CN114605213A - Method for producing propylene from synthesis gas and dimethyl ether - Google Patents
Method for producing propylene from synthesis gas and dimethyl ether Download PDFInfo
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- CN114605213A CN114605213A CN202011446855.9A CN202011446855A CN114605213A CN 114605213 A CN114605213 A CN 114605213A CN 202011446855 A CN202011446855 A CN 202011446855A CN 114605213 A CN114605213 A CN 114605213A
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- 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
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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
- B01J29/40—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
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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
- B01J29/78—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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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‑1And synthesis gas: dimethyl ether is 0.5:1-10:1, and the reaction pressure is 0.2-7.0 MPa; 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 technology for preparing chemicals by taking coal as a raw material is vigorously developed, so that the method has extremely important strategic significance for meeting the long-term development of energy safety and economic society in China. In recent years, the technology of preparing olefin from coal raw material by methanol changes the pattern of olefin obtained by the traditional process, and gradually becomes a vital force in the olefin market in China.
The worldwide propylene production in 2019 was 1.4 million tons, with the demand of China accounting for 30% of the world. The ethylene by-product from cracking remains the major 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 production of propylene from methanol, and have employed multiple catalyst beds to achieve higher propylene yields. The research work with industrial application prospect focuses on modification with SAPO-34 and ZSM-5 molecular sieves as matrixes. The defects of the process for preparing the propylene by using 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 regenerants and large material recycle of the catalyst result in 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 propylene, ethylene and C4-C7 hydrocarbon compounds;
iii) returning the ethylene and the C4-C7 hydrocarbon compounds as circulating gas to the step i) to be mixed with feed gas for 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 0.5:1-10: 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: 1-0.5: 10;
the reaction conditions are preferably:
the reaction temperature is 450-550 ℃;
the weight airspeed 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 mol 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% 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, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid X1;
(c1) soaking the solid X1 obtained in the step (b1) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20-50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and repeating for 0-3 times to obtain a silylation 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 (a2) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Y1;
(c2) soaking the solid Y1 obtained in the step (b2) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20% -50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and 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 (a3) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Z1;
(c3) soaking the solid Z1 obtained in the step (b3) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20-50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and repeating for 0-3 times to obtain a silylation reagent modifier Z2;
(d3) soaking the silanization reagent modifier Z2 obtained in the step (c3) in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a solid Z3;
(e3) and (d3) treating the silanization reagent modifier Z3 obtained in the step (d3) by using 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 (3) after spray forming, preparing the fluidized bed catalyst by 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 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 realizing the selective modulation of the catalyst acidity after being calcined. 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 or MCM-49 molecular sieve. The weight content of the modified oxide is 1-15%. The temperature of the steam treatment is preferably 350-800 ℃, and the treatment is carried out for 0.5-10 hours by 100 percent steam. 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 silanization has an effect on the effect of 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 circulating 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 0.5:1-10:1, the reaction pressure is 0.2-7.0 MPa; the reaction temperature of the reactor is 400-600 ℃. When the reaction is stable, the ratio of ethylene to C4-C7 hydrocarbon in the recycle gas is constant, but the ratio of ethylene to C4-C7 hydrocarbon product varies with the reactivity of different catalysts. All the 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 by-products is less than 15%. A small amount of propane in the reaction product can be used as circulating gas and returned to the reactor, and can also be used as dry gas for releasing.
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-5 II.
