CN112237942B - CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, preparation method and application thereof - Google Patents

CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, preparation method and application thereof Download PDF

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CN112237942B
CN112237942B CN201910643244.4A CN201910643244A CN112237942B CN 112237942 B CN112237942 B CN 112237942B CN 201910643244 A CN201910643244 A CN 201910643244A CN 112237942 B CN112237942 B CN 112237942B
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zinc
molecular sieve
catalyst
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silicon molecular
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CN112237942A (en
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乔健
刘松霖
袁志庆
张铁柱
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a high zinc-silicon ratio CHA topological structure zinc-silicon molecular sieve catalyst, a preparation method and application thereof, and mainly solves the problems of low stability, low selectivity of ethylene and propylene in low-carbon olefin, particularly low yield of propylene, of a catalyst for preparing olefin by using methanol in the prior art. The invention discloses a CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, which is characterized by comprising the following components in parts by weight: a) 10-99 parts of a high zinc-silicon ratio CHA topological structure zinc-silicon molecular sieve; b) The technical proposal of 1 to 90 parts of binder solves the problem well and can be used in the industrial production of the methanol-to-olefin.

Description

CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, preparation method and application thereof
Technical Field
The invention relates to a CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, a preparation method and application thereof.
Background
Early zeolite is aluminosilicate and is composed of SiO 4 Tetrahedra and AlO 4 Tetrahedra are basic structural units, and are connected through bridging oxygen to form a microporous compound with a cage-shaped or pore channel structure. Porous materials can be classified according to their pore diameters as defined by the International Union of Pure and Applied Chemistry (IUPAC): the material with the pore diameter smaller than 2nm is a microporous material (micropore materials); the material with the pore diameter between 2 and 50nm is a mesoporous material (mesopore materials); materials with pore diameters greater than 50nm are macroporous materials (macropore materials), and zeolite molecular sieve pore diameters are typically below 2nm and are therefore classified as microporous materials. And due to wide size distribution range of the inner cavity and abundant topological structureThe zeolite molecular sieve material is widely applied to the fields of adsorption, heterogeneous catalysis, carriers of various guest molecules, ion exchange and the like. They are characterized by selective adsorption, and their unique pore system gives them the ability to screen molecules of different sizes, which is also why such materials are called-molecular sieves ".
In the last 40 th century, barrer et al first synthesized artificial zeolite in the laboratory which was not present in nature, and in the last ten years thereafter Milton, breck and Sand et al synthesized type a, type X, type L and type Y zeolite and mordenite, etc. by adding alkali or alkaline earth metal hydroxide to aluminosilicate gel using hydrothermal techniques; in the sixties of the twentieth century, along with the introduction of organic alkali cations, a series of zeolite molecular sieves with brand new structures, such as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22, ZSM-48 and the like) zeolite molecular sieves, have the advantages of good catalytic activity, hydrothermal stability, high corrosion resistance and the like, are widely applied to the fields of petroleum processing, fine chemical industry and the like, and have been a research hot spot for many years.
In 1982, scientists Wilson S.T. and Flanigen E.M. of United states, inc. (UCC, inc.) used aluminum source, phosphorus source and organic template agent to successfully synthesize and develop a novel family of molecular sieves-aluminum phosphate molecular sieves AlPO 4 -n, n represents the model number (US 4310440). After two years, UCC company is in AlPO 4 On the basis of n, si atoms are used for partially replacing Al atoms and P atoms in an AlPO framework, and another series of silicoaluminophosphate molecular sieves SAPO-n, n representing the model (US 4440871, US 4499327) are successfully prepared. In the structure of SAPO-n, si atoms replace P or Al atoms in original AlPO to form SiO 4 、AlO 4 PO (Positive and negative) 4 Tetrahedrally composed, non-neutral molecular sieve frameworks in which silicon is present in two ways: (1) one Si atom replaces one P atom; (2) 2 silicon atoms replace a pair of aluminum atoms and phosphorus atoms respectively, and show certain acidity, oxidability and the like, greatly improve the catalytic activity and have wide application prospect in the petrochemical industry field
The SAPO-34 molecular sieve is taken as an important member in the SAPO-n, has a structure similar to chabazite, and belongs to a cubic crystal system. The SAPO-34 framework element is composed of AlO 2 - 、SiO 2 PO (Positive and negative) 2 + Tetrahedron is composed, skeleton contains ellipsoidal supercage and three-dimensional cross structure of 8-member ring pore canal, the aperture of 8-member ring pore canal is about 0.38nm, the aperture diameter of supercage is kept between 0.43-0.50 nm, topology symbol CHA.
