CN114605213B - Method for producing propylene from synthesis gas and dimethyl ether - Google Patents
Method for producing propylene from synthesis gas and dimethyl ether Download PDFInfo
- Publication number
- CN114605213B CN114605213B CN202011446855.9A CN202011446855A CN114605213B CN 114605213 B CN114605213 B CN 114605213B CN 202011446855 A CN202011446855 A CN 202011446855A CN 114605213 B CN114605213 B CN 114605213B
- Authority
- CN
- China
- Prior art keywords
- hours
- catalyst
- molecular sieve
- binder
- roasting
- 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
Classifications
-
- 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
- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application discloses a method for producing propylene by using synthesis gas and dimethyl ether, which takes the synthesis gas and the dimethyl ether as raw materials; the raw material gas is preheated and then continuously passes through a reactor provided with a catalyst bed layer, the reaction temperature of the reactor is 400-600 ℃, and the weight space velocity of dimethyl ether is 0.3-10h ‑1 And synthesis gas: dimethyl ether = 0.5; the catalyst consists of a molecular sieve and a binder, and is prepared by metal oxide modification, silanization treatment and water vapor treatment. The selectivity of propylene is up to 72%, the catalyst stability is good, and the catalyst has good industrial application prospect.
Description
Technical Field
The invention relates to a method for producing propylene by synthesis gas and dimethyl ether, belonging to the field of chemistry and chemical engineering.
Background
Propylene is one of the basic raw materials of three major synthetic materials, and the largest amount is used for producing polypropylene. In addition. The propylene can be used for preparing acrylonitrile, propylene oxide, isopropanol, acrylic acid and esters thereof, epichlorohydrin and the like.
Chinese coal resources are relatively rich, and the rapid development of the technology for preparing chemicals by taking coal as a raw material has extremely important strategic significance for meeting the energy safety of China and the long-term development of economic society. In recent years, the technology of preparing olefin from coal raw material by methanol changes the pattern of obtaining olefin by the traditional process, and gradually becomes a vital force in the olefin market in China.
The worldwide propylene production in 2019 is 1.4 million tons, wherein the demand of China accounts for 30 percent of the world. The ethylene cracking by-product remains the main source of propylene; secondly, a byproduct propylene of an FCC device in an oil refinery; propane dehydrogenation and methanol to propylene are increasing year by year. Scientists have conducted a great deal of research around the preparation of propylene from methanol, and have employed multiple catalyst beds to obtain higher yields of propylene. The research work with industrial application prospect focuses on modification by taking SAPO-34 and ZSM-5 molecular sieves as matrixes. The defects of the process for preparing the propylene by taking the methanol or the dimethyl ether as the raw material are mainly short service life of the catalyst and low once-through yield of the propylene. Frequent regenerators of the catalyst and large material circulation lead to poor economics.
The process route for producing propylene by taking the synthesis gas and the dimethyl ether as raw materials overcomes the defects of the traditional process route for preparing propylene by using methanol, the dimethyl ether efficiently generates propylene on the catalyst with moderate acid strength under the atmosphere of the synthesis gas, the service life of the catalyst is greatly prolonged, the once-through yield of the propylene is up to 70 percent, the alkane amount in the product is small, and the process route has good industrial application prospect.
Disclosure of Invention
The invention aims to provide a method for preparing propylene from synthesis gas and dimethyl ether, which takes the synthesis gas and the dimethyl ether as raw materials to produce the propylene with high selectivity, has good catalyst stability, is easy to realize large-scale device and has good industrial application prospect.
The technical problems solved are that the traditional production technology for preparing propylene from methanol has the defects of short service life of the catalyst, frequent regeneration of the catalyst, low space-time yield of propylene and the like. The invention provides a method for producing propylene by synthesis gas dimethyl ether, which takes synthesis gas and dimethyl ether as raw materials to produce propylene on a catalyst containing a molecular sieve with high selectivity, and has simple process flow and good economical efficiency.
The invention provides a method for producing propylene by synthesis gas and dimethyl ether, which at least comprises the following steps:
i) Preheating raw material gas containing synthesis gas and dimethyl ether, and continuously passing through a reactor provided with a catalyst bed layer to obtain a product mixture; producing propylene;
ii) separating the product mixture to obtain products of propylene, ethylene and C4-C7 hydrocarbon compounds;
iii) Taking the ethylene and the C4-C7 hydrocarbon compound as circulating gas, returning to the step i), mixing with raw material gas, preheating, and then entering a reactor;
the catalyst is obtained by molding a mixture containing a molecular sieve and a modified binder and then carrying out post-treatment;
the modified binder is a binder modified by a metal oxide.
Optionally, the post-treatment is selected from at least one of metal oxide modification, silanization agent modification, water vapor treatment.
Alternatively, the reaction conditions are:
the reaction temperature is 400-600 ℃;
the reaction pressure is 0.3-7.0 MPa;
the molar ratio of synthesis gas to dimethyl ether is 0.5:1 to 10:1;
the weight space velocity of the dimethyl ether fed is 0.3 to 10h -1 ；
The molar ratio of carbon monoxide to hydrogen in the synthesis gas is 10;
the reaction conditions are preferably:
the reaction temperature is 450-550 ℃;
the weight space velocity of dimethyl ether feeding is 1-10 h -1 。
Preferably, the molecular sieve is selected from at least one of ZSM-5, MCM-22 and MCM-49 molecular sieves;
the molar ratio of silicon to aluminum of the molecular sieve is 20-500.
Optionally, the molecular sieve is a hydrogen type or ammonium type molecular sieve; the mass percentage of the molecular sieve in the catalyst is 30-85%.
Preferably, the modified binder is obtained by impregnating a binder with a solution containing a metal element and then roasting; the binder is selected from at least one of boehmite, alumina, diatomite, silica or kaolin; the metal element is at least one of chromium, nickel, calcium, zinc and magnesium.