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 precursor A0. A1 was prepared by immersing 20 g of A0 sample in an aqueous solution of zinc nitrate and nickel nitrate for 12 hours, drying at 120 deg.C, and calcining at 600 deg.C for 3 hours, the weight content of zinc oxide being 3% and the weight content of nickel oxide being 1.5%. Adding 20 g of cyclohexane solution of benzyl silicone oil with the weight of 20% 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 A2 to obtain A3. 20 g of A3 was subjected to steam treatment at 350 ℃ under 1.0MPa in a 100% steam atmosphere 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 precursor B0. A20 g sample of B0 was immersed in an aqueous solution of zirconium nitrate for 12 hours, dried at 120 ℃ and calcined at 550 ℃ for 10 hours to yield B1 with a zirconia content of 15% by weight. Adding 10g of 50 wt% dimethyl silicone oil solution in cyclohexane 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 solution of 30% by weight of ethyl orthosilicate in cyclohexane (10 g) 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. A20 g sample of B3 was immersed in an aqueous solution of magnesium nitrate for 12 hours, dried at 120 ℃ and calcined at 550 ℃ for 10 hours to yield B4 with magnesium oxide weight content of 1%. 20 g of B4 was subjected to steam treatment at 800 ℃ under 2.0MPa for 0.5 hour in a 100% steam atmosphere, 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 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 precursor D0. 20 g of D0 sample is dipped in zinc nitrate and chromium nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 600 ℃ for 3 hours, and the weight percentage of zinc oxide and chromium oxide in the catalyst is 4% and 3%, thus obtaining D1. Adding 10g of 40 wt% ethyl orthosilicate solution in cyclohexane 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 identical to D2 to yield D3. 20 g of D3 was subjected to steam treatment at 350 ℃ and 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 precursor E0. A20 g sample of E0 was immersed in an aqueous solution of zinc nitrate and calcium nitrate for 24 hours, dried at 120 ℃ and calcined at 650 ℃ for 3 hours to obtain E1, wherein the weight content of zinc oxide was 10% and the weight content of calcium oxide was 3%. Adding 10g of 40 wt% ethyl orthosilicate cyclohexane solution into 20 g of E1, soaking at room temperature for 6 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain E2. A solution of 35% by weight of ethyl orthosilicate in cyclohexane (10 g) was added to 20 g of E2, and the mixture was immersed at room temperature for 6 hours. The same firing procedure as E2 gave E3. A solution of 30% by weight of ethyl orthosilicate in cyclohexane (10 g) was added to 20 g of E3, and the mixture was immersed at room temperature for 2 hours. The same firing procedure as E2 gave E4. 20 g of E4 was subjected to steam treatment at 450 ℃ under 3.0MPa in a 100% steam atmosphere 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: dissolving 21 g of calcium nitrate tetrahydrate in 200 g of deionized water, 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 precursor F0. 20 g of F0 sample is soaked in zinc nitrate and nickel nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 650 ℃ for 3 hours, and the weight content of zinc oxide is 3 percent and the weight content of nickel oxide is 2 percent, thus obtaining F1. Adding 10g of 40 wt% ethyl orthosilicate cyclohexane solution into 20 g of F1, soaking at room temperature for 24 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain F2. A solution of 35% by weight of ethyl orthosilicate in cyclohexane (10 g) was added to 20 g of F2, and the mixture was immersed at room temperature for 24 hours. The same firing procedure as F2 gave F3. A solution of 30% by weight of ethyl orthosilicate in cyclohexane (10 g) was added to 20 g of F3, and the mixture was immersed at room temperature for 2 hours. The same firing procedure as F2 gave F4. 20 g of F4 was subjected to steam treatment at 450 ℃ under 3.0MPa in a 100% steam atmosphere 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 was immersed in zinc nitrate and magnesium nitrate aqueous solution for 36 hours, dried at 120 ℃ and calcined at 600 ℃ for 3 hours to obtain G1, wherein the weight content of zinc oxide was 10% and the weight content of magnesium oxide was 3%. 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 ethyl orthosilicate solution in n-hexane (10G) was added to G2 (20G), and the mixture was immersed at room temperature for 2 hours. The firing procedure was the same as G2 to produce G3. 20G of G3 was subjected to steam treatment at 450 ℃ under 2.0MPa in an atmosphere of 100% steam 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. A20% by weight solution of dimethylsilicone oil in n-hexane (10 g) was added to 20 g of H2, and the mixture was immersed at room temperature for 4 hours. The calcination procedure was the same as H2 to produce H3. 20 g of H3 was subjected to steam treatment at 550 ℃ under 1.0MPa for 4 hours in a 100% steam atmosphere, and calcined at 550 ℃ for 3 hours to obtain catalyst H. 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 prepare a columnar catalyst precursor 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 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 was treated with steam at 350 ℃ under 1.0MPa in a 100% steam atmosphere for 10 hours, and calcined at 550 ℃ for 3 hours to obtain catalyst I. 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 precursor 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 ethyl orthosilicate normal hexane solution 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% 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 make J3. A20 g J3 sample is soaked in magnesium nitrate solution for 24 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, and the weight content of magnesium oxide is 2%, so that J4 is prepared. 20 g of J4 was subjected to steam treatment at 350 ℃ and 3.0MPa in a 100% steam atmosphere 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 precursor K0. 