CN115106122A - Preparation method and application of molecular sieve catalyst - Google Patents

Preparation method and application of molecular sieve catalyst Download PDF

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CN115106122A
CN115106122A CN202110309379.4A CN202110309379A CN115106122A CN 115106122 A CN115106122 A CN 115106122A CN 202110309379 A CN202110309379 A CN 202110309379A CN 115106122 A CN115106122 A CN 115106122A
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molecular sieve
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carbon monoxide
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CN115106122B (en
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丁湘浓
刘红超
朱文良
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment

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Abstract

The application discloses a preparation method and application of a molecular sieve catalyst, wherein the method comprises the following steps: (1) heating a material containing a mordenite molecular sieve and an organic alkali source to obtain an intermediate product; (2) and roasting the intermediate product to obtain the molecular sieve based catalyst. The catalyst prepared by the invention is used for carbonylation reaction of small molecular compound dimethyl ether, methanol or halogenated methane, and has high activity and stable performance.

Description

Preparation method and application of molecular sieve catalyst
Technical Field
The application relates to a preparation method and application of a molecular sieve catalyst, belonging to the field of catalysis.
Background
The continuous increase of energy demand and the urgent desire of improving the environmental quality make the energy development of China face unprecedented challenges. Based on the energy safety requirement and the energy structure characteristics of rich coal, poor oil and less gas in China, the high-efficiency conversion and clean utilization of energy are the inevitable choices for the energy development in China. Small molecule compounds such as methanol, dimethyl ether and methyl halide are important platform compounds that can be based on carbon dioxide, natural gas as feedstock. The directional conversion of small molecular compounds to prepare high value-added compounds such as low-carbon olefin, gasoline, aromatic hydrocarbon and p-xylene and oxygen-containing compounds such as acetic acid, methyl acetate, ethanol and the like is an effective way for high-efficiency and clean utilization of energy.
The C2 compound-acetic acid and methyl acetate synthesized by small molecular compounds (methanol, dimethyl ether and halogenated methane) and CO carbonylation in a directional way are one of important research directions for C1 chemical conversion, and have extremely important application backgrounds and good market prospects. MOR, FER and OFF with eight-membered ring channel structure have catalytic activity for ether carbonylation, wherein mordenite is used as catalyst, and space time yield of 0.163-MeOAc (g-Cat. h) -1 can be obtained at reaction pressure of 1MPa and temperature of 165 ℃. After introducing metal Cu and Ag on the MOR catalyst, the carbonylation performance of the MOR catalyst under the reaction condition (hydrogen atmosphere, 250 ℃ C. -. 300 ℃ C.) is superior to that of an unmodified MOR sample. The mordenite property is improved by utilizing the pre-adsorption of pyridine organic amine, and the pyridine substances can only adsorb and poison acid sites in twelve-membered ring channels due to size limitation, so that the carbonylation stability of the catalyst is improved by inhibiting the generation of carbon deposition, and the activity of the catalyst is kept stable within 48 hours of reaction. The silicon tetrachloride steam modified mordenite molecular sieve catalyst can greatly improve the stability of the catalyst in dimethyl ether carbonylation by selectively removing framework aluminum sites in 12-membered ring channels. An in-situ synthesis method for regulating and controlling the acid center position and distribution of mordenite successfully prepares a mordenite molecular sieve catalyst with excellent dimethyl ether carbonylation activity by regulating and controlling the position of an acid center. The above contents mainly relate to the research of catalyzing dimethyl ether carbonylation by mordenite. The research of the catalyst is not only suitable for dimethyl ether carbonylation reaction, but also suitable for methanol and halogenated methane carbonylation reaction has important application value.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a molecular sieve catalyst, which comprises the steps of mixing a mordenite molecular sieve with an organic base, heating and roasting to obtain the molecular sieve catalyst. The method is simple and convenient, and has strong operability. Can realize the regulation and control of the acid position of the molecular sieve catalyst, and enables the catalyst to have higher activity and target product selectivity.
According to one aspect of the present invention, there is provided a method of preparing a molecular sieve catalyst, the method comprising: (1) heating a material containing a mordenite molecular sieve and an organic alkali source to obtain an intermediate product; (2) and roasting the intermediate product to obtain the molecular sieve catalyst.
Optionally, the organic base source is selected from organic amines; the organic amine is at least one selected from the group consisting of a monobasic organic amine, a binary organic amine and a ternary organic amine.