Preferably, the metal oxide in the post-treatment is modified to: putting a solid sample into a solution containing metal elements for soaking and then roasting; the metal element is at least one of calcium, zirconium, zinc, magnesium, nickel, zirconium and chromium.
Optionally, the solid sample is a sample obtained after forming a mixture containing the molecular sieve and the modified binder; or a sample obtained by molding a mixture containing the molecular sieve and the modified binder and carrying out metal oxide modification and silanization modification on the sample.
The method and the number of the modification of the metal oxide, and the content of the metal oxide generated by the modification of the metal oxide in the finally obtained catalyst can be selected by those skilled in the art according to actual conditions. Preferably, in the catalyst, the mass percentage of the metal oxide modification element is 1 to 15 percent based on the mass of the oxide of the metal oxide modification element. Further preferably, in the catalyst, the mass percentage of the oxide of the metal oxide modifying element is 1 to 10% based on the mass of the oxide of the metal oxide modifying element.
Preferably, the silanization reagent is selected from at least one of ethyl orthosilicate, benzyl silicone oil and dimethyl silicone oil.
Preferably, the water vapor treatment is 100 percent water vapor, the treatment temperature is 300-800 ℃, the treatment time is 0.5-10 hours, and the pressure is 1.0-3.0 MPa.
As a specific embodiment, the catalyst preparation process comprises the following steps:
(a1) Carrying out metal oxidation modification on the binder, soaking the binder in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a modified binder;
(b1) Mixing the modified binder obtained in the step (1) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve for molding, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid X1;
(c1) Soaking the solid X1 obtained in the step (b 1) in a cyclohexane and/or n-hexane solution of a silylation reagent for 2 to 24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silylation reagent in the solution is 20 to 50 percent; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, repeating for 0-3 times to obtain a silanization reagent modifier X2;
(d1) And (4) treating the silanization reagent modifier X2 obtained in the step (3) by using water vapor, drying, and roasting at 500-800 ℃ for 2-10 hours to obtain the catalyst.
As a specific embodiment, the catalyst preparation process comprises the following steps:
(a2) Carrying out metal oxide modification on the binder, soaking the binder in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a modified binder;
(b2) Mixing the modified binder obtained in the step (a 2) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve for molding, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Y1;
(c2) Soaking the solid Y1 obtained in the step (b 2) in a cyclohexane and/or n-hexane solution of a silylation reagent for 2 to 24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silylation reagent in the solution is 20 to 50 percent; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, repeating for 0-3 times to obtain the catalyst;
as a specific embodiment, the catalyst preparation process comprises the following steps:
(a3) Carrying out metal oxide modification on the binder, soaking the binder in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a modified binder;
(b3) Mixing the modified binder obtained in the step (a 3) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve for molding, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Z1;
(c3) Soaking the solid Z1 obtained in the step (b 3) in a cyclohexane and/or n-hexane solution of a silylation reagent for 2 to 24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silylation reagent in the solution is 20 to 50 percent; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, repeating for 0-3 times to obtain a silylation reagent modifier Z2;
(d3) Dipping the silanization reagent modifier Z2 obtained in the step (c 3) in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a solid Z3;
(e3) And (d) treating the silanization reagent modifier Z3 obtained in the step (d 3) by adopting water vapor, drying, and roasting at 500-800 ℃ for 2-10 hours to obtain the catalyst.
The method for producing propylene by using synthesis gas and dimethyl ether is characterized in that the preparation process of the catalyst comprises the following steps:
the catalyst can be used as a fluidized bed catalyst or a fixed bed catalyst according to different forming modes. And after spray forming, the fluidized bed catalyst can be prepared through the preparation steps. Extruding into a matrix, and preparing the fixed bed catalyst by the steps.
It should be further noted that in the preparation process, the characteristics of the catalyst structure and the number of the acid sites are considered, the modification step and the percentage of the modifier in the catalyst are optimized and controlled, and the modified silica, diatomite, alumina and kaolin are used for modulation of the catalyst acidity selectivity after calcination. The carrier or molecular sieve has dehydrogenation activity after being modified by oxide, and the acidic position of the catalyst is adjusted and the pore channel of the catalyst is changed by steam treatment, so that the hydrothermal stability of the catalyst is enhanced, and the synergistic effect of the modification processes is that the catalyst has a double-function catalyst with good acid catalysis and dehydrogenation functions, and can completely meet the industrial use requirements.
The preparation process of the catalyst is mixing and forming of the molecular sieve and the adhesive, and the forming mode can be spray drying or extrusion molding. The molecular sieve may be a hydrogen or ammonia form of ZSM-5, MCM-22 and MCM-49 molecular sieves. The weight content of the modified oxide is 1-15%. The temperature of the water vapor treatment is preferably 350 to 800 ℃, and the 100 percent water vapor treatment is carried out for 0.5 to 10 hours. The reagent adopted by silanization is benzyl silicone oil or dimethyl silicone oil, and the solvent adopts n-hexane and cyclohexane. The prepared solution of the organic silicon compound needs to be fully shaken, shaken up and kept stand overnight. Each step of the silanization has an effect on the silanization. The silanization treatment selectively modulates the acid sites on the outer surface to improve the para-position selectivity.
The method is characterized in that synthesis gas and dimethyl ether are used as raw materials and continuously pass through a reactor provided with a catalyst bed layer to produce propylene, reaction products of ethylene and C4-C7 hydrocarbons in the reaction products are separated and used as recycle gas to be mixed with raw material gas for preheating, and then the mixture enters the reactor to react and feed dimethyl ether with the weight space velocity of 0.3-10h < -1 > and the synthesis gas: dimethyl ether =0.5:1 to 10:1, the reaction pressure is 0.2-7.0MPa; the reaction temperature of the reactor is 400-600 ℃. When the reaction is stable, the ratio of ethylene to C4-C7 hydrocarbons in the recycle gas is constant, but the ratio of ethylene to C4-C7 hydrocarbon products varies with the reactivity of the different catalysts. All ethylene and C4-C7 hydrocarbon products in the reaction product are returned to the reactor as circulating gas. Thereby producing propylene to the maximum extent. A small amount of methane, ethane and aromatic hydrocarbon in the reaction product are treated as by-products, and the sum of the methane, the ethane and the aromatic hydrocarbon is less than 15%. A small amount of propane in the reaction product can be used as a circulating gas to return to the reactor, and can also be used as a dry gas to carry out purge.