20 g of K0 sample is soaked in nickel nitrate and zirconium nitrate aqueous solution for 24 hours, dried at 120 ℃, roasted at 600 ℃ for 3 hours, and the weight content of nickel oxide is 3 percent and the weight content of zirconium oxide is 3 percent, thus obtaining K1. 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, and obtaining K2. 10g of a 30% by weight solution of dimethylsilicone 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 K2 to obtain K3. 20 g of K3 was treated with steam at 350 ℃ and 1.0MPa in a 100% steam atmosphere for 6 hours, and calcined at 650 ℃ for 5 hours to obtain catalyst K. 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 to be used as an extrusion aid for extruding 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 precursor L0. A20 g L0 sample is soaked in a calcium nitrate and magnesium nitrate solution for 24 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight content of calcium oxide is 5 percent, and the weight content of magnesium oxide is 2 percent, so that L1 is prepared. Adding 10g of 40 wt% benzyl silicone oil solution in cyclohexane into 20 g of L1, soaking at room temperature for 2 hours, drying at 120 ℃, baking at 550 ℃ for 10 hours to obtain L2. A30% by weight solution of dimethylsilicone in n-hexane (10 g) was added to 20 g of L2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The firing procedure was the same as L2 to obtain L3. 20 g of L3 was treated with 100% steam at 600 ℃ under 1.0MPa 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 precursor M0. 20 g of M0 is dipped in zinc nitrate solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours, and the weight content of zinc oxide is 4 percent to prepare M1. Adding 10g of 50 wt% cyclohexane solution of benzyl silicone oil into 20 g of M1, soaking at room temperature for 2 hours, drying at 120 ℃, baking 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 obtain 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 precursor N0. 20 g of N0 sample is dipped in a calcium acetate and zirconium nitrate solution for 10 hours, dried at 120 ℃, and roasted at 650 ℃ for 3 hours, wherein the weight content of calcium oxide is 2 percent and the weight content of zirconium oxide is 6 percent, thus obtaining N1. Adding 10g of 40 wt% ethyl orthosilicate cyclohexane solution 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 20% by weight solution of dimethylsilicone in cyclohexane was added to 20 g of N2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The same firing procedure as N2 gave 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 precursor 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, thus obtaining P1. 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 ℃, baking at 550 ℃ for 10 hours to obtain P2. A30% by weight solution of dimethylsilicone in 10g in cyclohexane was added to 20 g of P2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The same firing procedure as P2 gave P3. 20 g of P3 was treated with steam at 350 ℃ under 2.0MPa in a 100% steam atmosphere 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, 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 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 R0. Drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain R0. Adding 10g of ethyl orthosilicate normal hexane solution with the weight of 40% into 20 g of R1, soaking at room temperature for 2 hours, drying at 120 ℃, roasting at 550 ℃ for 10 hours to obtain R2. 10g of a 30% by weight cyclohexane solution of benzyl silicone oil was added to 20 g of R2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The same firing procedure as R2 gave 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%, and roasted at 550 ℃ for 3 hours to obtain 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 precursor S0. 20 g of S0 sample is dipped in nickel nitrate and zinc nitrate aqueous solution for 20 hours, dried at 120 ℃, roasted at 700 ℃ for 3 hours, and the S1 is prepared, wherein the weight content of nickel oxide is 5 percent, and the weight content of zinc oxide is 6 percent. 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 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 same firing procedure as R2 gave R3. 20 g of S3 was subjected to steam treatment at 550 ℃ under 1.0MPa for 4 hours in a 100% steam atmosphere, 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 precursor 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 dimethyl silicone oil 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 a cyclohexane solution of benzyl silicone oil (20% by weight) was added to 20 g of T2, and the mixture was immersed at room temperature for 2 hours and dried at 120 ℃. The same firing procedure as for T2 gave T3. 20 g of T3 was subjected to steam treatment at 600 ℃ under 1.0MPa in a 100% steam atmosphere 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 precursor U0. A20 g U0 sample is soaked in a chromium nitrate and zinc nitrate solution for 24 hours, dried at 120 ℃, and roasted at 600 ℃ for 3 hours, wherein the weight content of chromium oxide is 3 percent, and the weight content of zinc oxide is 5 percent, so that U1 is prepared. Adding 10g of ethyl orthosilicate normal hexane solution 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 U2 produced U3. 20 g of U3 was subjected to steam treatment at 400 ℃ under 3.0MPa in a 100% steam atmosphere 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 prepare 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 the C4-C7 hydrocarbon products with raw material synthesis gas and dimethyl ether, 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-1The synthetic gas is dimethyl ether which is 0.5:1-10:1, and the reaction pressure is 0.2-7.0 MPa; the reactor reaction temperature was 400 ℃ and 600 ℃, the conversion of dimethyl ether was 100% under the reaction conditions of the examples, and the reaction results of the catalyst reaction for 72 hours in the various examples are shown in Table 1.