The SAPO-34 molecular sieve has proper protonic acidity, larger specific surface area, better adsorption performance, better thermal stability, better hydrothermal stability, excellent shape selectivity of pore channel structure to low-carbon olefin, and the like, so that the SAPO-34 molecular sieve is used as a catalyst for preparing low-carbon olefin (MTO) from methanol in the reaction, shows good catalytic activity and selectivity, the initial conversion rate can reach 100%, the diene (ethylene and propylene) selectivity can reach more than 80%, and C 5 The above products are present in very small amounts.
The traditional method for preparing the SAPO-34 is a hydrothermal crystallization method, (US 4440871, CN1037334C, CN1038125C, CN 1048428C) and is obtained by crystallizing in a high-temperature hydrothermal system, namely, directly crystallizing an aluminum source, a silicon source, a phosphorus source, a template agent and water at a certain temperature after strongly stirring uniformly according to a certain reaction ratio to form a crystallization mixed solution. The aluminum source is generally selected to be aluminum isopropoxide or pseudo-boehmite, the silicon source is generally acidic silica sol or white carbon black, the phosphorus source is phosphoric acid, the template agent is generally selected from tetraethylammonium hydroxide, triethylamine and morpholine, SAPO-34 crystal grains prepared from the tetraethylammonium hydroxide are generally smaller, and have better catalytic performance, but the template agent has higher cost, and SAPO-34 molecular sieve crystal grains synthesized from the triethylamine and the morpholine which are relatively low in price are larger.
Chinese patent CN1088483 discloses a method for preparing large-grain SAPO-34 molecular sieves using inexpensive organic templates.
Chinese patent CN101525141a discloses a method for preparing small-grain SAPO-34 molecular sieve by using ultrasonic technology, pretreatment is performed on crystallization liquid by ultrasonic wave, and small-grain SAPO-34 molecular sieve is obtained by shorter crystallization time.
Chinese patent CN101293660 provides a method for preparing SAPO-34 molecular sieves by controlling the feeding sequence, but the feeding sequence and the operation process involved in the method are complex.
Chinese patent CN101121529 discloses a method for rapidly synthesizing SAPO-34 molecular sieve by adopting triethylamine or ethylenediamine as an organic template agent and simultaneously adding alkyl quaternary ammonium salt as an organic amine accelerator into synthesized initial gel.
In addition, in 1985, the CHA topology aluminosilicate molecular sieve SSZ-13 was synthesized by the Chemies Zones S.I. of Chevron, inc., and its structure was composed of AlO 4 And SiO 4 Tetrahedra are orderly arranged into an ellipsoidal crystal structure with an eight-membered ring structure through end-to-end connection of oxygen atoms. Because of the large specific surface area and the eight-membered ring structure, SSZ-13 has good thermal stability, and can be used as a carrier of an adsorbent or a catalyst, such as an air purifying agent, an automobile exhaust catalyst and the like. Simultaneously SSZ-13 also has cation exchange property and acidity adjustability, thus having good catalytic performance for various reaction processes, including catalytic cracking, hydrocracking, olefin and arene structural reaction and the like of hydrocarbon compounds.
The molecular sieves are prepared by adopting a hydrothermal synthesis method. Therefore, it can be said that the hydrothermal synthesis method is the most commonly used method for synthesizing molecular sieves, and the main steps of a typical hydrothermal synthesis method are that firstly, a silicon source, an aluminum source, a structure directing agent, alkali, water and the like are reacted and uniformly mixed to obtain an initial sol, namely a crystallization mixture, and then the crystallization mixture is placed in a reaction kettle with polytetrafluoroethylene as a lining and stainless steel as an outer wall, and crystallization reaction is carried out at a certain temperature and under autogenous pressure after sealing, like the process of earth rock formation. The silicon source of the synthetic molecular sieve can be silica sol, silica gel, sodium silicate, white carbon black, organic silicon and the like, the aluminum source can be aluminum sulfate, aluminum nitrate, sodium metaaluminate, alumina sol, organic aluminum, pseudo-boehmite and the like, and the alkali can be organic alkali, ammonia water, naOH, KOH and the like. The alkali is an important factor affecting the synthesis of the molecular sieve, but excessive alkali can dissolve the molecular sieve to reduce the yield of the product, and meanwhile, the introduction of inorganic alkali can add one step to the preparation of the acidic molecular sieve, namely an exchange process of metal cations, which increases the process cost and the wastewater treatment capacity.
