反应中的应用;王政等;《石油学报（石油加工）》;20110831;第27卷(第4期);第1.2节 * |
| ZSM-5分子筛催化甲醇制丙烯过程研究;张锋涛;《中国优秀硕士学位论文全文数据库（电子期刊）》;20100915(第9期);第2.2.2节,第3.3节，第3.3.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107930685A (zh) | 2018-04-20 |
| CN107971020A (zh) | 2018-05-01 |
| CN107899610A (zh) | 2018-04-13 |
| CN104888867A (zh) | 2015-09-09 |
| CN107715924A (zh) | 2018-02-23 |
| CN107899620A (zh) | 2018-04-13 |
| CN107971021A (zh) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101384366B (zh) | 一种用于制造分子筛的高生产量的方法 | |
| CN103204516B (zh) | 一种高硅铝比fer沸石分子筛的制备方法 | |
| CN108658093A (zh) | 一种多级孔zsm-5分子筛的制备方法及其应用 | |
| CN104437605B (zh) | 一种w‑zsm‑5分子筛催化剂及其制备方法与应用 | |
| CN105692647A (zh) | 一种ssz-13分子筛的制备方法 | |
| CN105000574B (zh) | 一种特殊形貌的hzsm‑5分子筛及其制备方法与应用 | |
| CN107108242A (zh) | 具有cha晶体结构的沸石的合成，其合成方法及其在催化应用中的用途 | |
| CN105129815B (zh) | 一种结晶态磷酸硅铝材料的制备方法 | |
| CN104923293B (zh) | 邻甲酚异构化催化剂、其制备方法及利用其催化合成间对甲酚的方法 | |
| CN103191776A (zh) | Zsm-5分子筛催化剂的制备方法 | |
| CN103803576B (zh) | 一种低硅铝比zsm-48分子筛及其制备方法 | |
| CN107487777A (zh) | 纳米hzsm‑5分子筛催化剂的合成方法 | |
| CN105983435A (zh) | 一种丁烯异构化催化剂及其制备方法和应用 | |
| CN101618884B (zh) | 一种Magadiite/ZSM-35共晶分子筛的制备方法 | |
| CN102198950B (zh) | 一种高硅铝比NaY分子筛的制备方法 | |
| CN103058208B (zh) | Sapo-56分子筛的制备方法 | |
| CN104386707B (zh) | 一种超低钠高硅纳米zsm-5分子筛的合成方法 | |
| CN104888867B (zh) | 一种制备mto催化剂载体的方法 | |
| CN106145133B (zh) | 一种Hβ型分子筛及其制备方法 | |
| CN102897793B (zh) | 一种zsm-5分子筛的无钠合成方法 | |
| CN105776245B (zh) | 一种zsm‑5分子筛的合成方法及其产品在甲醇合成丙烯中的应用 | |
| CN104229821B (zh) | Beta分子筛合成方法 | |
| CN106467309A (zh) | 一种程序升温合成甲醇制丙烯用纳米zsm-5分子筛的方法 | |
| CN106829997B (zh) | 一种用于催化正丁烯骨架异构化反应的镁碱沸石分子筛催化剂的制备方法 | |
| CN102259890B (zh) | Zsm-5/ecr-1/丝光沸石三相共生材料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191128 Address after: 239500 intersection of Weier road and jingsan Road, economic development zone, Quanjiao County, Chuzhou City, Anhui Province Patentee after: ANHUI KECHANG MACHINERY MANUFACTURING INCORPORATED CO., LTD. Address before: 311821 Zhejiang city of Shaoxing province Zhuji City Hua Zhen Xin Zhai Cun on No. 100 Patentee before: Xuan Le |
|
| TR01 | Transfer of patent right |