CN108097324B - Catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof - Google Patents
Catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- 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
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- 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
Abstract
The invention relates to a catalyst for preparing acrylic acid and methyl acrylate and a preparation method thereof. The method comprises the following steps: (1) treating the molecular sieve with MOR configuration by using alkali, drying and roasting to obtain an alkali-modified molecular sieve with MOR configuration; (2) washing the alkali-modified molecular sieve with MOR configuration to neutrality, adding a binder, molding and roasting; (3) treating the base-modified MOR configuration molecular sieve of step (2) in an atmosphere containing pyridine and/or pyridine substitutes to produce a catalyst comprising the base-modified MOR molecular sieve.
Description
Technical Field
The invention relates to a catalyst for preparing acrylic acid and methyl acrylate and a preparation method thereof.
Background
Acrylic acid and methyl acrylate are important chemical raw materials, can be used as coatings, flocculating agents, dispersing agents, binding agents and the like, are widely applied to the industries of buildings, water treatment, daily chemical industry, soil treatment, leather and the like, and are closely related to the daily life of people. The most common process for the preparation of acrylic acid and methyl acrylate in the industry today is the two-stage oxidation of propylene, i.e. the first oxidation of propylene to acrolein, which is further oxidized to give acrylic acid. However, the raw material propylene is derived from petroleum, belongs to non-renewable resources and is not in accordance with the sustainable development concept.
With the rapid development of C1 chemistry, acetic acid and methyl acetate production capacity became excessive. The method for preparing acrylic acid and methyl acrylate by using cheap raw materials of acetic acid and methyl acetate as raw materials provides a feasible route for continuously preparing acrylic acid and methyl acrylate.
The catalysts adopted in the research are mostly alkaline catalysts or acid-base bifunctional catalysts, and the preparation process generally adopts methods such as impregnation, ion exchange and coprecipitation to load active components on a carrier, so that the defects of complex preparation, complex influencing factors, low repeatability, easy loss of active components and the like exist, and the requirement of industrial large-scale production cannot be met.
Disclosure of Invention
One of the objects of the present invention is to provide a catalyst for the production of acrylic acid and/or methyl acrylate from a feedstock comprising carbon monoxide and a formaldehyde-based compound selected from at least one of formaldehyde, methylal, trioxymethylene, said catalyst comprising a base-modified molecular sieve having the MOR configuration.
In one embodiment, the alkali modified molecular sieve having MOR configuration has a silicon to aluminum atomic ratio of from 3 to 100.
In one embodiment, it is preferred that the alkali modified molecular sieve having the MOR configuration has a silicon to aluminum atomic ratio of 6 to 30.
In one embodiment, the catalyst comprises a pyridine compound, or the base-modified molecular sieve having MOR configuration comprises a pyridine compound.
In one embodiment, the catalyst contains pyridine compound with mass content of 0.01-15%, or the alkali modified molecular sieve with MOR configuration contains pyridine compound with mass content of 0.01-15%.
In one embodiment, the catalyst contains pyridine compound with mass content of 1-10%, or the alkali modified molecular sieve with MOR configuration contains pyridine compound with mass content of 1-10%.
In one embodiment, the catalyst contains 3 to 7 mass% of pyridine compound, or the alkali-modified molecular sieve with MOR configuration contains 3 to 7 mass% of pyridine compound.
In one embodiment, the catalyst contains pyridine compounds with the mass content of 4% to 6%, or the alkali-modified molecular sieve with MOR configuration contains pyridine compounds with the mass content of 4% to 6%.
In one embodiment, the pyridines comprise pyridine and/or substituted pyridine selected from one to three of the five H in the pyridine ring independently selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2At least one of the compounds substituted with the substituent(s) in (1).
In one embodiment, the pyridine compound comprises monomethyl pyridine, dimethyl pyridine, trimethyl pyridine, ethyl pyridine, nitro pyridine, fluoro pyridine, chloro pyridine, bromo pyridine, and iodo pyridine.