The various modification methods of the catalyst are different depending on the acid strength of the parent molecular sieve and the density of different acid sites, and the desired catalyst is obtained by performing composite modification by the various modification methods used in the patent. For the molecular sieve precursor with smaller acid site density of the catalyst, the ideal acid strength can be obtained by adopting one or two modification methods of the patent. Therefore, the single modification method of various elements also belongs to the covered field of the patent. For example, a single modification such as metal oxide modification, acid treatment, steam treatment, etc. is within the scope of this patent.
Benefits of the present application include, but are not limited to:
(1) The application provides a method for producing propylene by synthesis gas and dimethyl ether, the space-time yield of the propylene is high, and the catalyst stability is good;
(2) The method for producing propylene has the characteristics of simple production flow, few reaction byproducts and high raw material utilization rate, can greatly reduce the production cost and has good economic benefit compared with the traditional production process for preparing propylene from methanol.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
The MCM-49 molecular sieve in the examples was synthesized according to the method in patent USP 5236575. The MCM-22 molecular sieve in the examples was synthesized according to the method in patent USP 4954325. ZSM-5 molecular sieve, manufactured by catalyst factory of southern Kai university, and named NKF-5II.
Example 1
The preparation process of the catalyst is as follows: adding 26.3 g of chromium nitrate hexahydrate into 100g of deionized water for dissolving, adding 75 g of diatomite, soaking for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 80 g of modified diatomite. 120 g of HZSM-5 molecular sieve with the molar silica-alumina ratio of 20 is mixed with 80 g of modified diatomite, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 500 deg.C for 10 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix A0. 20 g of A0 sample is soaked in zinc nitrate and nickel nitrate aqueous solution for 12 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight content of zinc oxide is 3 percent, and the weight content of nickel oxide is 1.5 percent to prepare A1. Adding 10g of a cyclohexane solution of benzyl silicone oil with the weight of 20 percent into 20 g of A1, soaking at room temperature for 10 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain A2. 20 g of A2 was added to 10g of a 20% by weight cyclohexane solution of benzyl silicone oil, and the mixture was immersed at room temperature for 12 hours. The calcination procedure was the same as for A2 to obtain A3. 20 g of A3 was subjected to steam treatment at 350 ℃ under 1.0MPa in an atmosphere of 100% steam for 10 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst A. The content of the molecular sieve is 60 percent.
Example 2
The preparation process of the catalyst is as follows: adding 52.6 g of chromium nitrate hexahydrate into 200 g of deionized water for dissolving, adding 130 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 700 ℃ to obtain 140 g of modified alumina. 60 g of HZSM-5 molecular sieve with the molar silica-alumina ratio of 30, 100g of silica sol with the weight of 40 percent and 140 g of modified alumina are mixed, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 700 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix B0. And (3) soaking 20 g of the B0 sample in a zirconium nitrate aqueous solution for 12 hours, drying at 120 ℃, and roasting at 550 ℃ for 10 hours to obtain B1, wherein the weight content of zirconium oxide is 15%. Adding 10g of a cyclohexane solution of 50 wt% of simethicone into 20 g of B1, soaking at room temperature for 8 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain B2. A cyclohexane solution (10 g) of 30% by weight of ethyl orthosilicate was added to 20 g of B2, and the mixture was immersed at room temperature for 8 hours. The firing procedure was the same as B2 to obtain B3. And (3) soaking 20 g of the B3 sample in a magnesium nitrate aqueous solution for 12 hours, drying at 120 ℃, and roasting at 550 ℃ for 10 hours to obtain B4, wherein the weight content of magnesium oxide is 1%. 20 g of B4 was subjected to steam treatment at 800 ℃ under 2.0MPa in an atmosphere of 100% steam for 0.5 hour, and calcined at 600 ℃ for 3 hours to obtain catalyst B. The molecular sieve content in the catalyst is 30%.