Optionally, the mono-organic amine is selected from at least one of the compounds having the formula shown in formula I:
Figure BDA0002989141450000021
wherein R is 1 ，R 2 ，R 3 Is independently selected from H, C 1 ～C 10 Any one of the alkyl groups of (a); r 1 ，R 2 ，R 3 Not both can be H.
Alternatively, in formula I, R 1 ，R 2 ，R 3 Independently selected from H, C 1 ～C 7 Any one of the alkyl groups of (a); r 1 ，R 2 ，R 3 Not both can be H.
Alternatively, in formula I, R 1 ，R 2 ，R 3 Independently selected from H, CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、CH 3 (CH 2 ) 2 CH 2 -、CH 3 (CH 2 ) 3 CH 2 -、CH 3 (CH 2 ) 4 CH 2 -、CH 3 (CH 2 ) 5 CH 2 -、(CH 3 ) 2 CH-、(CH 3 ) 2 CHCH 2 -、CH 3 CH 2 (CH 3 ) In CH-Either one of them.
Alternatively, in formula I, R 1 ，R 2 ，R 3 Is independently selected from H, CH 3 、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、CH 3 (CH 2 ) 2 CH 2 -one of the above.
Alternatively, in formula I, R 1 ，R 2 ，R 3 Independently selected from H, CH 3 、CH 3 CH 2 -one of the above.
Alternatively, R 1 ，R 2 ，R 3 Identical, but different is H.
Alternatively, R 1 ，R 2 ，R 3 Are not identical.
Preferably, the organic monoamine is at least one selected from triethylamine and n-butylamine.
Preferably, the organic diamine is selected from diethylamine.
Alternatively, the mono-organic amine is selected from alkyl ammonium hydroxides; the alkyl ammonium hydroxide is selected from at least one of compounds having a chemical formula shown in formula II:
Figure BDA0002989141450000031
wherein R is 4 ，R 5 ，R 6 ，R 7 Independently selected from C 1 ～C 10 Any one of the alkyl groups of (1).
Alternatively, in formula II, R 4 ，R 5 ，R 6 ，R 7 Independently selected from C 1 ～C 7 Any one of the alkyl groups of (1).
Alternatively, in formula II, R 4 ，R 5 ，R 6 ，R 7 Independently selected from CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、CH 3 (CH 2 ) 2 CH 2 -、CH 3 (CH 2 ) 3 CH 2 -、CH 3 (CH 2 ) 4 CH 2 -、CH 3 (CH 2 ) 5 CH 2 -、(CH 3 ) 2 CH-、(CH 3 ) 2 CHCH 2 -、CH 3 CH 2 (CH 3 ) Any one of CH-.
Alternatively, in formula II, R 4 ，R 5 ，R 6 ，R 7 Independently selected from CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -CH 3 (CH 2 ) 2 CH 2 -、CH 3 (CH 2 ) 3 CH 2 -、CH 3 (CH 2 ) 4 CH 2 -、CH 3 (CH 2 ) 5 CH 2 -one of the above.
Alternatively, R 4 ，R 5 ，R 6 ，R 7 Different.
Alternatively, R 4 ，R 5 ，R 6 ，R 7 The same is true.
Preferably, the alkyl ammonium hydroxide is selected from at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, and tetrabutyl ammonium hydroxide.
Optionally, the preparation method comprises: (1) mixing the mordenite molecular sieve with an organic alkali source, and heating under a closed condition to obtain an intermediate; (2) and roasting the intermediate to obtain the molecular sieve based catalyst.
Optionally, the heating conditions are: the temperature is 50-220 ℃ and the time is 5-100 hours.
Optionally, the upper temperature limit of the heating is selected from 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 200 ℃, 210 ℃ or 220 ℃; the lower limit is selected from 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 120 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 200 deg.C or 210 deg.C.
Optionally, the upper limit of time for the heating is selected from 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 80 hours, 90 hours, or 100 hours; the lower limit is selected from 5 hours, 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 80 hours, 90 hours, or 99 hours.
Optionally, in the step (1), the mordenite molecular sieve and the organic alkali source are mixed, and the mixture is treated in a closed reaction kettle at a temperature of 50-220 ℃ for 5-100 hours.
Optionally, the heating conditions are: the temperature is 80-200 ℃ and the time is 12-72 hours.
Preferably, the heating conditions are: the temperature is 100-200 ℃ and the time is 18-60 hours.
Optionally, the roasting conditions are: the temperature is 450-650 ℃, and the time is 1.5-10 hours.