In a specific embodiment, the formaldehyde-based compound is at least one of formaldehyde, methylal and trioxymethylene.
A second object of the present invention provides a process for preparing a catalyst according to the first object of the present invention, which comprises the steps of: (1) treating the molecular sieve with MOR configuration by using alkali to obtain an alkali-modified molecular sieve with MOR configuration; (2) washing the alkali-modified molecular sieve with MOR configuration to neutrality, adding a binder, molding and roasting; (3) and (3) carrying out ammonium exchange, washing, drying and roasting on the alkali-modified molecular sieve with the MOR configuration in the step (2), and then treating in an atmosphere containing a pyridine compound to obtain the catalyst containing the alkali-modified MOR molecular sieve.
In one embodiment, in step (1), the molecular sieve having MOR configuration is treated in an alkaline solution at 30 ℃ to 100 ℃ for 1h to 10 h.
In one embodiment, in step (1), the molecular sieve having MOR configuration is treated in an alkaline solution at 40 ℃ to 90 ℃ for 2h to 5 h.
In one embodiment, the base is sodium hydroxide and/or potassium hydroxide.
In one embodiment, the concentration of the base in the solution is from 0.05mol/L to 1 mol/L; preferably, the concentration of the base in the solution is 0.1mol/L to 0.7 mol/L.
In one embodiment, the binder is selected from at least one of silica, zirconia, alumina, magnesia, titania, pseudo-boehmite, kaolin, montmorillonite.
In one embodiment, it is preferable that the binder is contained in the catalyst in an amount of 1 to 70% by mass.
In one embodiment, it is more preferable that the binder is contained in the catalyst in an amount of 10 to 50% by mass.
In one embodiment, in step (3), the pyridine compound-containing atmosphere has a volume percentage of 0.01% to 15%.
In one embodiment, in step (3), the volume percentage of the pyridine compound in the atmosphere containing the pyridine compound is 1% to 10%.
In one embodiment, the pyridines comprise pyridine and/or substituted pyridine selected from one to three of the five H in the pyridine ring independently selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2At least one of the compounds substituted with the substituent(s) in (1).
In one embodiment, the pyridine compound comprises monomethyl pyridine, dimethyl pyridine, trimethyl pyridine, ethyl pyridine, nitro pyridine, fluoro pyridine, chloro pyridine, bromo pyridine, and iodo pyridine.
In one embodiment, the conditions of the calcination in steps (2) and (3) are independently: air atmosphere, 350-680 ℃, 1-10 h.
In one embodiment, it is preferred that the conditions of the calcination in steps (2) and (3) are independently: air atmosphere, 400 to 600 ℃ and 2 to 6 hours.
In one embodiment, in step (3), the treatment conditions are: 240 ℃ to 400 ℃, 0.5 hour to 24 hours.
In one embodiment, preferably in step (3), the treatment conditions are: 250 to 350 ℃ for 2 to 10 hours.
In one embodiment, the reaction conditions for the preparation of acrylic acid and/or methyl acrylate are as follows: the temperature is 180 ℃ to 400 ℃, the pressure is 0.2MPa to 15.0MPa, and the total feeding space velocity of the raw material gas is 0.05h-1To 10.0h-1。
In one embodiment, the reaction conditions for the preparation of acrylic acid and/or methyl acrylate are as follows: the temperature is 300-350 ℃, the pressure is 0.2-5.0 Mpa, and the total feed space velocity of the raw material gas is 0.3h-1To 2h-1。
In one embodiment, the ratio of the molar amount of carbon monoxide to the total molar amount of formaldehydes is from 1:1 to 200: 1.
In one embodiment, the ratio of the molar amount of carbon monoxide to the total molar amount of formaldehydes is from 2:1 to 100: 1.
In one embodiment, the ratio of the molar amount of carbon monoxide to the total molar amount of formaldehydes is 2: 1.
In a specific embodiment, the formaldehyde-based compound is at least one of formaldehyde, methylal and trioxymethylene.
In a specific embodiment, the reactor of the reaction zone is selected from one of a tank reactor, a fixed bed reactor, a moving bed reactor, and a fluidized bed reactor.
In one embodiment, there may be one reactor, or a plurality of reactors connected in series or parallel.
The beneficial effects of the invention include but are not limited to:
(1) the catalyst for producing acrylic acid and methyl acrylate based on methylal and carbon monoxide has the advantages of simple industrial preparation, high selectivity of target products, good catalyst stability and the like. The activity and the stability of the catalyst are effectively improved, the regeneration times of the catalyst are reduced, the production process of acrylic acid and methyl acrylate by methylal and the production cost of the catalyst are simplified, and the production operation cost is reduced.
(2) The catalyst consumption of unit product is reduced, and the investment is reduced.
(3) The regeneration, activation and loading and unloading frequency of the catalyst are reduced, the emission of waste gas in the regeneration process of the catalyst is reduced, and the production and maintenance cost is reduced.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
In the present invention, methylal is reacted with carbon monoxide to produce compounds such as dimethyl ether, acetic acid, methyl acetate, acrylic acid and methyl acrylate. The generation of the product can be directionally controlled by controlling reaction conditions of different temperatures and pressures, raw material compositions in different proportions and other conditions through thermodynamic and kinetic factors, and the method is carried out according to the following equation. Ideally, the total carbon selectivity of acrylic acid in the product is 60% and the total carbon selectivity of acetic acid is 40%, with no other by-products being formed. If the product selectivity is calculated by taking methylal as a single reaction raw material, the carbon mole selectivity of acrylic acid is 50 percent, and the carbon mole selectivity of acetic acid is 50 percent.
The raw materials and products of the invention are detected by an Aligent 7890A gas chromatography of Agilent and an FFAP capillary column of Agilent.
According to one embodiment of the present invention, a fixed bed reactor is used, the catalyst packing mass is 0.5 to 3.0g, the reaction temperature is 180 to 350 ℃, and the reaction pressure is 0.1 to 10 MPa. The raw material methylal is carbon monoxide, and saturated steam carrying methylal enters a fixed bed reactor under different water bath temperatures (0-50 ℃) to obtain methylal raw material gas with different volume contents. The saturated vapor pressure of the starting methylal under different temperature conditions is calculated as shown in the following formula:
ln(p1*/p2*)＝-ΔvapHm/8.3145×(1/T1-1/T2)
wherein p1 and p2 represent the saturated vapor pressures of the acetal at different temperatures (T1, T2), respectively. The molar evaporation enthalpy Δ vapHm is known to be 43.99KJ/mol, boiling point 42.3 ℃, so that the saturated vapor pressure of methylal at any temperature can be calculated. The amount of starting methylal material entering the reactor per unit time can be calculated from the saturated vapor pressure.
The conversion and selectivity in the examples of the invention were calculated as follows:
methylal conversion [ (moles of methylal in feed) - (moles of methylal in discharge) ]/(moles of methylal in feed) × (100%)
Acrylic acid selectivity 2/3 (moles of acrylic acid in output) ÷ [ (moles of methylal carbon in input) - (moles of methylal carbon in output) ] × (100%)
Methyl acrylate selectivity 3/4 (moles of methyl acrylate carbon on discharge) ÷ [ (moles of methylal carbon on feed) - (moles of methylal carbon on discharge) ] × (100%)
Acetic acid selectivity 1/2 (moles of acetic acid in the output) ÷ [ (moles of methylal carbon in the input) - (moles of methylal carbon in the output) ] × (100%)
Methyl acetate selectivity is 2/3 (moles of methyl acetate carbon in the output) ÷ [ (moles of methylal carbon in the input) - (moles of methylal carbon in the output) ] × (100%).
Analyzing organic matters in the catalyst/molecular sieve, and operating the following steps:
weighing 100mg of catalyst sample, and filling the catalyst sample into a polytetrafluoroethylene bottle with a cover; adding 1ml of 20% hydrofluoric acid aqueous solution, shaking uniformly, standing for 1h to completely dissolve the molecular sieve catalyst; to the dissolved solution was added 1ml of methylene Chloride (CH)2Cl2) Extracting an organic phase, shaking uniformly, transferring to a separating funnel of a polytetrafluoroethylene piston, standing for layering, and discharging lower-layer oily liquid; by using an agilawoodLorentz GC-MS (Agilent 7890A/5975C GC/MSD) analysis. Chlorobenzene or hexachloroethane was added as an internal standard to the dichloromethane solution (1. mu. l C)6H5Cl/100ml CH2Cl2Or 10ppm of C2Cl6). The analysis was performed using an HP-5MS column with an initial column box temperature of 35 deg.C, 5 deg.C/min ramp to 300 deg.C and hold for 10 min.
Example 1
100 g of MOR (Si/Al ═ 6.5) molecular sieve was placed in 1000mL of 0.5mol/L NaOH solution at 80 ℃ for 2 hours, filtered and washed to neutrality. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding and forming, roasting at 550 ℃ for 4 hours, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 4 hours, treating the prepared sample at 300 ℃ for 2 hours in an atmosphere containing 7.5% volume of pyridine in a gas phase, and preparing the catalyst No. 1. The pyridine content in analyzed catalyst # 1 was 6%.
Example 2
100 g of MOR molecular sieve with Si/Al ratios of 5, 25, 50 and 100 were placed in 1000ml of 0.5mol/L KOH solution at 80 ℃ for 2 hours, filtered and washed to neutrality. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding and forming, roasting at 550 ℃ for 4 hours, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 4 hours, treating the prepared sample at 300 ℃ under the atmosphere of pyridine with 10% volume in gas phase for 2 hours to prepare methylal conversion catalysts 2#, 3#, 4#, and 5 #. The pyridine content in analyzed catalyst 2# was 5.8%; the pyridine content in catalyst 3# was 5.9%; the pyridine content in catalyst 4# was 6.0%; the pyridine content in catalyst # 5 was 5.8%.
Example 3
100 g of MOR molecular sieve is put into 1000mL of NaOH solutions with the concentrations of 0.05mol/L, 0.1mol/L, 0.7mol/L and 1mol/L respectively to be treated for 2 hours at the temperature of 80 ℃, and the other conditions are consistent with those of the example 1, so that methylal conversion catalysts 6#, 7#, 8#, and 9# are prepared. The pyridine content in analyzed catalyst # 6 was 6.1%; the pyridine content in catalyst 7# was 6.0%; the pyridine content in catalyst 8# was 5.9%; the pyridine content in catalyst # 9 was 6.0%.
Example 4
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L respectively to be treated for 2 hours at 30 ℃, 40 ℃, 70 and 90 ℃ respectively, and the rest conditions are consistent with the conditions in the example 1, thus preparing the methylal carbonylation conversion catalysts 10#, 11#, 12#, 13#, and 14 #. The pyridine content in analyzed catalyst 10# was 6.0%; the pyridine content in catalyst 11# was 5.9%; the pyridine content in catalyst 12# was 5.8%; the pyridine content in catalyst 13# was 5.8%; the pyridine content in catalyst # 14 was 6.1%.
Example 5
The weight contents of the binding agent pseudo-boehmite are 10%, 30% and 50%, and the other conditions are the same as the examples, and the catalysts 15#, 16#, and 17# are prepared. The pyridine content in analyzed catalyst 15# was 5.0%; the pyridine content in catalyst 16# was 4.2%; the pyridine content in catalyst 17# was 3.5%.
The binding agent pseudo-boehmite is respectively replaced by silica, titanium oxide, silica and alumina, silica and titanium oxide, alumina and titanium oxide, the weight content of the binding agent is 20 percent, and the other conditions are the same as those in the example 1, and the methylal conversion catalysts 18#, 19#, 20#, 21#, and 22# are prepared. The pyridine content in analyzed catalyst 18# was 4.5%; the pyridine content in catalyst 19# was 4.9%; the pyridine content in catalyst 20# was 4.3%; the pyridine content in catalyst 21# was 4.5%; the pyridine content in catalyst 22# was 4.5%.
Example 6
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L to be respectively treated for 1, 6 and 10 hours at the temperature of 80 ℃, and the other conditions are consistent with the example 1, thus preparing the methylal conversion catalysts 23#, 24#, and 25 #. The pyridine content in analyzed catalyst # 23 was 6.1%; the pyridine content in catalyst No. 24 was 6.0%; the pyridine content in catalyst # 25 was 6.1%.
Example 7
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding and forming, roasting at 550 ℃ for 4 hours, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 400 ℃, 500 ℃ and 650 ℃ for 4 hours respectively, treating the obtained sample at 300 ℃ in a gas phase under the atmosphere of pyridine with the volume of 1% for 2 hours, and preparing the methylal conversion catalysts 26#, 27#, and 28 #. The pyridine content in analyzed catalyst 26# was 4.1%; the pyridine content in catalyst 27# was 4.2%; the pyridine content in catalyst No. 28 was 4.0%.
Example 8
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding and forming, roasting at 550 ℃ for 4 hours, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 2, 6 and 10 hours respectively, treating the obtained sample at 300 ℃ in an atmosphere containing 15% volume of pyridine in a gas phase for 2 hours, and preparing methylal conversion catalysts 29#, 30#, and 31 #. The pyridine content in analyzed catalyst 29# was 4.0%; the pyridine content in catalyst # 30 was 4.1%; the pyridine content in catalyst # 31 was 4.2%.
Example 9
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding into strips, forming, roasting, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 4 hours respectively, treating the obtained samples at 240 ℃, 280 ℃, 350 ℃, 400 ℃ and under the atmosphere of pyridine containing 0.01% in gas phase for 2 hours respectively, and preparing methylal conversion catalysts 32#, 33#, 34#, and 35 #. The pyridine content in analyzed catalyst 32# was 3.8%; the pyridine content in catalyst # 33 was 3.9%; the pyridine content in catalyst 34# was 3.8%; the pyridine content in catalyst # 35 was 3.7%.
Example 10
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding and forming, roasting, exchanging three times (2 hours/time) with 0.5mol/L ammonium nitrate, washing with deionized water, drying, roasting at 550 ℃ for 4 hours respectively, and treating the obtained sample at 300 ℃ for 2 hours in an atmosphere of 7.5% by volume of monomethyl pyridine, dimethyl pyridine, trimethyl pyridine, ethyl pyridine, nitro pyridine, fluoro pyridine, chloro pyridine, bromo pyridine and iodo pyridine in a gas phase respectively to obtain the methylal conversion catalysts 36#, 37#, 38#, 39#, 40#, 41#, 42#, 43#, and 44. The content of pyridine compound in the analyzed catalyst 36# was 3.9%; the content of the pyridine compound in the catalyst 37# is 4.0%; the content of the pyridine compound in the catalyst 38# was 4.1%; the content of the pyridine compound in the catalyst 39# was 3.9%; the content of the pyridine compound in the catalyst 40# is 3.8%; the content of the pyridine compound in the catalyst 41# was 4.1%; the content of the pyridine compound in the catalyst 42# was 4.2%; the content of the pyridine compound in the catalyst 43# was 4.2%; the content of the pyridine compound in catalyst 44# was 4.0%.
Example 11
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding into strips, forming, roasting, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 4 hours respectively, treating the obtained sample at 300 ℃ for 2 hours in an atmosphere containing 0.01%, 2%, 8% and 15% of pyridine in volume in gas phase respectively, and preparing the methylal conversion catalysts 45#, 46#, 47#, and 48 #. The pyridine content in analyzed catalyst 45# was 0.1%; the pyridine content in catalyst 46# was 1.0%; the pyridine content in catalyst 47# was 6.0%; the pyridine content in catalyst 48# was 10.2%.
Example 12
100 g of MOR molecular sieve is put into 1000mL of NaOH solution with the concentration of 0.5mol/L for 2 hours at 80 ℃, and filtered and washed to be neutral. Taking out 80g of MOR molecular sieve after alkali treatment, mixing 28g of pseudo-boehmite and 10% of dilute nitric acid uniformly, extruding into strips, forming, roasting, exchanging with 0.5mol/L ammonium nitrate for three times (2 hours/time), washing with deionized water, drying, roasting at 550 ℃ for 4 hours respectively, treating obtained samples at 300 ℃ for 0.5, 2, 4, 10, 20 and 24 hours in an atmosphere containing 7.5% of pyridine respectively, and preparing the methylal conversion catalysts 49#, 50#, 51#, 52#, 53#, and 54 #. The pyridine content in analyzed catalyst 49# was 1.8%; the pyridine content in catalyst 50# was 3.9%; the pyridine content in catalyst 51# was 5.2%; the pyridine content in catalyst 52# was 6.1%; the pyridine content in catalyst 53# was 6.2%; the pyridine content in catalyst 54# was 6.5%.
Comparative example 1 preparation of Cs-based catalyst
(1) Weighing 82.9g of cesium acetate, 5.5g of zirconium nitrate and 5.0g of cerium nitrate, and adding 120mL of deionized water for dissolving to prepare an aqueous solution;
(2) weighing 170g of silicon dioxide and 28g of magnesium oxide, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 4 hours, and roasting at 400 ℃ for 4 hours to obtain a metal oxide catalyst, wherein the sample is marked as D0#。
Comparative example 2
The catalyst containing the unmodified MOR molecular sieve of atomic silica to alumina ratio 6.5 of example 1 was numbered D1 #.
Comparative example 3
The catalysts containing unmodified MOR molecular sieves with atomic Si/Al ratios of 5, 25, 50, 100 in example 2 were numbered D2#, D3#, D4#, D5 #.
EXAMPLE 13 evaluation of catalyst
10g of the prepared catalyst sample was placed in a stainless steel fixed bed reaction tube having an inner diameter of 8.5mm, and introducedCarbon monoxide, and boosting the pressure of a reaction system to 5 MPa; then according to the reaction space velocity WHSV of 3000h-1The research on the carbonylation conversion of methylal and carbon monoxide is carried out under the condition of the reaction temperature of 240 ℃. The raw materials and the obtained product were analyzed on-line by Agilent 7890A gas chromatography (column: HP-PLOT-Q capillary column, Porapak-Q packed column; detector: FID, TCD), and the reaction conditions and results are shown in Table 1, wherein the reaction pressures of test numbers 2, 3, 4, 5 are 0.2MPa, 4MPa, 5MPa, and 15MPa, respectively, and the rest of the test pressures are 3 MPa. .
TABLE 1
As can be seen from the data in Table 1, the selectivity of acrylic acid and methyl acrylate is remarkably high in the technical scheme of the invention compared with the technical scheme of the comparative example; in particular, test No. 1 in Table 1 compares with test Nos. 56 and 58, catalyst D1 of the comparative example#The conversion rate and selectivity decrease rapidly with the increase of the reaction time, and the catalyst 1 prepared by the technical scheme of the invention#After 1500h of reaction, the conversion rate and the selectivity are still high, and the service life is far longer than that of the catalyst D1 of comparative example 2#Also much larger than catalyst D0 of comparative example 1#。
The above description is only for the purpose of illustrating the present invention and is not intended to limit the present invention in any way, and the present invention is not limited to the above description, but rather should be construed as being limited to the scope of the present invention.
Claims (19)
1. A process for the preparation of a catalyst for the production of acrylic acid and/or methyl acrylate from a feedstock comprising carbon monoxide and a formaldehyde-based compound, the process comprising the steps of:
(1) treating the molecular sieve with MOR configuration by using alkali to obtain an alkali-modified molecular sieve with MOR configuration;
(2) washing the alkali-modified molecular sieve with MOR configuration to neutrality, adding a binder, molding and roasting;
(3) after the alkali-modified MOR-configuration molecular sieve treated in the step (2) is subjected to ammonium exchange, washing, drying and roasting, the alkali-modified MOR-configuration molecular sieve is treated in an atmosphere containing pyridine compounds, so that a catalyst containing the alkali-modified MOR molecular sieve is prepared;
in the step (3), the treatment conditions under the atmosphere containing the pyridine compound are as follows: 240 ℃ to 400 ℃, 0.5 hour to 24 hours;
the alkali-modified molecular sieve with MOR configuration contains pyridine compounds with the mass content of 0.01-15% after the pyridine compounds are treated; the pyridine compound comprises pyridine and/or substituted pyridine, wherein one to three H in five H selected from pyridine rings are independently selected from F, Cl, Br, I and CH3、CF3、CH3CH2、NO2At least one of the compounds substituted with the substituent(s) in (b);
the formaldehyde compound is at least one selected from formaldehyde, methylal and trioxymethylene.
2. The process according to claim 1, wherein the base-modified molecular sieve having MOR configuration comprises a pyridine compound content of 4 to 6% by mass after the pyridine compound treatment.
3. The method according to claim 1, wherein in step (3), the treatment conditions under the atmosphere containing the pyridine compound are as follows: 250 to 350 ℃ for 2 to 10 hours.
4. The process of claim 1, wherein the base-modified molecular sieve having the MOR configuration has a silicon to aluminum atomic ratio of from 3 to 100.
5. The process of claim 1, wherein the base-modified molecular sieve having the MOR configuration has a silicon to aluminum atomic ratio of from 6 to 30.
6. The process according to claim 1, characterized in that in step (1), the molecular sieve having MOR configuration is treated in alkaline solution at 30 to 100 ℃ for 1 to 10 h.
7. The process according to claim 1, characterized in that in step (1), the molecular sieve having MOR configuration is treated in alkaline solution at 40 to 90 ℃ for 2 to 5 h.
8. The method of claim 1, wherein the base is sodium hydroxide and/or potassium hydroxide.
9. The method of claim 1, wherein the concentration of the base in the solution is 0.05mol/L to 1 mol/L.
10. The method of claim 1, wherein the concentration of the base in the solution is 0.1mol/L to 0.7 mol/L.
11. The method of claim 1, wherein the binder is selected from at least one of silica, zirconia, alumina, magnesia, titania, pseudoboehmite, kaolin, and montmorillonite.
12. The method of claim 1, wherein the binder is present in the catalyst in an amount of 1 to 70% by mass.
13. The method of claim 1, wherein the binder is present in the catalyst in an amount of 10 to 50% by mass.
14. The method of claim 1, wherein in step (3), the pyridine compound is contained in the atmosphere containing the pyridine compound in an amount of 0.01 to 15 vol%.
15. The method according to claim 1, wherein in step (3), the pyridine compound-containing atmosphere contains 1 to 10 vol% of pyridine compound.
16. The method of claim 1, wherein the firing conditions in steps (2) and (3) are independently: air atmosphere, 350-680 ℃, 1-10 h.
17. The method of claim 1, wherein the firing conditions in steps (2) and (3) are independently: air atmosphere, 400 to 600 ℃ and 2 to 6 hours.
18. The process according to claim 1, characterized in that the reaction conditions for the preparation of acrylic acid and/or methyl acrylate are as follows:
the temperature is 180 ℃ to 400 ℃, the pressure is 0.2MPa to 15.0MPa, and the total feeding space velocity of the raw material gas is 0.05h-1To 10.0h-1。
19. The process according to claim 1, characterized in that the reaction conditions for the preparation of acrylic acid and/or methyl acrylate are as follows:
the temperature is 300-350 ℃, the pressure is 0.2-5.0 Mpa, and the total feed space velocity of the raw material gas is 0.3h-1To 2h-1。
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| CN111517956A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate and co-producing methyl acrylate by dimethyl ether |
| CN111514940A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Catalyst for one-step preparation of acetone, preparation method and application thereof |
| CN114249626A (en) * | 2020-09-24 | 2022-03-29 | 中国科学院大连化学物理研究所 | Preparation method of olefin |
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