Example 3
The preparation process of the catalyst is as follows: adding 19.5 g of nickel nitrate hexahydrate into 100g of deionized water for dissolving, adding 20 g of diatomite and 25 g of kaolin, soaking for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 700 ℃ to obtain 50 g of modified binder. 200 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum being 100 is mixed with the binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix D0. 20 g of D0 sample is dipped in zinc nitrate and chromium nitrate aqueous solution for 24 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight percentage of zinc oxide in the catalyst is 4 percent, and the weight percentage of chromium oxide is 3 percent, so as to prepare D1. Adding 10g of a cyclohexane solution of ethyl orthosilicate with the weight of 40% into 20 g of D1, soaking at room temperature for 12 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain D2. 20 g of D2 was added to 10g of a 20% by weight cyclohexane solution of benzyl silicone oil, and the mixture was immersed at room temperature for 12 hours. The firing procedure was the same as for D2 to produce D3. 20 g of D3 was subjected to steam treatment at 350 ℃ under 3.0MPa in a 100% steam atmosphere for 10 hours, and calcined at 650 ℃ for 3 hours to obtain catalyst D. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 4
The preparation process of the catalyst is as follows: adding 39 g of nickel nitrate hexahydrate into 200 g of deionized water for dissolution, adding 20 g of diatomite and 20 g of alumina, soaking at 80 ℃ for 12 hours, drying at 120 ℃, and roasting at 700 ℃ for 10 hours to obtain 50 g of modified binder. 200 g of ammonia type ZSM-5 molecular sieve with the mol ratio of 50 is mixed with 50 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix E0. 20 g of E0 sample is soaked in zinc nitrate and calcium nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 650 ℃ for 3 hours, and the E1 is prepared, wherein the weight content of zinc oxide is 10 percent, and the weight content of calcium oxide is 3 percent. Adding 10g of 40 wt% ethyl orthosilicate solution in cyclohexane into 20 g of E1, soaking at room temperature for 6 hours, drying at 120 ℃, baking at 550 ℃ for 10 hours, and obtaining E2. 20 g of E2 was added to 10g of a 35% by weight cyclohexane solution of ethyl orthosilicate, and the mixture was immersed at room temperature for 6 hours. The calcination procedure was the same as for E2 to obtain E3. 20 g of E3 was added to 10g of a 30% strength by weight cyclohexane solution of ethyl orthosilicate, and the mixture was immersed at room temperature for 2 hours. The calcination procedure was the same as for E2 to give E4. 20 g of E4 was subjected to steam treatment at 450 ℃ under 3.0MPa in an atmosphere of 100% steam for 10 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst E. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 5
The preparation process of the catalyst is as follows: adding 21 g of calcium nitrate tetrahydrate into 200 g of deionized water for dissolution, adding 20 g of diatomite and 25 g of alumina, soaking at 80 ℃ for 12 hours, drying at 120 ℃, and roasting at 650 ℃ for 10 hours to obtain 50 g of modified binder. 200 g of ammonia type ZSM-5 molecular sieve with the mol ratio of 150 to the aluminum is mixed with 50 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid to extrude and form strips.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix F0. And (3) soaking 20 g of F0 sample in zinc nitrate and nickel nitrate aqueous solution for 24 hours, drying at 120 ℃, roasting at 650 ℃ for 3 hours, wherein the weight content of zinc oxide is 3%, and the weight content of nickel oxide is 2%, so as to obtain F1. Adding 10g of a cyclohexane solution of ethyl orthosilicate with the weight of 40% into 20 g of F1, soaking at room temperature for 24 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain F2. 20 g of F2 was added to 10g of a 35% by weight cyclohexane solution of ethyl orthosilicate, and the mixture was immersed at room temperature for 24 hours. The firing procedure was the same as F2 to obtain F3. 20 g of F3 was added to 10g of a 30% strength by weight cyclohexane solution of ethyl orthosilicate, and the mixture was immersed at room temperature for 2 hours. The calcination procedure was the same as for F2 to give F4. 20 g of F4 was subjected to steam treatment at 450 ℃ under 3.0MPa in an atmosphere of 100% steam for 10 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst F. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 6
The preparation process of the catalyst is as follows: adding 42 g of calcium nitrate tetrahydrate into 200 g of deionized water for dissolution, adding 40 g of boehmite, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 50 g of modified binder. 200 g of ammonia type ZSM-5 molecular sieve with the mol ratio of 200 is mixed with 50 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst precursor G0. 20G of G0 sample is soaked in zinc nitrate and magnesium nitrate aqueous solution for 36 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight content of zinc oxide is 10 percent, and the weight content of magnesium oxide is 3 percent, so that G1 is prepared. Adding 10G of n-hexane solution of 35 wt% of ethyl orthosilicate into 20G of G1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain G2. A30% by weight n-hexane solution of ethyl orthosilicate (10G) was added to G2 (20G), and the mixture was immersed at room temperature for 2 hours. The firing procedure was the same as for G2 to produce G3. 20G of G3 was subjected to steam treatment in a 100% steam atmosphere at 450 ℃ under 2.0MPa for 10 hours and calcined at 650 ℃ for 3 hours to obtain catalyst G. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 7
The preparation process of the catalyst is as follows: adding 21 g of calcium nitrate hexahydrate into 100g of deionized water for dissolution, adding 55 g of kaolin, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 700 ℃ to obtain 50 g of modified binder. 140 g of ammonia type ZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 200 is mixed with 50 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst precursor H0. 20 g of H0 sample is soaked in a chromium nitrate and zirconium nitrate aqueous solution for 20 hours, dried at 120 ℃, and roasted at 650 ℃ for 4 hours, wherein the weight content of chromium oxide is 10 percent, and the weight content of zirconium oxide is 3 percent, so that H1 is prepared. Adding 10g of dimethyl silicone oil solution with the weight of 35% into 20 g of H1, soaking at room temperature for 4 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain H2. 20 g of H2 was added to 10g of a 20% by weight solution of dimethylsilicone oil in n-hexane, and the mixture was immersed at room temperature for 4 hours. The calcination procedure was the same as for H2 to produce H3. 20 g of H3 is subjected to steam treatment for 4 hours in an atmosphere of 100 percent steam, the treatment temperature is 550 ℃, the pressure is 1.0MPa, and the catalyst H is prepared by roasting 3 at 550 ℃. The content of the molecular sieve in the prepared catalyst is 70%.
Example 8
The preparation process of the catalyst is as follows: adding 18.3 g of zinc nitrate hexahydrate into 100g of deionized water for dissolving, adding 25 g of diatomite, soaking for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 700 ℃ to obtain 30 g of modified binder. 170 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum being 30 is mixed with 30 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid to extrude and form strips.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix I0. And (3) soaking 20 g of the I0 sample in a calcium nitrate aqueous solution for 24 hours, drying at 120 ℃, and roasting at 700 ℃ for 5 hours to obtain I1, wherein the weight content of calcium oxide is 3%. Adding 10g of dimethyl silicone oil solution with the weight of 35% into 20 g of I1, soaking at room temperature for 4 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain I2. A20% by weight solution of dimethylsilicone oil in n-hexane (10 g) was added to 20 g of I2, and the mixture was immersed at room temperature for 4 hours. The calcination procedure was the same as I2 to obtain I3. 20 g of I3 is subjected to steam treatment for 10 hours in an atmosphere of 100% steam, the treatment temperature is 350 ℃, the pressure is 1.0MPa, and the catalyst I is prepared by roasting for 3 hours at 550 ℃. The content of the molecular sieve in the prepared catalyst is 85%.