Optionally, the upper temperature limit of the roasting is 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ or 650 ℃; the lower limit is selected from 450 deg.C, 480 deg.C, 500 deg.C, 520 deg.C, 550 deg.C or 600 deg.C.
Alternatively, the upper time limit for the calcination is selected from 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, or 10 hours; the lower limit is selected from 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, or 9.5 hours.
Optionally, the roasting conditions are: the temperature is 450-600 ℃, and the time is 2-8 hours.
Optionally, the roasting conditions are: the temperature is 450-550 ℃ and the time is 3-7 hours.
Preferably, the roasting conditions are as follows: the temperature is 500 ℃ and 580 ℃ and the time is 3-6 hours.
Optionally, the mordenite molecular sieve has a silicon to aluminium atomic ratio of: Si/Al is 6-50.
Optionally, the mordenite molecular sieve has an upper limit on the silicon to aluminium atomic ratio selected from 8, 10, 15, 20, 25, 30, 35, 40, 50; the lower limit is selected from 6, 8, 10, 15, 20, 25, 30, 35, 40 or 49.
Optionally, the mordenite molecular sieve is selected from Na-MOR, NH 4 At least one of-MOR, H-MOR molecular sieves.
Optionally, the organic base source further comprises a solvent; the solvent is selected from water.
Optionally, the organic alkali in the organic alkali solution is 0.5% to 99.9% by mass.
Alternatively, the upper limit of the mass content of the organic base in the organic base solution is selected from 0.8%, 1.0%, 1.5%, 2.0%, 5.0%, 10.0%, 20.0%, 25.0%, 30.0%, 40.0%, 50.0%, 60.0%, 70.0%, 75.0%, 80.0%, 90.0%, or 99.9%; the lower limit is selected from 0.5%, 0.8%, 1.0%, 1.5%, 2.0%, 5.0%, 10.0%, 20.0%, 25.0%, 30.0%, 40.0%, 50.0%, 60.0%, 70.0%, 75.0%, 80.0%, or 90.0%.
Optionally, the ratio of the added amounts of the mordenite molecular sieve and the organic alkali source is 1g:2 ml-1 g:20 ml.
Optionally, the upper limit of the ratio of the added amounts of the mordenite molecular sieve and the organic base source is selected from 1g: 4ml, 1g: 6ml, 1g:8ml, 1g:10ml, 1g: 12ml, 1g: 14ml, 1g:15ml, 1g: 16ml, 1g: 18ml or 1g:2 ml; the lower limit is selected from 1g:2ml, 1g: 4ml, 1g: 6ml, 1g:8ml, 1g:10ml, 1g: 12ml, 1g: 14ml, 1g:15ml, 1g: 16ml or 1g: 18ml of the solution.
According to another aspect of the present application, there is provided a molecular sieve catalyst comprising a molecular sieve catalyst obtained according to the preparation process of any one of the above.
According to still another aspect of the present application, a method for preparing acetic acid and methyl acetate is provided, wherein compound I and a mixed gas containing carbon monoxide are subjected to contact reaction in the presence of a catalyst to obtain methyl acetate or acetic acid; wherein the catalyst is at least one of the molecular sieve catalyst described above or the molecular sieve catalyst prepared according to the method described above; the compound I is selected from at least one of methanol, halogenated methane and dimethyl ether.
Optionally, the reaction conditions are: the temperature is 150-320 ℃, the pressure is 0.5-25.0 MPa, and the time is 10-24 h.
Optionally, the upper pressure limit of the reaction is selected from 1MPa, 1.5MPa, 2MPa, 3MPa, 3.5MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 22MPa, or 25 MPa; the lower limit is selected from 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa, 3.5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa or 22 MPa.
Optionally, the upper temperature limit of the reaction is selected from 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 260 ℃, 280 ℃, 300 ℃ or 320 ℃; the lower limit is selected from 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 250 deg.C, 260 deg.C, 280 deg.C or 300 deg.C.
Alternatively, the upper time limit of the reaction is selected from 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, or 24 h; the lower limit is selected from 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23 h.
Optionally, the reaction conditions are: the temperature is 160-320 ℃, the pressure is 1.0-20.0 MPa, and the time is 10-24 h.
Preferably, the reaction conditions are: the temperature is 170-300 ℃, the pressure is 1.0-15.0 MPa, and the time is 10-24 h.
Optionally, the mass space velocity of the feed of the compound I is 0.05-5 h -1 。
Alternatively, the upper limit of the feed mass space velocity of the compound I is selected from 0.08h -1 、0.1h -1 、0.25h -1 、0.5h -1 、0.8h -1 、1.0h -1 、1.50h -1 、1.75h -1 、2.00h -1 、2.50h -1 、3.00h -1 、3.50h -1 、4.00h -1 、4.50h -1 Or 5.00h -1 (ii) a The lower limit is selected from 0.05h -1 、0.08h -1 、0.1h -1 、0.25h -1 、0.5h -1 、0.8h -1 、1.0h -1 、1.50h -1 、1.75h -1 、2.00h -1 、2.50h -1 、3.00h -1 、3.50h -1 、4.00h -1 Or 4.50h -1 。
Optionally, the mass space velocity of the feed of the compound I is 0.1-4.5 h -1 。
Preferably, the mass space velocity of the compound I is 0.1-4 h -1 。
Optionally, the molar ratio of the carbon monoxide to the compound I is 0.1: 1-50: 1.
Alternatively, the upper limit of the molar ratio of carbon monoxide to compound I is selected from 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 6:1, 8:1, 10:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, or 50: 1; the lower limit is selected from 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 6:1, 8:1, 10:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 45: 1.
Optionally, the molar ratio of the carbon monoxide to the compound I is 0.5: 1-50: 1.
Optionally, the molar ratio of the carbon monoxide to the compound I is 0.1: 1-40: 1.
Optionally, the molar ratio of the carbon monoxide to the compound I is 0.5: 1-40: 1.
Preferably, the molar ratio of the carbon monoxide to the compound I is 0.5: 1-25: 1.
Optionally, the volume fraction of carbon monoxide in the carbon monoxide-containing mixed gas is 20-100%.
Optionally, the carbon monoxide-containing gas mixture further comprises an inert gas. The inactive gas is at least one selected from hydrogen, nitrogen, argon, carbon dioxide, methane and ethane.
Optionally, the reactor is a fixed bed reactor.
Alternatively, when compound I is selected from dimethyl ether, the selectivity to methyl acetate is greater than 98%.
Alternatively, when the compound I is selected from methanol, the selectivity to acetic acid is greater than 85%.
Alternatively, when the compound I is selected from methyl halides, the selectivity of methyl acetate + acetic acid is greater than 80%.
The beneficial effects that this application can produce include:
1) the invention provides a catalyst for preparing methyl acetate andor acetic acid, the strong acid amount of the mordenite molecular sieve treated by organic alkali and the proportion of strong acid sites in 8-membered ring channels are obviously increased, and the catalyst has higher activity and target product selectivity.
2) The invention provides a method for modifying a molecular sieve, which comprises the following steps that through organic alkali water heat treatment, hydroxide ions can dissolve framework atoms, and non-framework atoms can be crystallized again to form the framework atoms under the induction of organic alkali cations, so that the acid distribution, the acid amount and the acid density of mordenite can be regulated and controlled on the premise of not obviously influencing the crystal morphology size and the pore structure, the acid placement of a molecular sieve catalyst can be regulated and controlled, and a new strategy is provided for the preparation of the molecular sieve catalyst.
3) The catalyst of the invention can be applied to a plurality of reactions including dimethyl ether carbonylation, methanol carbonylation and halogenated methane carbonylation, and has wide adjustable range of reaction process conditions and universality.
Detailed Description
The present application will be described in detail with reference to specific examples, but the present application is not limited to the following examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.
The product analysis method in the examples of the present application is as follows: the reacted gas is led into an on-line gas chromatograph for analysis through a pipeline. The gas chromatograph is of Agilent 7890A type and is provided with a PLOT Q capillary column and a TDX-1 packed column, and outlets of the PLOT Q capillary column and the TDX-1 packed column are respectively connected to a FID detector and a TCD detector.
The conversion of small molecules and selectivity of products in the examples of this application are calculated as follows:
in the examples, the conversion of dimethyl ether or methanol or methyl chloride and the selectivity of the product are calculated on the basis of the moles of small molecules:
conversion of dimethyl ether [ (mole number of dimethyl ether carbon in raw material gas) - (mole number of dimethyl ether carbon in product) ]/(mole number of dimethyl ether carbon in raw material gas) × (100%)
Methanol conversion rate [ (methanol carbon mole number in raw material gas) - (methanol carbon mole number in product) ] ÷ (methanol carbon mole number in raw material gas) × (100%)
Methyl chloride conversion rate [ (moles of methyl chloride carbon in feed gas) - (moles of methyl chloride carbon in product) ]/(moles of methyl chloride carbon in feed gas) × (100%)
Selectivity of methyl acetate for carbonylation of dimethyl ether was (2/3) × (methyl acetate carbon mole number in product) ÷ [ (dimethyl ether carbon mole number in feed gas) - (dimethyl ether carbon mole number in product) ] × (100%)
Selectivity of acetic acid in carbonylation of methanol (1/2) × (mole number of carbon acetate in product) ÷ [ (mole number of carbon methanol in raw material gas) - (mole number of carbon methanol in product) ] × (100%)
Selectivity of acetic acid in carbonylation of methyl halide (1/2) × (moles of acetic acid in product) ÷ [ (moles of methyl chloride carbon in feed gas) - (moles of methyl chloride carbon in product) ] × (100%)
Example 1
Adding 10 g of NH 4 the-MOR (Si/Al 10) molecular sieve is respectively put into 100ml of tetraethylammonium hydroxide solution with the mass fraction of 3.0% (the solid-to-liquid ratio is 1g:10ml), stirred until the mixture is uniform, then transferred into a 150ml high-pressure sealed reaction kettle, treated at 180 ℃ for 48 hours, filtered, washed by deionized water and dried to obtain a solid sample. The prepared sample is roasted for 4 hours at 550 ℃ in air atmosphere to prepare the catalyst No. 1.
Example 2
NH in example 1 4 Catalysts # 2, # 3 were prepared sequentially by replacing-MOR (Si/Al ═ 10) with Na-MOR (Si/Al ═ 10) and H-MOR (Si/Al ═ 10), keeping the other conditions the same as in example 1
Example 3
NH in example 1 4 The Si/Al atomic molar ratios of the MOR were changed to 6, 15, 20 and 50, respectively, and then catalysts No. 4, No. 5, No. 6 and No. 7 were prepared in this order in accordance with example 1.
Example 4
Catalysts # 8, # 9, and # 10 were prepared in the same order as in example 1 except that the tetraethylammonium hydroxide in example 1 was replaced with tetramethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
Example 5
Catalysts No. 11, No. 12, No. 13, No. 14, No. 15 and No. 16 were prepared by changing the treatment temperature in example 1 to 50 deg.C, 100 deg.C, 150 deg.C, 170 deg.C, 200 deg.C, 220 deg.C, and keeping the same conditions.
Example 6
The treatment time in example 1 was changed to 5 hours, 12 hours, 18 hours, 36 hours, 72 hours, and 100 hours, and the other conditions were kept the same, thereby preparing catalysts # 17, # 18, # 19, # 20, # 21, and # 22 in this order.
Example 7
The solid-to-liquid ratio in example 1 was changed to 1g:2ml, 1g:8ml, 1g:15ml, 1g:20ml, and the other conditions were kept the same, and catalysts # 23, # 24, # 25, and # 26 were prepared in this order.
Example 8
The mass concentration of tetraethyl ammonium hydroxide in the embodiment 1 is changed into 1.5%, 4.5%, 7.5%, 10.5% and 15.0%, and the other conditions are kept consistent, so that the catalysts 27#, 28#, 29#, 30#, and 31# are prepared in sequence.
Example 9
The tetraethyl ammonium hydroxide in example 1 was replaced with ethylenediamine, triethylamine, and n-butylamine organic amine, and the other conditions were kept the same, to prepare catalysts # 32, # 33, and # 34 in this order.
Example 10
The tetraethyl ammonium hydroxide in example 1 was replaced with triethylamine, and the triethylamine was contained in an aqueous solution in an amount of 0.5%, 10%, 25%, 50%, 75%, 100% by mass, under otherwise the same conditions as in example 1, to prepare catalysts # 35, # 36, # 37, # 38, # 39, and # 40 in this order.
Example 11
The time for calcining the solid sample prepared in the example 1 in the dry air is changed into 1.5 hours, 3 hours, 5 hours, 6 hours and 10 hours, and the other conditions are kept consistent, so that the catalysts 41#, 42#, 43#, 44#, and 45# are obtained in sequence.
Example 12
The calcination temperature in example 1 was changed to 450 ℃, 500 ℃, 600 ℃, 650 ℃ in this order, and the other conditions were kept the same, to prepare catalysts 46#, 47#, 48#, and 49# in this order.
Example 13
The catalyst is used for inspecting the performance of dimethyl ether carbonylation for producing methyl acetate according to the following conditions.
0.5 g of catalyst is loaded into a fixed bed reactor with the inner diameter of 8 mm, the temperature is increased to 400 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, the temperature is maintained for 2 hours, then the temperature is reduced to 200 ℃ under the same atmosphere, the pressure of a reaction system is increased to 2MPa by using reaction mixed gas, and simultaneously the reaction mixed gas passes through a catalyst bed layer from top to bottom. Wherein the space velocity of dimethyl ether feeding is 1.0h -1 (ii) a The molar ratio of carbon monoxide to dimethyl ether was 6:1, the carbon monoxide feed gas contained hydrogen, and the catalytic reaction was run for 10 hours, with the reaction results shown in table 1.
TABLE 1 results of dimethyl ether carbonylation catalytic evaluation of different catalysts
Figure BDA0002989141450000101
Figure BDA0002989141450000111
Figure BDA0002989141450000121
Example 14
The above catalyst was examined for the performance of methanol carbonylation to produce acetic acid under the following conditions.
The experimental catalysts are 1#, 5#, 10#, and 15# samples, 1g of the catalyst is loaded into a fixed bed reactor with an inner diameter of 8 mm, the temperature is increased to 400 ℃ at a speed of 2 ℃/min under the nitrogen atmosphere, and the temperature is keptKeeping for 2 hours, then cooling to the reaction temperature of 280 ℃ under the same atmosphere, using reaction mixed gas to increase the pressure of a reaction system to 2MPa, and simultaneously leading the reaction mixed gas to pass through a catalyst bed layer from top to bottom. Wherein the space velocity of methanol feeding is 1.0h -1 The molar ratio of carbon monoxide to methanol was 50:1, the carbon monoxide feed gas contained hydrogen, the catalytic reaction was run for 10 hours, and the reaction structure is shown in table 2.
TABLE 2 results of catalytic evaluation of methanol carbonylation with different catalysts
Figure BDA0002989141450000122
Example 15
The performance of the catalyst in the carbonylation of methyl halide to produce acetic acid was examined under the following conditions.
The experimental catalyst was a No. 5 sample, 1g of the catalyst was loaded into a fixed bed reactor with an internal diameter of 8 mm, the temperature was raised to 400 ℃ at a rate of 2 ℃/min under nitrogen atmosphere, the reaction temperature was maintained for 2 hours, the temperature was then lowered to 260 ℃ under the same atmosphere, the pressure of the reaction system was raised to 2.5MPa with the reaction mixture (methyl chloride/CO or methyl bromide/CO or methyl iodide/CO) while the reaction mixture passed through the catalyst bed from top to bottom. Wherein the space velocity of the feeding of the halogenated methane is 0.5h -1 The molar ratio of carbon monoxide to methyl halide is 20:1, carbon monoxide raw material gas does not contain other gases, the catalytic reaction is operated for 20 hours, and the reaction structure is shown in table 3.
TABLE 3 catalytic evaluation results of halomethane carbonylation
Figure BDA0002989141450000123
Figure BDA0002989141450000131
Example 16
The carbonylation of dimethyl ether to produce methyl acetate at different reaction temperatures.
The catalyst tested was a # 1 sample, 0.5 g of the catalyst was loaded into a fixed bed reactor having an internal diameter of 8 mm, raised to 400 ℃ at a rate of 2 ℃/min under nitrogen atmosphere, held for 2 hours, and then lowered to the reaction temperature under the same atmosphere. The system pressure is raised to 2MPa by the reaction mixed gas, and the reaction gas passes through the catalyst bed layer from top to bottom. Wherein the space velocity of dimethyl ether feeding is 1.0h -1 (ii) a The molar ratio of carbon monoxide to dimethyl ether is 6:1, the carbon monoxide feed gas contains hydrogen, and the reaction temperatures are 170 ℃, 190 ℃, 210 ℃, 230 ℃ and 300 ℃ respectively. The catalytic reaction was run for 10 hours and the results are shown in table 4.
TABLE 4 reaction results at different reaction temperatures
Reactor inlet temperature (. degree.C.) 170 190 210 230 300
Dimethyl ether conversion (%) 26.7 31.2 40.1 46.5 53.2
Methyl acetate selectivity (%) 98.6 99.2 98.9 98.5 98.2
Other Material Selectivity (%) 1.4 0.8 1.1 1.5 1.8
Example 17
The carbonylation of dimethyl ether to produce methyl acetate is carried out at different reaction pressures.
The experimental catalyst was 1# sample, the reaction pressure was 1, 3, 5 and 15Mpa, the reaction temperature was 200 ℃, and the other operation procedures were the same as in example 16. The reaction was run for 10 hours and the results are shown in table 5.
TABLE 5 reaction results at different reaction pressures
Reaction pressure (MPa) 1 3 5 15
Conversion ratio of dimethyl ether (%) 16.8 42.5 62.4 72.1
Methyl acetate selectivity (%) 98.6 99.0 99.4 99.6
Other Material Selectivity (%) 1.4 1.0 0.6 0.4
Example 18
Dimethyl ether carbonylation reaction results under different dimethyl ether space velocities.
The experimental catalyst is a 1# sample, and the mass space velocity of the dimethyl ether fed is 0.1h -1 、1.5h -1 、1.75h -1 、2.0h -1 、2.5h -1 And 4h -1 The reaction temperature was 200 ℃ and the other operating conditions were the same as in example 16, and the reaction results are shown in Table 6.
TABLE 6 reaction results at different space velocities of dimethyl ether
Dimethyl ether feed space velocity (h) -1 ) 0.1 1.5 1.75 2.0 4.0
Conversion ratio of dimethyl ether (%) 100 55.8 36.7 24.8 5.7
Methyl acetate selectivity (%) 99.7 99.6 99.5 99.6 99.3
Other Material Selectivity (%) 0.3 0.4 0.5 0.4 0.7
Example 19
The reaction results at different molar ratios of carbon monoxide to dimethyl ether.
The catalyst used in the experiment was sample # 1, the molar ratios of carbon monoxide to dimethyl ether were 0.1:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 15:1 and 25:1, the reaction temperature was 200 ℃, the other operating conditions were the same as in example 16, and the reaction results are shown in table 7.
TABLE 7 reaction results at different molar ratios of carbon monoxide to dimethyl ether
Figure BDA0002989141450000141
Example 20
Dimethyl ether carbonylation reaction results when the carbon monoxide-containing raw material gas contains inert gas.
The experimental catalyst is 1# sample, and the space velocity of dimethyl ether feeding is 0.5h -1 The raw material gas containing carbon monoxide contains inactive gas, the molar ratio of the raw material gas containing carbon monoxide to dimethyl ether is selected to be 5:1, other conditions are the same as in example 13, and the reaction results are shown in Table 8.
TABLE 8 results of reactions with inert gases in carbon monoxide-containing feed gases
Figure BDA0002989141450000151
Example 21
The carbonylation of methyl chloride at different reaction temperatures produced acetic acid/methyl acetate.
The catalyst tested was a # 5 sample, 1.0 gram of catalyst was loaded into a fixed bed reactor with an internal diameter of 8 mm, ramped up to 400 ℃ at a rate of 2 ℃/min under nitrogen atmosphere for 2 hours, and then ramped down to reaction temperature under the same atmosphere. The pressure of the system is raised to 2.5MPa by using reaction mixed gas, and the reaction gas passes through the catalyst bed layer from top to bottom. Wherein the space velocity of chloromethane feeding is 0.5h -1 (ii) a The molar ratio of carbon monoxide to methyl chloride is 20:1, and the reaction temperature is 180 ℃, 230 ℃, 280 ℃ and 300 ℃. The catalytic reaction was run for 20 hours and the results are shown in table 9.
TABLE 9 carbonylation results at different reaction temperatures for methyl chloride
Reactor inlet temperature (. degree.C.) 180 230 280 300
Methyl chloride conversion (%) 15.6 26.7 45.6 71.9
Acetic acid + methyl acetate selectivity (%) 99.7 96.7 88.5 80.5
Other Material Selectivity (%) 0.3 3.3 11.5 19.5
Example 22
The carbonylation of methyl chloride to produce acetic acid/methyl acetate was carried out at different reaction pressures.
The experimental catalyst 14# was used under the reaction pressures of 1.5, 3.5, 5 and 15MPa and the reaction temperature of 260 ℃ and the same procedure as in example 21. The reaction was run for 20 hours and the results are shown in table 10.
TABLE 10 results of methyl chloride carbonylation at various reaction pressures
Figure BDA0002989141450000152
Figure BDA0002989141450000161
Example 23
Results of reactions at different carbon monoxide to methyl chloride molar ratios.
The molar ratios of carbon monoxide to methyl chloride were 0.1:1, 5:1, 10:1 and 25:1, the reaction temperature was 260 ℃, the other operating conditions were the same as in example 21, and the reaction results are shown in table 11.
TABLE 11 reaction results for different carbon monoxide to methyl chloride molar ratios
Carbon monoxide/methyl chloride molar ratio 0.1:1 5:1 10:1 25:1
Methyl chloride conversion (%) 6.7 13.2 21.8 40.9
Acetic acid + methyl acetate selectivity (%) 86.1 90.1 98.2 98.8
Other Material Selectivity (%) 13.9 9.9 1.8 1.2
Example 24
Adding 10 g of NH 4 the-MOR (Si/Al 10) molecular sieve is respectively put into 100ml of tetraethylammonium hydroxide solution with the mass fraction of 3.0% (the solid-to-liquid ratio is 1g:10ml), stirred and mixed evenly, treated for 48 hours at 50 ℃, 100 ℃ and 150 ℃ under normal pressure, filtered, washed by deionized water and dried to obtain a solid sample. The prepared sample is calcined for 4 hours at 550 ℃ in air atmosphere to prepare catalysts 50#, 51# and 52 #. And the carbonylation of dimethyl ether to methyl acetate was examined under the same conditions as in example 13, as shown in Table 12.
TABLE 12 comparison of dimethyl ether carbonylation performance of catalyst treated under non-hermetic and hermetic conditions
Figure BDA0002989141450000162
Although the present invention has been described with reference to a specific embodiment, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A method of preparing a molecular sieve catalyst, the method comprising:
(1) heating a material containing a mordenite molecular sieve and an organic alkali source to obtain an intermediate product;
(2) and roasting the intermediate product to obtain the molecular sieve based catalyst.
2. The method according to claim 1, wherein the organic base source is selected from organic amines; the organic amine is selected from at least one of unitary organic amine, binary organic amine and ternary organic amine;
preferably, the mono-organic amine is at least one selected from compounds having the formula shown in formula I:
Figure FDA0002989141440000011
wherein R is 1 ，R 2 ，R 3 Is independently selected from H, C 1 ～C 10 Any one of the alkyl groups of (a);
R 1 ，R 2 ，R 3 cannot be simultaneously H;
preferably, the mono-organic amine is selected from alkyl ammonium hydroxides; the alkyl ammonium hydroxide is selected from at least one of compounds having a chemical formula shown in formula II:
Figure FDA0002989141440000012
wherein R is 4 ，R 5 ，R 6 ，R 7 Independently selected from C 1 ～C 10 Any one of the alkyl groups of (1).
3. The method according to claim 1, wherein the heating conditions are: the temperature is 50-220 ℃, and the time is 5-100 hours;
preferably, the roasting conditions are as follows: the temperature is 450-650 ℃, and the time is 1.5-10 hours.
4. The preparation method of claim 1, wherein the mordenite molecular sieve has a silicon-aluminum atomic ratio of: Si/Al is 6-50;
preferably, the mordenite molecular sieve is selected from Na-MOR, NH 4 At least one of-MOR, H-MOR molecular sieves.
5. The method according to claim 1, wherein the organic base source further comprises a solvent; the solvent is selected from water;
preferably, the mass content of the organic alkali in the organic alkali source is 0.5-99.9%;
preferably, the ratio of the addition amount of the mordenite molecular sieve and the organic alkali source is 1g:2 ml-1 g:20 ml.
6. A molecular sieve catalyst, characterized in that the molecular sieve catalyst comprises the molecular sieve catalyst obtained by the preparation method according to any one of claims 1 to 5.
7. A method for preparing acetic acid and/or methyl acetate is characterized in that a compound I and mixed gas containing carbon monoxide are contacted and reacted in the presence of a catalyst to obtain methyl acetate or acetic acid;
wherein the catalyst is selected from at least one of the molecular sieve catalyst of claim 6, the molecular sieve catalyst prepared by the process of any one of claims 1 to 5;
the compound I is selected from at least one of methanol, halogenated methane and dimethyl ether.
8. The method according to claim 7, wherein the reaction conditions are: the temperature is 150-320 ℃, the pressure is 0.5-25.0 MPa, and the time is 10-24 h;
preferably, the mass space velocity of the feed of the compound I is 0.05-5 h -1 。
9. The method according to claim 7, wherein the molar ratio of the carbon monoxide to the compound I is 0.1:1 to 50: 1;
preferably, the volume fraction of carbon monoxide in the mixed gas containing carbon monoxide is 20-100%.
10. The production method according to claim 7, wherein the mixed gas containing carbon monoxide further comprises an inert gas; the inactive gas is at least one selected from hydrogen, nitrogen, argon, carbon dioxide, methane and ethane.
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