Propylene selectivity (mass fraction of propylene in the discharge) ÷ (sum of mass fractions of materials in the 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-1Synthesis gas in fresh feed: dimethyl ether 3: 1, the reaction pressure is 1.0 MPa. 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 (10)
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) returning the ethylene and the C4-C7 hydrocarbon compounds as circulating gas to the step i) to be mixed with feed gas for 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.
2. The method of claim 1, wherein the post-treatment is selected from at least one of metal oxide modification, silylation agent modification, and water vapor treatment.
3. 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 0.5:1-10: 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: 1-0.5: 10;
the reaction conditions are preferably:
the reaction temperature is 450-550 ℃;
the weight airspeed of dimethyl ether feeding is 1-10 h-1。
4. The process of claim 1, wherein 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.
5. 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%.
6. The method according to claim 1, wherein the modified binder is obtained by impregnating a binder with a solution containing a metal element and then roasting the impregnated binder;
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.
7. The method of claim 2, 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 metal element is at least one of calcium, zirconium, zinc, magnesium, nickel, zirconium and chromium;
the solid sample is a sample obtained after a mixture containing the molecular sieve and the modified binder is molded; 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.
8. The method according to claim 2, characterized in that the silylating agent is selected from at least one of ethyl orthosilicate, benzyl silicone oil, dimethyl silicone oil.
9. The method according to claim 2, 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 3.0 MPa.
10. The method of claim 1, wherein the catalyst is prepared by a process comprising the steps of:
(a1) 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;
(b1) mixing the modified binder obtained in the step (1) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid X1;
(c1) soaking the solid X1 obtained in the step (b1) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20-50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and repeating for 0-3 times to obtain a silylation reagent modifier X2;
(d1) 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;
alternatively, the catalyst preparation process comprises the steps of:
(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 (a2) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Y1;
(c2) soaking the solid Y1 obtained in the step (b2) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20-50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and repeating for 0-3 times to obtain the catalyst;
alternatively, the catalyst preparation process comprises 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 (a3) with a hydrogen type molecular sieve and/or an ammonium type molecular sieve, forming, drying, and roasting at 550-700 ℃ for 4-10 hours to obtain a solid Z1;
(c3) soaking the solid Z1 obtained in the step (b3) in a cyclohexane and/or n-hexane solution of a silanization reagent for 2-24 hours at room temperature by adopting an isometric soaking method, wherein the weight percentage of the silanization reagent in the solution is 20-50%; roasting for 1-10 hours at 550-700 ℃ in air atmosphere; cooling to room temperature, and repeating for 0-3 times to obtain a silylation reagent modifier Z2;
(d3) soaking the silanization reagent modifier Z2 obtained in the step (c3) in a solution containing metal elements, drying, and roasting at 550-700 ℃ for 3-10 hours to obtain a solid Z3;
(e3) and (d3) treating the silanization reagent modifier Z3 obtained in the step (d3) by using water vapor, drying, and roasting at 500-800 ℃ for 2-10 hours to obtain the catalyst.
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