Example 9
The preparation process of the catalyst is as follows: adding 26.3 g of chromium nitrate hexahydrate into 100g of deionized water for dissolving, adding 35 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 550 ℃ to obtain 40 g of modified binder. 160 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum being 300 is mixed with 40 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix J0. A20 g J0 sample is soaked in a zirconium nitrate solution for 24 hours, dried at 120 ℃, and roasted at 700 ℃ for 3 hours, wherein the weight content of zirconium oxide is 15%, and J1 is prepared. Adding 10g of n-hexane solution of ethyl orthosilicate with the weight of 40% into 20 g of J1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain J2. A30% strength by weight n-hexane solution of ethyl orthosilicate (10 g) was added to J2 (20 g) and the mixture was immersed at room temperature for 2 hours. The firing procedure was the same as J2 to produce J3. And (3) soaking 20 g of J3 sample in a magnesium nitrate solution for 24 hours, drying at 120 ℃, and roasting at 600 ℃ for 3 hours to obtain J4, wherein the weight content of magnesium oxide is 2%. 20 g of J4 was subjected to steam treatment at 350 ℃ under 3.0MPa in an atmosphere of 100% steam for 4 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst J. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 10
The preparation process of the catalyst is as follows: adding 52.6 g of chromium nitrate hexahydrate into 200 g of deionized water for dissolving, adding 30 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 40 g of modified binder. 160 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum being 400 is mixed with the modified binder 40, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix K0. And (3) soaking a 20 g K0 sample in a nickel nitrate and zirconium nitrate aqueous solution for 24 hours, drying at 120 ℃, and roasting at 600 ℃ for 3 hours to obtain K1, wherein the weight content of nickel oxide is 3%, and the weight content of zirconium oxide is 3%. Adding 10g of n-hexane solution of ethyl orthosilicate with the weight of 40% into 20 g of K1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain K2. 10g of a solution of 30% by weight of dimethylsilicone oil in n-hexane was added to 20 g of K2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The firing procedure was the same as for K2 to give K3. 20 g of K3 is subjected to steam treatment for 6 hours in a 100% steam atmosphere, the treatment temperature is 350 ℃, the pressure is 1.0MPa, and the catalyst K is prepared by roasting for 5 hours at 650 ℃. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 11
The preparation process of the catalyst is as follows: : adding 26.3 g of chromium nitrate hexahydrate into 100g of deionized water for dissolving, adding 35 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 40 g of modified binder. 160 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 500 is mixed with 40 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix L0. And (3) soaking 20 g of L0 sample in an aqueous solution of calcium nitrate and magnesium nitrate for 24 hours, drying at 120 ℃, and roasting at 600 ℃ for 3 hours to obtain L1, wherein the weight content of calcium oxide is 5% and the weight content of magnesium oxide is 2%. Adding 10g of 40 wt% cyclohexane solution of benzyl silicone oil into 20 g of L1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain L2. 10g of a solution of 30% by weight of dimethylsilicone oil in n-hexane was added to 20 g of L2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The calcination procedure was the same as for L2 to give L3. 20 g of L3 was subjected to steam treatment at 600 ℃ under 1.0MPa in an atmosphere of 100% steam for 2 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst L. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 12
The preparation process of the catalyst is as follows: adding 26.3 g of chromium nitrate hexahydrate into 100g of deionized water for dissolution, adding 25 g of kaolin, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 30 g of modified binder. 100g of HMCM-22 molecular sieve with the molar ratio of 20 to aluminum and 70 g of HZSM-5 molecular sieve with the molar ratio of 30 to aluminum are mixed with 30 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix M0. 20 g of M0 is soaked in zinc nitrate solution for 24 hours, dried at 120 ℃, roasted at 600 ℃ for 3 hours, and the weight content of zinc oxide is 4 percent to prepare M1. Adding 10g of cyclohexane solution of benzyl silicone oil with the weight of 50% into 20 g of M1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain M2. 20 g of M2 is soaked in magnesium nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 600 ℃ for 3 hours, the weight content of magnesium oxide is 15 percent, and roasted at 650 ℃ for 3 hours to prepare the catalyst M. The content of the molecular sieve in the prepared catalyst is 85%.
Example 13
The preparation process of the catalyst is as follows: adding 26.3 g of chromium nitrate hexahydrate into 100g of deionized water for dissolving, adding 25 g of diatomite, soaking at 80 ℃ for 12 hours, drying at 120 ℃, and roasting at 600 ℃ for 10 hours to obtain 30 g of modified binder. 70 g of HMCM-22 molecular sieve with the molar ratio of 60 to aluminum and 100g of HZSM-5 molecular sieve with the molar ratio of 300 to aluminum are mixed with 30 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix N0. And (3) soaking 20 g of an N0 sample in an aqueous solution of calcium acetate and zirconium nitrate for 10 hours, drying at 120 ℃, roasting at 650 ℃ for 3 hours, wherein the weight content of calcium oxide is 2%, and the weight content of zirconium oxide is 6%, and thus obtaining N1. Adding 10g of a cyclohexane solution of ethyl orthosilicate with the weight of 40% into 20 g of N1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain N2. 20 g of a cyclohexane solution of dimethylsilicone oil (20% by weight) was added to 20 g of N2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The calcination procedure was the same as for N2 to produce N3. 20 g of N3 was subjected to steam treatment at 350 ℃ under 2.0MPa in an atmosphere of 100% steam for 10 hours, and calcined at 650 ℃ for 3 hours to obtain catalyst N. The content of the molecular sieve in the prepared catalyst is 85%.