With the continuous expansion of the application field of zeolite and the development of scientific research on new properties and new performances, a great deal of effort is put into the synthesis and preparation of new zeolite molecular sieves, wherein the use of heteroatoms (metal elements with heavier atomic weights) to replace framework elements for preparing zeolite molecular sieves with novel framework structures and specific properties becomes one of the effective modes of synthesis and preparation of new zeolite molecular sieves. In 1991, the zinc-silicon molecular sieve VPI-7 is prepared, annen synthesizes a first high-silicon zinc-silicon molecular sieve VPI-8 with good thermal stability, has a twelve-membered ring pore channel system, and has application potential in petroleum macromolecule cracking industry. The synthesis of VPI-8 in Camblor requires the addition of expensive organic templates (such as TEAOH, etc.), which has great limitation on further practical application, the synthesis and development of zinc-silicon molecular sieves have been carried out in the period of the river until 2014 Tatsuya Okubo et al prepared VET-type zinc-silicon molecular sieves in a seed-guided manner, so that the zinc-silicon molecular sieves are returned to the field of scientific researchers, mark E.Davis et al prepared Ni-CIT-6 and Ni-Zn-MCM-41, both of which show better propylene oligomerization performance, and 2017 Tatsuya Okubo et al reported CHA-type zinc-silicon molecular sieves with lower zinc-silicon ratios prepared under complex systems and severe conditions.
At present, a small amount of reports on a high zinc-silicon ratio CHA topological structure zinc-silicon molecular sieve exist, the preparation process is complex, and the zinc-silicon ratio is low.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, a catalyst for preparing hydrocarbon by using methanol has low stability, ethylene and propylene in low-carbon olefin, particularly propylene has low selectivity and low yield, and provides a CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio.
The second technical problem to be solved by the invention is to provide a novel preparation method of the high-zinc-silicon-ratio CHA topological structure zinc-silicon molecular sieve catalyst.
The invention provides the application of the CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio in the production of low-carbon olefin by methanol preparation.
In order to solve one of the technical problems, the invention adopts the following technical scheme: the CHA topological structure zinc-silicon molecular sieve catalyst comprises the following components in parts by weight:
a) 10-99 parts of CHA topological structure zinc-silicon molecular sieve; the molar ratio of zinc to silicon of the CHA topological structure zinc to silicon molecular sieve is 0.1-2, preferably 0.2-2; such as 0.24, 0.42, 1.23.
b) 1-90 parts of binder.
In the technical scheme, preferably, the CHA topological structure zinc-silicon molecular sieve in the catalyst is 20-90 parts by weight; the binder is at least one of alumina, silica or magnesia, and the weight part of the binder is 10-80; the catalyst comprises at least one selected from the group consisting of IIIA and IIIB elements of the periodic table or oxides thereof, and the content of the IIIA and IIIB elements is 0.1-5 parts by weight of the catalyst.
In the technical scheme, preferably, the CHA topological structure zinc-silicon molecular sieve in the catalyst is 30-80 parts by weight; the weight portion of the binder is 20 to 70 portions; the element selected from III A group of periodic table is gallium, indium or oxide thereof, and the content thereof is 0.5-4 parts by weight of the catalyst; the element selected from group IIIB of the periodic table is lanthanum, cerium or oxide thereof, and the content of the element is 0.5-4 parts by weight of the catalyst.
In the technical scheme, more preferably, the CHA topological structure zinc-silicon molecular sieve in the catalyst is 40-70 parts by weight; the weight portion of the binder is 30-60 portions; the element selected from III A group of periodic table is indium or oxide thereof, and the content of the element is 1.5 to 3.5 parts by weight of the catalyst; the element selected from III B group of periodic table is cerium or its oxide, and its content is 1.5-3 parts by weight of catalyst.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: a preparation method of a CHA topological structure zinc-silicon molecular sieve catalyst comprises the following steps:
1) Synthesizing a CHA topological structure zinc-silicon molecular sieve;
2) Performing ammonium exchange and roasting on the CHA type topological structure zinc-silicon molecular sieve to obtain a hydrogen type CHA type topological structure zinc-silicon molecular sieve, and performing active element modification on the hydrogen type CHA type topological structure zinc-silicon molecular sieve by adopting a dipping or loading method; wherein the active element is selected from gallium, indium or oxides thereof; the element selected from IIIB group of periodic table is lanthanum, cerium or oxide thereof;
3) Weighing the modified molecular sieve obtained in the step 2), uniformly mixing the modified molecular sieve with a binder and a pore-forming agent, then kneading and extruding the mixture with water and a dilute nitric acid solution to form a column-shaped sample, and drying the column-shaped sample at 80-120 ℃ and roasting the column-shaped sample at 500-650 ℃ to obtain a catalyst sample; wherein the pore-forming agent is at least one selected from sesbania powder, carboxymethyl cellulose or starch.
The synthesis method of the CHA type topological structure zinc-silicon molecular sieve comprises the following steps:
(1) According to nZnO/nSiO 2 N template T/nH 2 O=1:0.1-10:1-200:10-1000, wherein n represents the mole number, firstly, dissolving a zinc source and a template agent T in deionized water, and fully and uniformly stirring to obtain a solution A;
(2) Placing the solution A at 30-60 ℃, adding CHA topological structure type all-silicon molecular sieve seed crystals accounting for 0.5-10% of the total dry basis material mass of the reaction (accounting for 0.25-5% of the total dry basis material mass of the reaction) and the rest template agent under stirring, and hermetically stirring until the materials are uniformly mixed to obtain a solution B;
(3) Adding a silicon source and an additive (accounting for 0.25-5% of the total dry material mass of the reaction) into the solution B, hermetically stirring at 60-100 ℃ until a uniform crystallization mixed solution is formed, placing the crystallization mixed solution at 140-220 ℃ for crystallization for 1-7 days, and obtaining the CHA topological structure zinc-silicon molecular sieve product after filtering, washing, drying and roasting.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a process for preparing olefin by conversion of methanol features that methanol is used as raw material, the reaction temp. is 400-600 deg.C, reaction pressure is 0.1-10 MPa and weight space velocity of methanol is 0.1-20 hr -1 Under the conditions that the raw material passes through the catalyst bed layer and contacts any one of the catalysts to generate olefin.
In the technical proposal, the reaction temperature is preferably 450-550 ℃, the reaction pressure is preferably 0.5-5 Mpa, and the weight airspeed is preferably 2-10 h -1 。
The modified CHA topological structure zinc-silicon molecular sieve provided by the invention can be prepared by adopting physical and chemical methods such as dipping, chemical adsorption, chemical deposition, ion exchange and the like, and the preferable scheme is that an aqueous solution containing active components is subjected to isovolumetric dipping, wherein the active components are gallium, indium, lanthanum and cerium, sesbania powder and dilute nitric acid are added after stirring for a period of time, and the finished product is prepared by kneading and extruding. Drying at 80-120 deg.c and roasting in air atmosphere to obtain catalyst at 500-650 deg.c for 4-10 hr.
The CHA topological structure zinc-silicon molecular sieve provided by the invention has the pore canal structural characteristics of the CHA molecular sieve and the unique acidic characteristics caused by Zn heavy atoms, and the CHA molecular sieve show good synergistic effect, and the supported gallium and indium elements have good dehydrogenation performance for hydrocarbons, can effectively form an internal and external synergistic mechanism with a molecular sieve framework to enhance the reaction performance, and can effectively improve the carbon deposition resistance of the molecular sieve and inhibit the dealumination behavior of the molecular sieve under hydrothermal conditions, so that the selectivity and yield of ethylene and propylene are improved by means of increasing the synergistic effect, dehydrogenation effect, carbon deposition resistance and the like of the catalyst.
In a fixed bed reactor, the reaction temperature is 400-600 ℃, the reaction pressure is 0.1-10 Mpa, and the weight airspeed of the methanol is 0.1-20h -1 The method comprises the steps of carrying out a first treatment on the surface of the The preferable scheme is that the reaction temperature is 450-550 ℃, the reaction pressure is 0.5-5 Mpa, and the weight airspeed is 2-10 h -1 Under the condition of using the CHA topological structure zinc-silicon molecular sieve catalyst with high zinc-silicon ratio, using methanol as raw material, the raw material conversion rate is 100%, the yield of product diene (ethylene and propylene) can reach 89.6%, wherein the yield of propylene can reach 60.7%, and meanwhile, the catalyst has good stability, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Drawings
Figure 1 is an XRD pattern of the product of example 3.
FIG. 2 is an SEM photograph of the product of example 3.
FIG. 3 is a graph of the absorption edge EXAFS of zinc and potassium elements of the product of example 3, zinc silicate and zinc oxide.
Detailed Description
[ example 1 ]
312.36g of zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O,1.04 mol) was added to 8353.66g of distilled water, 2219.81g of amantadine (TMAGAOH, 40wt%,14.70 mol) was then added and stirred uniformly, then the uniformly mixed solution was transferred to a 30 ℃ oil bath environment, seed crystals of all silicon CHA type, which would be 0.25% of the total weight of the reactant dry basis, and 982.43g of amantadine (TMAGAOH, 40wt%,6.50 mol) were added under stirring, after sealed stirring for 5 hours, 1202.76g of silica sol (40 wt%,8.02 mol) and lithium hydroxide (LiOH), which would be 5% of the total weight of the reactant dry basis, were put into the reaction solution and the oil bath was warmed to 60 ℃ and stirred continuously, the molar ratio of the crystallization mixture was controlled as follows: nZnO/nSiO 2 N template T/nH 2 O=1:7.71:20.38: 587.42 after completely and uniformly mixing, placing the crystallized mixture into a polytetrafluoroethylene-lined pressure-resistant container, crystallizing for 3d at 140 ℃, filtering and washing the product, drying the product at 100 ℃, heating to 500 ℃ and roasting at constant temperature to obtain a Zn-high Zn-Si ratio CHA topological structure Zn-Si molecular sieve product ZnC-1, wherein the final Zn-Si molar ratio of the product is 0.18 measured by a plasma Perkin-Elmer 3300DV ICP analyzer.
[ example 2 ]
20.13g of zinc acetate (Zn (OAc)) was weighed out 2 ·2H 2 O,0.09 mol) was added to 333.35g of distilled water, then 12.98g of triethylenediamine (DABCO, > 98wt%,0.12 mol) and 110.42g of triethylamine (TEA, 1.09 mol) were added, stirred uniformly, then the uniformly mixed solution was transferred to an oil bath atmosphere at 60℃and under stirring, all-silica CHA type seed crystals 5% by weight based on the total weight of the dry reaction mass and 27.02 g of triethylenediamine (DABCO, > 98wt%,0.24 mol) and 89.58g of triethylamine (TEA, 0.88 mol) were added, and after sealed stirring for 2.5 hours, 3.62g of white carbon black (SiO 2 99% by weight, 0.06 mol) of magnesium hydroxide (Mg (OH) in an amount of 0.25% by weight based on the total weight of the dry reactant 2 ) Adding the mixture into the reaction liquid, heating the oil bath to 100 ℃, continuously stirring, and controlling the mole ratio of the crystallization mixed liquid to be: nZnO/nSiO 2 N template T/nH 2 O=1:0.67:25.89: 205.78, after being completely and uniformly mixed, placing the crystallization mixture into a pressure-resistant container with polytetrafluoroethylene lining, crystallizing for 0.5d at 220 ℃, filtering and washing the product, drying the product at 80 ℃, heating the product to 550 ℃ and roasting the product at constant temperature to obtain a Zn-high Zn-Si ratio and high Zn-Si ratio CHA topological structure Zn-Si molecular sieve product ZnC-2, wherein the final Zn-Si molar atomic ratio of the product is 1.23 measured by a plasma Perkin-Elmer 3300DV ICP analyzer.
[ example 3 ]
1039.99g of zinc sulfate (ZnSO) was weighed out 4 ·6H 2 O,36.17 mol) into 5335.66g of distilled water, then 1259.84g of amantadine (TMADaOH, 98wt%,8.32 mol) and 3254.12g of di-n-propylamine (DPA, 32.16 mol) were added, the uniformly mixed solution was then transferred to an oil bath atmosphere at 50℃and, under stirring, 2.9% of all-silicon CHA seed crystals and 712.43g of TMADaOH (98 wt%,4.71 mol) and 5654.52g of di-n-propylamine (DPA, 55.88 mol) were added, and after stirring in a closed state for 5 hours, 21126.22g of silica sol (40 wt%,140.84 mol) and 4.9% of lithium hydroxide (LiOH) and magnesium hydroxide (Mg (OH) were added 2 ) Adding into the reaction solution, heating the oil bath to 80 ℃ and continuously stirring, and controlling the mol of the crystallization mixed solutionThe molar ratio is as follows: nZnO/nSiO 2 N template T/nH 2 O=1:3.89:2.79:27.66, after being completely and uniformly mixed, the crystallization mixture is placed in a pressure-resistant container with polytetrafluoroethylene lining and crystallized for 2.5d at 160 ℃, the product is dried at 90 ℃ after being filtered and washed, and then the product is heated to 600 ℃ for constant-temperature roasting, so that the Zn-high Zn-Si ratio and CHA topological structure Zn-Si molecular sieve product ZnC-3 is obtained, and the final Zn-Si mole atomic ratio of the product is measured to be 0.24 by a product plasma Perkin-Elmer 3300DV ICP analyzer. The obtained sample is compared with zinc phosphate and zinc oxide after being characterized by EXAFS, and zinc element in the ZnC-3 sample is found to be completely in the framework structure of the molecular sieve (see figure 3 in the specification).
[ example 4 ]
66.66g of zinc oxide (ZnO, 0.82 mol) was weighed and added to 888.65g of distilled water, 1122.63g of tetraethylammonium hydroxide (TEAOH, 25wt%,1.91 mol) and 204.78g of diethylenetriamine (DETA, 1.98 mol) were then stirred well, the well-mixed solution was then transferred to an oil bath environment at 45 ℃, 4.5% of all-silicon CHA seed crystals and 888.83g of tetraethylammonium hydroxide (TEAOH, 25wt%,1.09 mol) and 156.22g of diethylenetriamine (DETA, 1.51 mol) were added while stirring, after stirring for 3.9 hours in a closed condition, 126.23g of white carbon black (99 wt%,2.01 mol) and 1.5% of lithium hydroxide (LiOH) were put into the reaction solution and the oil bath was heated to 75 ℃ for continuous stirring, and the molar ratio of the crystallization mixture was controlled to: nZnO/nSiO 2 N template T/nH 2 O=1:2.45:5.83: 196.76, after being completely and uniformly mixed, the crystallization mixture is placed in a pressure-resistant container with polytetrafluoroethylene lining and crystallized for 1.5d at 190 ℃, the product is dried at 90 ℃ after being filtered and washed, and then the product is heated to 580 ℃ for constant-temperature roasting, so that the Zn-high Zn-Si ratio and high Zn-Si ratio CHA topological structure Zn-Si molecular sieve product ZnC-4 is obtained, and the final Zn-Si molar atomic ratio of the product is 0.42 measured by a plasma Perkin-Elmer 3300DV ICP analyzer.
Examples 5 to 20
According to the method of example 3, the raw materials are shown in table 1, different proportions of the reaction materials are controlled (table 2), and the Zn-high Zn-Si ratio CHA topological structure Zn-Si molecular sieve is respectively synthesized, wherein the silicon-aluminum ratio of the seed crystal, the content of the seed crystal and the additive, and the silicon-aluminum atom ratio of the product are shown in table 3.
TABLE 1
TABLE 2
Examples Reactant proportioning composition
5 nZnO/nSiO 2 N template T/nH 2 O＝1∶0.1∶15∶999
6 nZnO/nSiO 2 N template T/nH 2 O＝1∶4.2∶44∶449
7 nZnO/nSiO 2 N template T/nH 2 O＝1∶8.8∶59∶99
8 nZnO/nSiO 2 N template T/nH 2 O＝1∶10∶5∶37
9 nZnO/nSiO 2 N template T/nH 2 O＝1∶0.9∶26∶85
10 nZnO/nSiO 2 N template T/nH 2 O＝1∶5∶74∶230
11 nZnO/nSiO 2 N template T/nH 2 O＝1∶7∶199∶856
12 nZnO/nSiO 2 N template T/nH 2 O＝1∶9.5∶104∶333
13 nZnO/nSiO 2 N template T/nH 2 O＝1∶0.5∶11∶65
14 nZnO/nSiO 2 N template T/nH 2 O＝1∶1.1∶104∶430
15 nZnO/nSiO 2 N template T/nH 2 O＝1∶2.5∶94∶703
16 nZnO/nSiO 2 N template T/nH 2 O＝1∶6∶49∶219
17 nZnO/nSiO 2 N template T/nH 2 O＝1∶0.3∶72∶223
18 nZnO/nSiO 2 N template T/nH 2 O＝1∶0.7∶141∶120
19 nZnO/nSiO 2 N template T/nH 2 O＝1∶3.8∶134∶667
20 nZnO/nSiO 2 N template T/nH 2 O＝1∶1.5∶185∶556
[ example 21 ]
Preparation and modification of catalysts
The preparation method of the catalyst comprises the following steps:
(1) Modification treatment of CHA topological structure zinc-silicon molecular sieve with high zinc-silicon ratio
20 g of ZnC-1 molecular sieve, 2.5mL of gallium nitrate solution with the concentration of 0.39mol/L, 10.2mL of indium nitrate solution with the concentration of 0.12mol/L and 10.2mL of lanthanum nitrate solution with the concentration of 0.12mol/L are taken, then stirred and evaporated to dryness at the temperature of 100 ℃, and after drying and roasting, the gallium-indium-lanthanum modified high-zinc-silicon-ratio CHA topological structure zinc-silicon molecular sieve raw powder is prepared.
(2) Preparation of the catalyst
9.95g of modified molecular sieve prepared in the step (1) and gamma-Al are taken 2 O 3 Mixing 4.26g and 1.45g sesbania powder, adding 23.66mL of 1.5wt% dilute nitric acid, kneading, extruding, forming, drying at 100deg.C for 12 hr, roasting at 550deg.C for 6.0 hr, crushing, sieving to obtain 20-40 mesh particle size, placing into fixed bed reactor, reacting at 470 deg.C under 2.5MPa with weight airspeed of 4.9 hr -1 The results of the evaluation under the conditions of (2) are shown in Table 4.
TABLE 3 Table 3
Examples 22 to 40
The catalyst composition and evaluation results of the modified and evaluated composite molecular sieves prepared in different examples are shown in Table 4.
[ example 41 ]
The ZnC-16 molecular sieve was evaluated under the conditions of example 32 without selecting any element for loading, and the evaluation results are shown in Table 4.
[ example 42 ]
The ZnC-16 molecular sieve was carried with only indium element according to the modification method of example 32, and evaluated under the conditions of example 22, and the evaluation results are shown in Table 4.
Example 43
The ZnC-16 molecular sieve was used as a catalyst, and only cerium was carried in the modification method of example 32, and evaluated under the conditions of example 22, and the evaluation results are shown in Table 4.
[ comparative example 1 ]
The VPI-7 molecular sieve was modified and evaluated as in example 23 to produce a catalyst, the evaluation results of which are shown in Table 4.
VPI-7：
At room temperature, according to n (Na 2 O)：n(SiO 2 )：n(ZnO)：n(H 2 O) =0.55: 1:0.28:40 sequentially taking stoichiometric NaOH, H 2 O、SiO 2 、Zn(NO 3 ) 2 4H 2 Adding O into a stainless steel self-pressure reaction kettle with a polytetrafluoroethylene lining, uniformly stirring, sealing, and placing in a baking oven at 200 ℃ for crystallization for 7d to obtain VPI-7.
[ comparative example 2 ]
The VPI-8 molecular sieve was modified and evaluated as in example 23 to produce a catalyst, the evaluation results of which are shown in Table 4.
VPI-8:
At room temperature, according to n (ZnO): n (SiO) 2 )：n(Li 2 O)：n(TEABr)：n(H 2 O) =0.1: 1:0.3:0.4:30 sequentially taking stoichiometric H 2 O、Zn(NO 3 ) 2 4H 2 O、TEABr、SiO 2 And LiOH, adding into a stainless steel self-pressure reaction kettle with a polytetrafluoroethylene lining, uniformly stirring, sealing, and placing into a 180 ℃ oven for crystallization for 8d to obtain VPI-8.
[ comparative example 3 ]
Zinc-silicon CHA molecular sieves (Zinc-silicon ratio=0.02) were prepared according to the method in literature (chem. Eur. J.2018,24, 808-812), according to which the synthesis ratio SiO is given 2 :x ZnO:0.42TMAdaOH:0.08LiOH:30H 2 O, x=0.02-0.06, according to the maximum zinc-silicon ratio SiO 2 0.06ZnO is added and reacts for 7d at 150 ℃ to obtain a comparative sample, and the actual test of ICP is SiO 2 0.03ZnO. Catalysts were modified and evaluated in the same manner as in example 23, and the evaluation results thereof are shown in Table 4.
[ comparative example 4 ]
The zinc oxide powder was mechanically blended with all-silica SSZ-13 molecular sieves in accordance with the zinc-silica ratio of example 20, and evaluated in accordance with the modification and manner of example 23 to produce a catalyst, the evaluation results of which are shown in Table 4.
[ comparative example 5 ]
The zinc oxide powder was mechanically blended with all-silica SSZ-13 molecular sieves in the zinc-silica ratio of example 11 and evaluated in the manner of modification and evaluation of example 26 to produce a catalyst, the evaluation results of which are shown in Table 4.
[ comparative example 6 ]
The zinc oxide powder was mechanically mixed with all-silica SSZ-13 molecular sieve in accordance with the zinc-silica ratio of example 10, and evaluated in accordance with the modification and manner of example 30 to produce a catalyst, the evaluation results of which are shown in Table 4.
TABLE 4 Table 4
[ example 44 ]
The catalyst obtained in example 21 was taken at a reaction temperature of 400℃under a reaction pressure of 2.0MPa and a weight space velocity of 1.5h -1 Under the conditions of (2) and the results are shown in Table 5
Examples 45 to 54
The catalyst obtained in example 21 was evaluated under different conditions of reaction temperature, reaction pressure and weight space velocity, and the reaction conditions and the evaluation results thereof are shown in Table 5.
TABLE 5
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Claims (13)

1. The CHA topological structure zinc-silicon molecular sieve catalyst comprises the following components in parts by weight:
a) 20-99 parts of CHA topological structure zinc-silicon molecular sieve; the molar ratio of zinc to silicon of the CHA topological structure zinc to silicon molecular sieve is 0.24-2;
b) 1-80 parts of binder;
the catalyst comprises at least one of elements of IIIA group or oxides thereof and at least one of elements of IIIB group or oxides thereof, and the content of the elements of IIIA and IIIB group is 0.1-5 parts by weight of the catalyst;
wherein the catalyst is selected from gallium, indium or oxides thereof; the element selected from group IIIB of the periodic Table is lanthanum, cerium or an oxide thereof.
2. The CHA-type topologically structured zinc-silicon molecular sieve catalyst of claim 1, wherein the CHA-type topologically structured zinc-silicon molecular sieve is 20-90 parts by weight.
3. The CHA-type topologically structured zinc-silicon molecular sieve catalyst of claim 1, wherein the CHA-type topologically structured zinc-silicon molecular sieve is 30-80 parts by weight.
4. The CHA-type topologically structured zinc-silicon molecular sieve catalyst of claim 1, wherein the CHA-type topologically structured zinc-silicon molecular sieve is 40-70 parts by weight.
5. The CHA topology zinc-silicon molecular sieve catalyst of claim 1, wherein the binder is 20-70 parts by weight.
6. The CHA topology zinc-silicon molecular sieve catalyst of claim 1, wherein the binder is present in an amount of 30 to 60 parts by weight.
7. The CHA topology zinc silicalite catalyst of claim 1, wherein said binder is selected from at least one of alumina, silica and magnesia.
8. The CHA topological zinc-silicon molecular sieve catalyst of claim 1, wherein the catalyst is selected from the group consisting of gallium, indium, and oxides thereof, and comprises 0.5-4 parts by weight of the catalyst; the element selected from group IIIB of the periodic table is lanthanum, cerium or oxide thereof, and the content of the element is 0.5-4 parts by weight of the catalyst.
9. The CHA topology zinc-silicon molecular sieve catalyst of claim 8, wherein the catalyst is selected from the group consisting of indium or its oxide as group iiia of the periodic table of elements, and comprises 1.5 to 3.5 parts by weight of the catalyst; the element selected from III B group of periodic table is cerium or its oxide, and its content is 1.5-3 parts by weight of catalyst.
10. The method for preparing CHA-type topological zinc-silicon molecular sieve catalyst of claim 1, comprising the steps of:
1) Synthesizing a CHA topological structure zinc-silicon molecular sieve;
2) Performing ammonium exchange and roasting on the CHA type topological structure zinc-silicon molecular sieve to obtain a hydrogen type CHA type topological structure zinc-silicon molecular sieve, and performing active element modification on the hydrogen type CHA type topological structure zinc-silicon molecular sieve by adopting a dipping or loading method; wherein the active element is selected from gallium, indium or oxides thereof; the element selected from IIIB group of periodic table is lanthanum, cerium or oxide thereof;
3) Weighing the modified molecular sieve obtained in the step 2), uniformly mixing the modified molecular sieve with a binder and a pore-forming agent, then kneading and extruding the mixture with water and a dilute nitric acid solution to form a column-shaped sample, and drying the column-shaped sample at 80-120 ℃ and roasting the column-shaped sample at 500-650 ℃ to obtain a catalyst sample; wherein the pore-forming agent is at least one selected from sesbania powder, carboxymethyl cellulose or starch.
11. A process for preparing hydrocarbon by conversion of methanol features that methanol is used as raw material, the reaction temp is 400-600 deg.C, reaction pressure is 0.1-10 MPa and weight space velocity of methanol is 0.1-20 hr -1 Under the conditions that the raw material passes through the catalyst bed layer and contacts with any one of the catalysts in claims 1-9 to generate hydrocarbons.
12. The method for producing hydrocarbon by converting methanol according to claim 11, wherein the reaction temperature is 450-550 ℃, the reaction pressure is 0.5-5 mpa, and the weight space velocity is 2-10 h -1 。
13. The CHA-topology zinc silicalite catalyst of any one of claims 1-9 for use in a reaction of methanol to lower olefins.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683079A (en) * 2004-04-16 2005-10-19 中国石油化工股份有限公司 Catalyst for reaction to produce olefine with methanol
CN108014846A (en) * 2016-11-04 2018-05-11 中国石油化工股份有限公司 Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst, preparation method and applications
JP2019089666A (en) * 2017-11-13 2019-06-13 国立大学法人 東京大学 Method for producing zeolite, chabazite-type zeolite, and ion exchanger comprising the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683079A (en) * 2004-04-16 2005-10-19 中国石油化工股份有限公司 Catalyst for reaction to produce olefine with methanol
CN108014846A (en) * 2016-11-04 2018-05-11 中国石油化工股份有限公司 Cu-SSZ-13/SAPO-11 composite molecular sieves catalyst, preparation method and applications
JP2019089666A (en) * 2017-11-13 2019-06-13 国立大学法人 東京大学 Method for producing zeolite, chabazite-type zeolite, and ion exchanger comprising the same

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