Example 14
The preparation process of the catalyst is as follows: adding 21 g of calcium nitrate tetrahydrate into 100g of deionized water for dissolving, adding 25 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 30 g of modified binder. 70 g of HMCM-49 molecular sieve with the molar ratio of 50 to aluminum and 100g of HZSM-5 molecular sieve with the molar ratio of 400 to aluminum are mixed with 30 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix P0. 20 g of P0 sample is soaked in a chromium nitrate and zinc nitrate aqueous solution for 36 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight content of chromium oxide is 2 percent, and the weight content of zinc oxide is 6 percent, so that P1 is prepared. Adding 10g of 30 wt% cyclohexane solution of benzyl silicone oil into 20 g of P1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain P2. 20 g of P2 was added to 10g of a 30% by weight solution of dimethylsilicone oil in cyclohexane, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The firing procedure was the same as for P2 to give P3. 20 g of P3 was subjected to steam treatment at 350 ℃ under 2.0MPa in an atmosphere of 100% steam for 10 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst P. The content of the molecular sieve in the prepared catalyst is 85 percent.
Example 15
The preparation process of the catalyst is as follows: adding 21 g of calcium nitrate tetrahydrate into 100g of deionized water for dissolving, adding 35 g of diatomite, soaking at 80 ℃ for 12 hours, drying at 120 ℃, and roasting at 600 ℃ for 10 hours to obtain 30 g of modified binder. 60 g of HMCM-22 molecular sieve with the molar ratio of 40 to aluminum and 160 g of HZSM-5 molecular sieve with the molar ratio of 500 to aluminum are mixed with 40 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix R0. Drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain R0. Adding 10g of an n-hexane solution of 40% ethyl orthosilicate by weight into 20 g of R1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain R2. 20 g of R2 was added to 10g of a 30% by weight cyclohexane solution of benzyl silicone oil, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The calcination procedure was the same as for R2 to produce R3. 20 g of R3 sample is soaked in magnesium nitrate solution for 20 hours, dried at 120 ℃, roasted at 700 ℃ for 3 hours, the weight content of magnesium oxide is 10 percent, and roasted at 550 ℃ for 3 hours to prepare the catalyst R. The content of the molecular sieve in the prepared catalyst is 80 percent.
Example 16
The preparation process of the catalyst is as follows: adding 64 g of magnesium nitrate hexahydrate into 200 g of deionized water for dissolving, adding 130 g of diatomite, soaking at 80 ℃ for 12 hours, drying at 120 ℃, and roasting at 700 ℃ for 10 hours to obtain 140 g of modified binder. 60 g of MCM-22 molecular sieve with the molar silica-alumina ratio of 30 and 60 g of HZSM-5 molecular sieve with the molar silica-alumina ratio of 40 are mixed with 140 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extruding strips and forming.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix S0. And (3) soaking 20 g of the S0 sample in nickel nitrate and zinc nitrate aqueous solution for 20 hours, drying at 120 ℃, and roasting at 700 ℃ for 3 hours to obtain S1, wherein the weight content of nickel oxide is 5%, and the weight content of zinc oxide is 6%. Adding 10g of n-hexane solution of 30 wt% ethyl orthosilicate into 20 g of S1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain S2. 20 g of R2 was added to 10g of a cyclohexane solution of benzyl silicone oil (20% by weight), and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The calcination procedure was the same as for R2 to produce R3. 20 g of S3 was subjected to steam treatment at 550 ℃ under a pressure of 1.0MPa in an atmosphere of 100% steam for 4 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst S. The content of the molecular sieve in the prepared catalyst is 30 percent.
Example 17
The preparation process of the catalyst is as follows: adding 32 g of magnesium nitrate hexahydrate into 100g of deionized water for dissolving, adding 55 g of alumina, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 60 g of modified binder. 140 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 200 is mixed with 60 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix T0. 20 g of T0 sample is soaked in calcium nitrate and zinc nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 600 ℃ for 3 hours, and the T1 is prepared by calcium oxide with the weight content of 2% and zinc oxide with the weight content of 5%. Adding 10g of a dimethyl silicone oil n-hexane solution with the weight of 30% into 20 g of T1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain T2. 20 g of T2 was added to 10g of a 20% by weight cyclohexane solution of benzyl silicone oil, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The calcination procedure was the same as for T2 to give T3. 20 g of T3 was subjected to steam treatment at 600 ℃ under 1.0MPa in an atmosphere of 100% steam for 2 hours, and calcined at 550 ℃ for 5 hours to obtain catalyst T. The content of the molecular sieve in the prepared catalyst is 70%.
Example 18
The preparation process of the catalyst is as follows: adding 32 g of magnesium nitrate hexahydrate into 100g of deionized water for dissolving, adding 35 g of kaolin, dipping for 12 hours at 80 ℃, drying at 120 ℃, and roasting for 10 hours at 600 ℃ to obtain 40 g of modified binder. 160 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum being 100 is mixed with 40 g of the modified binder, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid to extrude and form strips.
Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain a columnar catalyst matrix U0. And (3) soaking 20 g of U0 sample in a chromium nitrate and zinc nitrate solution for 24 hours, drying at 120 ℃, roasting at 600 ℃ for 3 hours, wherein the weight content of chromium oxide is 3%, and the weight content of zinc oxide is 5%, so as to prepare U1. Adding 10g of n-hexane solution of ethyl orthosilicate with the weight of 40% into 20 g of U1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain U2. 10g of a 40% by weight solution of benzyl silicone oil in cyclohexane was added to 20 g of U2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The same firing procedure as for U2 gave U3. 20 g of U3 was subjected to steam treatment at 400 ℃ under a pressure of 3.0MPa in an atmosphere of 100% steam for 5 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst U. The content of the molecular sieve in the prepared catalyst is 80 percent.
Comparative example 1
The preparation process of the catalyst is as follows: 30 g of alumina is mixed with 70 g of HMCM-49 molecular sieve with the mol ratio of 50 and 100g of HZSM-5 molecular sieve with the mol ratio of 400, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. The catalyst is cut into 1-3 mm to obtain the columnar catalyst W.
Example 19
The catalysts obtained in examples 1 to 18 and the catalyst obtained in comparative example 1 were reacted with dimethyl ether in a fixed bed reactor to produce propylene. Separating ethylene and C4-C7 hydrocarbon products in the reaction products, preheating the ethylene and C4-C7 hydrocarbon products with raw material synthesis gas and dimethyl ether, and returning the preheated products to the reactor, and carrying out online chromatographic analysis on the reaction products. The gas chromatography is Agilent 7890A, and the chromatographic column is PLOTQ. The loading of the catalyst is 100.0 g, and the weight space velocity of the dimethyl ether fed is 0.3-10h -1 Dimethyl ether =0.5, reaction pressure is 0.2-7.0MPa; the reactor reaction temperature was 400 to 600 c, the conversion of dimethyl ether was 100% under the reaction conditions of the examples, and the reaction results of the catalysts in the respective examples for 72 hours are shown in table 1.
Propylene selectivity = (mass fraction of propylene in discharge) ÷ (mass fraction sum of materials in discharge) × 100%
TABLE 1 reaction conditions and reaction Properties
Examples 20 to 23
The catalyst evaluation apparatus and the test method were the same as in example 19. The loading of the reaction catalyst was 100.0 g. The weight space velocity of the dimethyl ether fed is 1.0h -1 Synthesis gas in fresh feed: dimethyl ether =3:1, the reaction pressure is 1.0MPa. The dimethyl ether conversion was 100% throughout the reaction time and no sign of catalyst deactivation was observed. The reaction results of the catalysts in the examples are shown in Table 2.
TABLE 2 reactivity of the catalysts
| Examples | Catalyst and process for preparing same | Reactor temperature/. Degree.C | Running time/h | Propylene selectivity/%) |
| 20 | D | 470 | 2000 | 72 |
| 21 | G | 550 | 2200 | 70 |
| 22 | N | 500 | 2000 | 72 |
| 23 | P | 480 | 2200 | 70 |
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. A method for producing propylene by synthesis gas and dimethyl ether is characterized by at least comprising the following steps:
i) Preheating raw material gas containing synthesis gas and dimethyl ether, and continuously passing through a reactor provided with a catalyst bed layer to obtain a product mixture; producing propylene;
ii) separating the product mixture to obtain propylene, ethylene and C4-C7 hydrocarbon compounds;
iii) Taking the ethylene and the C4-C7 hydrocarbon compound as circulating gas, returning to the step i), mixing with raw material gas, preheating, and then entering a reactor;
the catalyst is obtained by molding a mixture containing a molecular sieve and a modified binder and then carrying out post-treatment;
the modified binder is a binder modified by metal oxide;
the molecular sieve is at least one selected from ZSM-5, MCM-22 and MCM-49 molecular sieves;
the molar silica-alumina ratio of the molecular sieve is 20-500;
the binder is selected from at least one of boehmite, alumina, diatomite, silica or kaolin;
the metal element in the binder modified by the metal oxide is selected from at least one of chromium, nickel, calcium, zinc and magnesium;
the post-treatment is metal oxide modification, silanization reagent modification and water vapor treatment;
the metal element in the metal oxide modification in the post-treatment is at least one selected from calcium, zirconium, zinc, magnesium, nickel, zirconium and chromium;
the silanization reagent is at least one of ethyl orthosilicate, benzyl silicone oil and dimethyl silicone oil.
2. The method of claim 1, wherein the reaction conditions are:
the reaction temperature is 400-600 ℃;
the reaction pressure is 0.3-7.0 MPa;
the molar ratio of synthesis gas to dimethyl ether is 0.5:1 to 10:1;
the weight space velocity of the dimethyl ether fed is 0.3 to 10h -1 ；
The molar ratio of carbon monoxide to hydrogen in the synthesis gas is 10.
3. The method of claim 1, wherein the reaction conditions are:
the reaction temperature is 450-550 ℃;
the weight space velocity of dimethyl ether feeding is 1-10 h -1 。
4. The method of claim 1, wherein the molecular sieve is a hydrogen type or ammonium type molecular sieve;
the mass percentage of the molecular sieve in the catalyst is 30-85%.
5. The method of claim 1, wherein the modified binder is obtained by impregnating a binder with a solution containing a metal element and then calcining the impregnated binder.
6. The method of claim 1, wherein the metal oxide in the post-treatment is modified to: putting a solid sample into a solution containing metal elements for soaking and then roasting;
the solid sample is a sample obtained after forming a mixture containing the molecular sieve and the modified binder.
7. The process according to claim 1, wherein the steam treatment is 100% steam, the treatment temperature is 300 ℃ to 800 ℃, the treatment time is 0.5 to 10 hours, and the pressure is 1.0 to 3.0MPa.
8. The method of claim 1, wherein the catalyst is prepared by a process comprising the steps of:
(a3) Carrying out metal oxide modification on the binder, soaking the binder in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a modified binder;
(b3) Mixing the modified binder obtained in the step (a 3) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve for molding, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Z1;
(c3) Soaking the solid Z1 obtained in the step (b 3) in a cyclohexane and/or n-hexane solution of a silylation reagent for 2 to 24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silylation reagent in the solution is 20 to 50 percent; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, repeating for 0-3 times to obtain a silylation reagent modifier Z2;
(d3) Dipping the silanization reagent modifier Z2 obtained in the step (c 3) in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a solid Z3;
(e3) And (d) treating the silanization reagent modifier Z3 obtained in the step (d 3) by adopting water vapor, drying, and roasting at 500-800 ℃ for 2-10 hours to obtain the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011446855.9A CN114605213B (en) | 2020-12-09 | 2020-12-09 | Method for producing propylene from synthesis gas and dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011446855.9A CN114605213B (en) | 2020-12-09 | 2020-12-09 | Method for producing propylene from synthesis gas and dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114605213A CN114605213A (en) | 2022-06-10 |
| CN114605213B true CN114605213B (en) | 2023-01-31 |
Family
ID=81855980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011446855.9A Active CN114605213B (en) | 2020-12-09 | 2020-12-09 | Method for producing propylene from synthesis gas and dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605213B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0083160A2 (en) * | 1981-12-30 | 1983-07-06 | Mobil Oil Corporation | Catalyst and process for light olefin production |
| CN101176849A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof |
| WO2009055996A1 (en) * | 2007-10-31 | 2009-05-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A process for producing propylene |
| CN102516004A (en) * | 2011-10-21 | 2012-06-27 | 中国科学院广州能源研究所 | Method for preparing low-carbon olefin by taking biomass synthetic gas as raw material with dimethyl ether two-step method |
| CN103570504A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by gas-phase alkylation of phenol and methanol |
| CN103570485A (en) * | 2012-07-20 | 2014-02-12 | 李坚 | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO |
| CN104209139A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气集团公司 | Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof |
| CN105772059A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene from methyl alcohol or/and dimethyl ether and preparation method of catalyst |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012357510B2 (en) * | 2011-12-19 | 2016-03-24 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
-
2020
- 2020-12-09 CN CN202011446855.9A patent/CN114605213B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0083160A2 (en) * | 1981-12-30 | 1983-07-06 | Mobil Oil Corporation | Catalyst and process for light olefin production |
| CN101176849A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof |
| WO2009055996A1 (en) * | 2007-10-31 | 2009-05-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A process for producing propylene |
| CN102516004A (en) * | 2011-10-21 | 2012-06-27 | 中国科学院广州能源研究所 | Method for preparing low-carbon olefin by taking biomass synthetic gas as raw material with dimethyl ether two-step method |
| CN103570485A (en) * | 2012-07-20 | 2014-02-12 | 李坚 | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO |
| CN103570504A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by gas-phase alkylation of phenol and methanol |
| CN104209139A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气集团公司 | Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof |
| CN105772059A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene from methyl alcohol or/and dimethyl ether and preparation method of catalyst |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
Non-Patent Citations (8)
| Title |
|---|
| HZSM-5催化剂上甲醇制丙烯反应条件的研究;李海波等;《化学世界》;20091225(第12期);第727-730页 * |
| 二甲醚脱水制低级烯烃;吕胜初;《天然气化工(C1化学与化工)》;19820225(第01期);第31-38页 * |
| 反应气氛对Ca/ZSM-5上二甲醚转化制丙烯反应的影响;满建明等;《燃料化学学报》;20110115(第01期);第42-46页 * |
| 合成气制低碳烯烃研究进展;杨光杰等;《现代化工》;20200430(第04期);第61-64页 * |
| 增产丙烯技术研究进展;魏飞等;《石油化工》;20081015(第10期);第979-986页 * |
| 循环烃在丙烯生产中作用;李志明;《化工设计通讯》;20181028(第10期);第135页 * |
| 碱溶液改性ZSM-5分子筛直接催化合成气制低碳烯烃;林雄超等;《现代化工》;20200331(第03期);第126-136页 * |
| 酸性催化剂催化异丙醇脱水制丙烯反应;刘春燕等;《工业催化》;20110515(第05期);第40-44页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114605213A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101550202B1 (en) | Process for methanol coupled catalytic cracking reaction of naphtha using a modified zsm-5 molecular sieve catalyst | |
| US20100234658A1 (en) | Catalyst Composition and Process For Converting Aliphatic Oxygenates to Aromatics | |
| KR101971085B1 (en) | Catalyst for manufacturing olefin and continuous reaction regeneration method for manufacturing olefin using the same | |
| JP5881856B2 (en) | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use | |
| JP5518727B2 (en) | Process for the production of light olefins from synthesis gas using a continuous two-stage reaction | |
| Maftei et al. | Conversion of industrial feedstock mainly with butanes and butenes over HZSM-5 and Zn/HZSM-5 (nitrate) catalysts | |
| WO2022022510A1 (en) | Core-shell composite catalyst, preparation method for same, and use thereof | |
| KR101731165B1 (en) | Catalysts for ethanol dehydration and production method of ethylene using same | |
| JP7023382B2 (en) | A catalyst for producing a light olefin, a method for producing the same, and a method for producing a light olefin using the catalyst. | |
| CN107847908B (en) | Catalyst and hydrocarbon conversion process using said catalyst | |
| CN102806100A (en) | Catalyst for producing propane and high octane number gasoline by using butane, and preparation method thereof | |
| US11141712B2 (en) | Catalyst for producing olefin having enhanced stability, conversion rate and selectivity, and preparation method thereof | |
| CN104588089B (en) | A kind of method of the de-olefin of reforming oil catalyst of ammonium fluoride modification preparation | |
| CN114605213B (en) | Method for producing propylene from synthesis gas and dimethyl ether | |
| KR20170003371A (en) | Method for manufacturing olefin using continuous reaction-regeneration | |
| JP6446033B2 (en) | Process for producing unsaturated hydrocarbons | |
| CN106221786B (en) | Naphtha conversion method | |
| CN110721732A (en) | Method for producing p-tert-butylphenol | |
| CN110072613B (en) | Catalyst system and process for converting hydrocarbon feedstock using the same | |
| KR102471188B1 (en) | Hydrocarbon Conversion Catalyst System | |
| JP5779398B2 (en) | Method for activating zeolite catalyst | |
| CN110947417A (en) | Catalyst for producing propane and gasoline from paraffin, preparation method and application | |
| CN107175126B (en) | Preparation method of Zn/binderless ZSM-11 molecular sieve catalyst | |
| CN112521241B (en) | Method for preparing durene from carbon monoxide and methanol | |
| US20110230333A1 (en) | Olefin Cracking Catalyst and Manufacturing Process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |