CN119608224A - A modified molecular sieve catalyst and its preparation method and application - Google Patents
A modified molecular sieve catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN119608224A CN119608224A CN202411544328.XA CN202411544328A CN119608224A CN 119608224 A CN119608224 A CN 119608224A CN 202411544328 A CN202411544328 A CN 202411544328A CN 119608224 A CN119608224 A CN 119608224A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- treatment
- sieve catalyst
- methyl acrylate
- acetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a modified molecular sieve catalyst, a preparation method and application thereof. The modified molecular sieve catalyst comprises a molecular sieve and an active component loaded on at least part of pores and/or at least part of surfaces of the molecular sieve, wherein the active component comprises a palladium simple substance, a nickel simple substance and a copper simple substance. The modified molecular sieve catalyst has excellent catalytic activity, can be used in the catalytic reaction of synthesizing methyl acrylate by acetylene carbonyl, can improve the conversion rate of acetylene and the selectivity of methyl acrylate, can be recycled, and reduces the catalytic cost.
Description
Technical Field
The invention relates to a modified molecular sieve catalyst, a preparation method and application thereof, and belongs to the technical field of chemical industry.
Background
Among the existing bulk chemicals, methyl acrylate is an important fine chemical raw material, can be used as an intermediate for organic synthesis and a monomer for synthesizing a high molecular compound, and a high polymer prepared from the methyl acrylate not only has colorless and transparent optical properties, but also has the characteristics of excellent ultraviolet light resistance, heat resistance, oil resistance, water light resistance, strong adhesion, strong stability and the like, and has wide application in the fields of paint, leather processing, adhesives, coatings, papermaking, medicine, chemical fiber and the like.
The acetylene carbonylation process is one of the processes for preparing methyl acrylate by catalytic reaction of acetylene, carbon monoxide and methanol in the presence of a catalyst to produce methyl acrylate. Acetylene carbonylation processes are receiving increasing attention and application because acetylene, carbon monoxide and methanol are all readily available industrial materials, and the process is simple and environmentally friendly and the reaction conditions are mild. However, the catalysts used in the current acetylene carbonylation processes have problems of low conversion of acetylene and poor selectivity to methyl acrylate during the catalytic reaction.
Disclosure of Invention
The invention provides a modified molecular sieve catalyst which has excellent catalytic activity, can be used for the catalytic reaction of synthesizing methyl acrylate by acetylene carbonyl, can improve the conversion rate of acetylene and the selectivity of methyl acrylate, can be recycled and used, and reduces the catalytic cost.
The invention also provides a preparation method of the modified molecular sieve catalyst, which can prepare the modified molecular sieve catalyst, is simple and is suitable for wide popularization and application.
The invention also provides a method for synthesizing methyl acrylate by using the acetylene carbonylation, which uses the modified molecular sieve catalyst to carry out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide to obtain methyl acrylate. The method can realize the recycling of the modified molecular sieve catalyst and reduce the catalytic cost.
The invention provides a modified molecular sieve catalyst, which comprises a molecular sieve and an active component loaded on at least part of pores and/or at least part of surfaces of the molecular sieve;
the active component comprises a palladium simple substance, a nickel simple substance and a copper simple substance.
The modified molecular sieve catalyst as described above, the molecular sieve comprising at least one of a ZSM-5 molecular sieve, a ZSM-35 molecular sieve, a MOR molecular sieve, and an EMT molecular sieve, and/or,
In the modified molecular sieve catalyst, the mass ratio of the palladium simple substance to the nickel simple substance to the copper simple substance is (0.35-1.42): 1.50-5.25): 0.85-2.35.
The invention also provides a preparation method of the modified molecular sieve catalyst, which comprises the following steps:
the method comprises the steps of carrying out impregnation treatment on a molecular sieve by using a mixed solution comprising a palladium source, a nickel source and a copper source to obtain a molecular sieve catalyst precursor, or respectively carrying out impregnation treatment on the molecular sieve by using a palladium source solution, a nickel source solution and a copper source solution to obtain a molecular sieve precursor;
and sequentially roasting and reducing the molecular sieve catalyst precursor to obtain the modified molecular sieve catalyst.
The preparation method of the modified molecular sieve catalyst comprises the steps of roasting, namely, the preparation method comprises the steps of pre-roasting and main roasting;
the temperature of the pre-firing treatment is less than the temperature of the main firing treatment.
The preparation method of the modified molecular sieve catalyst comprises the steps of pre-roasting at 320-460 ℃ for 0.5-4 hours and/or,
In the main roasting treatment, the temperature is 460-620 ℃ and the time is 3-5 h, and/or,
In the reduction treatment, the temperature is 330-380 ℃ and the time is 2-4 hours.
The invention also provides a method for synthesizing methyl acrylate by using the acetylene carbonylation, which comprises the step of carrying out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide by using the modified molecular sieve catalyst to obtain the methyl acrylate.
The method for synthesizing methyl acrylate by carbonylation of acetylene comprises the steps of (1.5-3.5): 3-10% of the molar ratio of acetylene, carbon monoxide and methanol in the raw material system and/or,
The weight ratio of the modified molecular sieve catalyst in the total weight of the raw material system is 0.001-6%.
According to the method for synthesizing methyl acrylate by carbonylation of acetylene, in the catalytic reaction, the temperature is 80-220 ℃, the pressure is 3-12 MPaG, and the time is 0.1-1 h.
The method for synthesizing methyl acrylate by the carbonylation of acetylene, which is described above, further comprises post-treatment after the catalytic reaction,
The post-treatment comprises the steps of carrying out gas-liquid separation treatment on the mixed material obtained after the catalytic reaction to obtain a gas phase and a liquid phase;
Carrying out rough distillation treatment on the liquid phase to obtain a light component comprising methanol and methyl acrylate and methanol;
and under the action of an entrainer, carrying out azeotropic distillation treatment on the light component to obtain methyl acrylate.
The method for synthesizing methyl acrylate by the carbonylation of acetylene, which is described above, uses a rough distillation column for the rough distillation treatment, wherein the reflux ratio of the rough distillation column is (0.8-6): 1, and/or,
The molar ratio of the entrainer to the light component is 1 (5-15).
The modified molecular sieve catalyst provided by the invention comprises a molecular sieve and an active component loaded on at least part of pores and surfaces of the molecular sieve, wherein the active component comprises a palladium simple substance, a nickel simple substance and a copper simple substance. The modified molecular sieve catalyst has excellent catalytic activity, can be used in the catalytic reaction of synthesizing methyl acrylate by acetylene carbonyl, can improve the conversion rate of acetylene and the selectivity of methyl acrylate, can be recycled, and reduces the catalytic cost.
The preparation method of the modified molecular sieve catalyst provided by the invention can prepare the modified molecular sieve catalyst, is simple and is suitable for wide popularization and application.
The method for synthesizing methyl acrylate by carbonylation of acetylene, provided by the invention, uses the modified molecular sieve catalyst to carry out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide to obtain methyl acrylate. The method not only can realize the recycling of the modified molecular sieve catalyst and reduce the catalytic cost, but also can fully utilize CO, avoid environmental pollution, reduce carbon emission and realize the aim of greatly assisting double carbon.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings that are required to be used in the description of the embodiments of the present invention or the related technologies are briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a flow chart of the carbonylation of acetylene to methyl acrylate in some embodiments of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a modified molecular sieve catalyst, which comprises a molecular sieve and an active component loaded on at least part of pores and/or at least part of surfaces of the molecular sieve, wherein the active component comprises a palladium simple substance, a nickel simple substance and a copper simple substance.
In the invention, the active component can be loaded on part of pores of the molecular sieve and can also be loaded on the whole pores of the molecular sieve, and/or the active component can be loaded on part of the surface of the molecular sieve and can also be loaded on the whole surface of the molecular sieve.
According to the modified molecular sieve catalyst, active components comprising palladium simple substances, nickel simple substances and copper simple substances are loaded on at least part of pores and/or at least part of surfaces of the molecular sieve, the modified molecular sieve catalyst has excellent catalytic performance, the modified molecular sieve catalyst is used in the catalytic reaction of synthesizing methyl acrylate by acetylene carbonyl, the conversion rate of acetylene and the selectivity to the methyl acrylate can be improved, the modified molecular sieve catalyst can be recycled, and the catalytic cost is reduced.
In a specific embodiment, the molecular sieve comprises at least one of a ZSM-5 molecular sieve, a ZSM-35 molecular sieve, a MOR molecular sieve, and an EMT molecular sieve.
The molecular sieve has a good crystal structure and a higher specific surface area, and when the molecular sieve is selected, the palladium simple substance, the nickel simple substance and the copper simple substance can be more fully loaded on at least part of pores and/or at least part of surfaces of the molecular sieve, so that a modified molecular sieve catalyst with more excellent catalytic performance is obtained. Further, the molecular sieve may preferably be a ZSM-5 molecular sieve.
In a specific embodiment, in the modified molecular sieve catalyst, the mass ratio of the palladium simple substance to the nickel simple substance to the copper simple substance is (0.35-1.42): 1.50-5.25): 0.85-2.35.
When the mass ratio of the palladium simple substance, the nickel simple substance and the copper simple substance in the modified molecular sieve catalyst is in the range, the simple substances can be more fully matched with the molecular sieve to generate a synergistic effect, so that the modified molecular sieve catalyst is obtained.
The method for measuring the mass of the palladium simple substance, the nickel simple substance and the copper simple substance in the modified molecular sieve catalyst is not particularly limited. In some embodiments, the mass of the palladium element, nickel element, and copper element in the modified molecular sieve catalyst may be determined using X-ray fluorescence spectroscopy (XRD) or inductively coupled plasma mass spectrometry (ICP-MS).
Illustratively, in the modified molecular sieve catalyst, the mass ratio of elemental palladium, elemental nickel, and elemental copper may be in the range of any one of, and any three of, 0.35:1.50:0.85, 1.42:5.25:2.35, 0.35:5.25:2.35, 0.35:1.50:2.35, 1.42:1.50:0.85, 1.42:5.25:2.35, and 1.42:5.25:0.85.
The invention also provides a preparation method of the modified molecular sieve catalyst, which comprises the following steps:
Impregnating the molecular sieve with a mixed solution comprising a palladium source, a nickel source and a copper source to obtain a molecular sieve catalyst precursor;
And (3) roasting and reducing the molecular sieve catalyst precursor in sequence to obtain the modified molecular sieve catalyst.
The preparation method comprises the steps of carrying out impregnation treatment on a molecular sieve by using a mixed solution comprising a palladium source, a nickel source and a copper source, carrying out ion exchange on metal ions (palladium ions, nickel ions and copper ions) in the mixed solution and cations in the molecular sieve, loading the metal ions and the cations on at least partial pores and/or at least partial surfaces of the molecular sieve to obtain a molecular sieve catalyst precursor, carrying out roasting treatment on the molecular sieve catalyst precursor to uniformly distribute the metal ions on the surfaces and the pores of the molecular sieve to form stable metal oxides, carrying out reduction treatment on the roasted molecular sieve catalyst precursor, reducing the metal oxides into metal simple substances to form active components distributed on the surfaces and the pores of the molecular sieve to obtain the modified molecular sieve catalyst, and carrying out the catalytic reaction on the modified molecular sieve catalyst in the catalytic reaction of synthesizing methyl acrylate by acetylene carbonyl, so that the conversion rate of acetylene and the selectivity of methyl acrylate can be improved.
In another embodiment, the preparation method of the modified molecular sieve catalyst comprises the steps of respectively carrying out impregnation treatment on a molecular sieve by using a palladium source solution, a nickel source solution and a copper source solution to obtain a molecular sieve precursor, and sequentially carrying out roasting treatment and reduction treatment on the molecular sieve catalyst precursor to obtain the modified molecular sieve catalyst.
The preparation method comprises the steps of carrying out impregnation treatment on a molecular sieve by using a palladium source solution, a nickel source solution and a copper source solution respectively, carrying out ion exchange on metal ions in the solutions (palladium ions in the palladium source solution, nickel ions in the nickel source solution and copper ions in the copper source solution) and cations in the molecular sieve, loading the metal ions and the cations on at least partial pores and/or at least partial surfaces of the molecular sieve to obtain a molecular sieve catalyst precursor, carrying out roasting treatment on the molecular sieve catalyst precursor to uniformly distribute the metal ions on the surface and the pores of the molecular sieve to form stable metal oxides, carrying out reduction treatment on the roasted molecular sieve catalyst precursor, reducing the metal oxides into metal simple substances to form active components distributed on the surface and the pores of the molecular sieve, and obtaining the modified molecular sieve catalyst.
The method is not limited to the sequence of the palladium source solution, the nickel source solution and the copper source solution for carrying out the dipping treatment on the molecular sieve, the palladium source solution is firstly used for carrying out the dipping treatment on the molecular sieve, the nickel source solution is used for carrying out the dipping treatment on the molecular sieve, and the copper source solution is used for carrying out the dipping treatment on the molecular sieve, the nickel source solution is firstly used for carrying out the dipping treatment on the molecular sieve, the palladium source solution is used for carrying out the dipping treatment on the molecular sieve, and the copper source solution is used for carrying out the dipping treatment on the molecular sieve, and the nickel source solution is used for carrying out the dipping treatment on the molecular sieve.
The preparation method of the invention can prepare the modified molecular sieve catalyst, the modified molecular sieve catalyst can be recycled, the catalytic cost is reduced, and the preparation method is simple and is suitable for wide popularization and application.
In some embodiments, the palladium source may be one or more of palladium acetate, palladium chloride, palladium bromide, palladium iodide, the nickel source may be one or more of nickel nitrate, nickel chloride, nickel bromide, or nickel iodide, and the copper source may be one or more of copper nitrate, copper chloride, copper acetate.
The specific atmosphere type of the reduction treatment is not particularly limited, and can be selected according to actual needs. In some embodiments, the reduction treatment may be performed under a hydrogen atmosphere.
In one embodiment, the firing process includes a pre-firing process and a main firing process in that order, the pre-firing process being at a temperature less than the main firing process.
The method comprises the steps of carrying out pre-roasting treatment on the molecular sieve catalyst precursor at a lower temperature to remove solvent and moisture in the molecular sieve catalyst precursor, improving the purity of the molecular sieve catalyst precursor, facilitating the subsequent main roasting treatment, and carrying out main roasting treatment on the molecular sieve catalyst precursor subjected to the pre-roasting treatment at a higher temperature to uniformly distribute metal ions on the surface and/or in pores of the molecular sieve and form stable metal oxide, thereby improving the catalytic performance of the molecular sieve catalyst. To obtain a modified molecular sieve catalyst.
In one embodiment, the pre-bake treatment is performed at a temperature of 320-460 ℃ for a time of 0.5-4 hours.
When the parameters of the temperature and time of the pre-calcination treatment are within the above ranges, the solvent and moisture in the molecular sieve catalyst precursor can be effectively removed, which is advantageous for preparing the modified molecular sieve catalyst having more excellent catalytic activity. In some embodiments, the pre-firing treatment may be performed by increasing the temperature from room temperature to 400 ℃ at a rate of increase of 5 ℃ per minute.
Illustratively, in the pre-firing treatment, the temperature may be in a range consisting of any one of 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃ and any two thereof;
the time may be in the range of any one of 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, and any two.
In one embodiment, the main firing process is performed at a temperature of 460-620 ℃ for 3-5 hours.
When the parameters of the temperature and time of the main calcination treatment are within the above ranges, it is possible to more uniformly distribute the metal ions in the molecular sieve surface and pores and form more stable metal oxides, thereby preparing a modified molecular sieve catalyst having more excellent catalytic activity. In some embodiments, the main firing process may be performed with a temperature ramp from 400 ℃ to 550 ℃ at a ramp rate of 5 ℃ per minute.
Illustratively, in the main firing treatment, the temperature may be in a range of any one of 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃ and any two of them;
the time may be in the range of any one of 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, and any two.
In one embodiment, the reducing treatment is performed at a temperature of 330-380 ℃ for 2-4 hours.
When the parameters of the temperature and time of the reduction treatment are within the above ranges, the metal oxide can be sufficiently reduced to a metal simple substance to form an active component distributed on the surface and in the pores of the molecular sieve, thereby obtaining a modified molecular sieve catalyst having more excellent catalytic performance. In some embodiments, the reduction treatment may be performed by increasing the temperature from room temperature to 350 ℃ at a rate of 2 ℃ per minute.
Illustratively, in the reduction treatment, the temperature may be in a range consisting of any one of 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃ and any two thereof;
the time may be in the range of any one of 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, and any two.
In some embodiments, a magnetic stirrer is also used for the stirring process during the impregnation process.
The invention carries out stirring treatment in the dipping treatment process, can lead metal ions (palladium ions, nickel ions and copper ions) in the mixed solution and cations in the molecular sieve to be more fully subjected to ion exchange and be loaded on the pores and the surface of the molecular sieve, thereby being beneficial to the subsequent roasting treatment.
In one embodiment, the impregnation treatment is followed by a washing and drying treatment.
Specifically, washing the immersed product by using deionized water to remove unadsorbed metal ions, and then drying at 110-150 ℃ for 8-15 hours to primarily remove some water and solvent, thereby obtaining the dried molecular sieve catalyst precursor.
In one embodiment, a cooling process is also included after the reduction process.
Specifically, the modified molecular sieve catalyst after the reduction treatment is gradually cooled to room temperature for cooling treatment, so as to prevent active components loaded on at least part of pores and/or at least part of the surface of the molecular sieve from being oxidized, and then the modified molecular sieve catalyst is taken out under the protection of nitrogen.
FIG. 1 is a flow chart of the carbonylation of acetylene to methyl acrylate in some embodiments of the invention. As shown in FIG. 1, the invention provides a method for synthesizing methyl acrylate by carbonylation of acetylene, which comprises the step of carrying out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide by using a modified molecular sieve catalyst to obtain methyl acrylate.
Specifically, acetylene, methanol and carbon monoxide are used as raw material systems, and under the action of a modified molecular sieve catalyst, the raw material systems comprising the acetylene, the methanol and the carbon monoxide are subjected to chemical reaction to obtain methyl acrylate.
The method can improve the conversion rate of acetylene and the selectivity of methyl acrylate, can realize the recycling of the modified molecular sieve catalyst, reduce the catalytic cost, fully utilize CO, avoid environmental pollution, reduce carbon emission and realize the aim of greatly assisting the double carbon.
In some embodiments, the acetylene, methanol, and carbon monoxide (CO) described above may be obtained via coal. Specifically, coal is coked to form coke, then the coke reacts with limestone to prepare calcium carbide, then the calcium carbide reacts with water to obtain acetylene, and finally the acetylene is purified to obtain purified acetylene, and the purified acetylene is used as one of raw material systems for synthesizing methyl acrylate by carbonylation of acetylene. The CO-product tail gas is produced in the reaction process of coke and limestone, the CO-product tail gas is purified to obtain CO and intermediate by-product tail gas, the CO is used as one of raw material systems for synthesizing methyl acrylate by carbonylation of acetylene, the intermediate by-product tail gas can be subjected to tail gas conversion treatment, the CO 2 in the intermediate by-product tail gas is further converted into CO to obtain CO and tail gas, and the obtained CO can be recycled for tail gas purification treatment and also can be used as one of raw material systems for synthesizing methyl acrylate by carbonylation of acetylene. The methanol can be used as an acetylene absorbent, the acetylene is absorbed in a low-pressure acetylene absorption tower, and the methanol and CO after the acetylene absorption and the modified molecular sieve catalyst enter a high-pressure reactor for catalytic reaction. The high-pressure reactor is a continuous flow reactor, can continuously react, and can greatly reduce carbon deposition and side reaction in the reaction process.
The tail gas purification treatment can be performed by one or more combination of a PSA method, a complexing agent purification method or membrane separation.
The specific components of the by-product tail gas generated in the process of reacting coke with limestone are shown in table 1:
TABLE 1 specific Components of by-product tail gas
| Gas composition | CO | H2 | CO2 | O2 | N2 |
| Concentration% | 70~90 | 2~5 | 1~3 | 0.2~1 | 2~5 |
The invention synthesizes methyl acrylate by adopting the carbonylation reaction of acetylene produced by coal, and the reaction process belongs to ideal atomic economy reaction, which not only is beneficial supplement to the prior novel coal chemical technology, but also can expand the chain of acetylene products, and simultaneously can use the byproduct tail gas of calcium carbide as an air source.
In a specific embodiment, the molar ratio of acetylene, carbon monoxide and methanol in the raw material system is 1 (1.5-3.5): 3-10.
When the molar ratio of acetylene, carbon monoxide and methanol in the raw material system is in the above range, the catalytic cost can be reduced while the respective raw materials can be allowed to more sufficiently perform the catalytic reaction, so that the reaction can be efficiently performed to obtain methyl acrylate.
Illustratively, the molar ratio of acetylene, carbon monoxide and methanol in the feed system may be in the range of any one of, and any three of, 1:1.50:3, 1:1.5:10, 1:3.5:3, 1:3.50:10, 1:2:3, 1:2:10 and 1:3.5:5.
In one specific embodiment, the modified molecular sieve catalyst has a mass fraction of 0.001 to 6% of the total mass of the feed system.
When the ratio of the mass of the modified molecular sieve catalyst in the total mass of the raw material system is within the above range, the catalytic reaction can be more efficiently performed while the amount of the modified molecular sieve catalyst is reduced, the catalytic rate and selectivity are improved, and the generation of byproducts is reduced to obtain methyl acrylate.
Illustratively, the mass of the modified molecular sieve catalyst can be in a range of any one of, and any two of, 0.001%, 0.01%, 0.1%, 1%, 2%, 3%, 4%, 5%, and 6% of the total mass of the feedstock system.
In one embodiment, the catalytic reaction is carried out at a temperature of 80-220 ℃, a pressure of 3-12 MPaG, and a time of 0.1-1 h.
When the temperature, pressure and time in the catalytic reaction are in the ranges, the catalytic reaction can be more efficiently carried out under the condition of saving energy consumption, the generation of byproducts is reduced, and the conversion rate of acetylene and the selectivity of methyl acrylate are improved.
Illustratively, in a catalytic reaction, the temperature may be in a range consisting of any one of, and any two of, 80 ℃,100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, and 220 ℃;
The pressure may be in a range consisting of any one of 3MPaG, 4MPaG, 5MPaG, 6MPaG, 7MPaG, 8MPaG, 9MPaG, 10MPaG, 11MPaG, and12 MPaG, and any two thereof;
The time may be in the range of any one and any two of 0.1h, 0.2h, 0.4h, 0.6h, 0.8h and 1 h.
In a specific embodiment, the catalyst further comprises post-treatment, wherein the post-treatment comprises the steps of carrying out gas-liquid separation treatment on a mixture obtained after the catalytic reaction to obtain a gas phase and a liquid phase, carrying out rough distillation treatment on the liquid phase to obtain a light component comprising methanol and methyl acrylate and methanol, and carrying out azeotropic distillation treatment on the light component under the action of an entrainer to obtain methyl acrylate.
The method comprises the steps of carrying out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide by using a modified molecular sieve catalyst to obtain a mixed material comprising methyl acrylate, carrying out gas-liquid separation treatment on the mixed material to obtain a gas phase comprising acetylene and CO and a liquid phase comprising methanol, the modified molecular sieve catalyst and methyl acrylate, recycling the separated gas phase, carrying out rough fractionation treatment on the liquid phase to obtain heavy components comprising methanol and the modified molecular sieve catalyst and light components comprising methanol and methyl acrylate, recycling the heavy components comprising methanol and the modified molecular sieve catalyst, carrying out azeotropic rectification treatment on the light components comprising methanol and methyl acrylate under the action of an entrainer, forming an azeotrope with a lower boiling point by the methanol and the entrainer, obtaining the azeotrope comprising the methanol and the entrainer and the methyl acrylate, and further separating and purifying the separated azeotrope comprising the methanol and the entrainer.
The invention can reduce the resource waste and the catalysis cost and improve the purity of the methyl acrylate at the same time through the post-treatment.
In some embodiments, the gas-liquid separation process is performed using a gas-liquid separator.
Specifically, the mixed material obtained after the catalytic reaction enters the gas-liquid separator through the inlet of the gas-liquid separator to be subjected to gas-liquid separation treatment, so that the mixed material is primarily separated to obtain a gas phase comprising acetylene and CO and a liquid phase comprising methanol, a modified molecular sieve catalyst and methyl acrylate.
In a specific embodiment, the crude distillation treatment is performed by using a crude distillation column, and the reflux ratio of the crude distillation column is (0.8-6): 1.
Specifically, the liquid phase is output from a liquid phase outlet of the gas-liquid separator, enters the coarse-fraction rectifying tower through an inlet of the coarse-fraction rectifying tower to carry out coarse-fraction rectifying treatment, so as to obtain methanol, light components comprising methanol and methyl acrylate, and the light components are output from the top of the coarse-fraction rectifying tower to carry out azeotropic rectifying treatment.
In the invention, when the reflux ratio of the rough separation rectifying tower is (0.8-6): 1, the efficiency of the rough separation rectifying treatment can be improved under the condition of saving energy consumption, and thus, the high-purity methyl acrylate can be obtained.
Illustratively, the reflux ratio of the crude distillation column is in the range of any one and any two of 0.8:1, 1:1, 2:1, 3:1, 4:1, 5:1, and 6:1.
In some embodiments, the azeotropic distillation treatment is performed using an azeotropic distillation column, with the outlet of the crude distillation column being in communication with the inlet of the azeotropic distillation column.
Specifically, an entrainer enters an azeotropic distillation tower from the tower top of the azeotropic distillation tower, a light component obtained through crude distillation treatment is output from the tower top of the crude distillation tower, enters the azeotropic distillation tower through an inlet of the azeotropic distillation tower, the light component comprising methanol and methyl acrylate is subjected to azeotropic distillation treatment under the action of the entrainer, the methanol in the light component and the entrainer form an azeotrope with lower boiling point to obtain the azeotrope comprising the methanol and the entrainer and methyl acrylate, wherein the azeotrope comprising the methanol and the entrainer is cooled by a condenser of the azeotropic distillation tower and then enriched and layered in a phase separation gas device at the tower top of the azeotropic distillation tower, the entrainer and the methanol are respectively obtained after layering, the entrainer obtained after layering can be returned to the azeotropic distillation tower again for recycling, and the obtained methanol can also be recycled to participate in synthesizing the methyl acrylate, and the obtained methyl acrylate is extracted from a tower kettle of the azeotropic distillation tower.
In one embodiment, the molar ratio of the entrainer to the light component is 1 (5-15).
When the molar ratio of the entrainer to the light component is in the above range, the light component including methanol and methyl acrylate can be separated efficiently under the action of the entrainer, thereby obtaining methyl acrylate with higher purity. In some embodiments, the entrainer may be one or more of n-heptane, n-pentane, n-hexane, n-butanol, isopropanol.
Illustratively, the molar ratio of entrainer to light component may be in the range of any one and any two of compositions of 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, and 1:15.
The technical scheme of the invention will be further described below with reference to specific examples.
Example 1
The methyl acrylate of this example was prepared by a process comprising the steps of:
(1) Preparation of modified molecular sieve catalysts
The preparation method comprises the steps of respectively dissolving 3.170g of nickel nitrate, 0.445g of palladium chloride and 2.850g of copper nitrate in 25ml of deionized water to prepare a nickel nitrate solution, a palladium chloride solution and a copper nitrate solution, respectively carrying out impregnation treatment on a ZSM-5 molecular sieve by using the nickel nitrate solution, the palladium chloride solution and the copper nitrate solution for 24 hours, repeatedly washing by using the deionized water, then drying for 12 hours at 120 ℃ to obtain a molecular sieve catalyst precursor, carrying out pre-roasting treatment on the molecular sieve catalyst precursor at a temperature of 5 ℃ to 400 ℃ at a temperature rising rate of 400 ℃ for 2 hours, then at a temperature of 5 ℃ to 550 ℃ at a temperature rising rate of 5 ℃ to carry out primary roasting treatment at 550 ℃ for 4 hours, placing the molecular sieve catalyst precursor after primary roasting treatment in a tubular furnace, carrying out reduction treatment at a temperature of 2 ℃ to 350 ℃ from room temperature to 350 ℃ for 3 hours under a hydrogen atmosphere, and then gradually cooling to room temperature to obtain the modified molecular sieve catalyst.
(2) Preparation of methyl acrylate
Adding 12kg of acetylene, 32kg of carbon monoxide (CO), 95kg of methanol and 3.3kg of modified molecular sieve catalyst into a carbonylation reactor, and carrying out catalytic reaction for 0.3h at the temperature of 150 ℃ and the pressure of 8MPa to obtain a mixed material;
the mixed material enters a gas-liquid separator through an inlet of the gas-liquid separator to be subjected to gas-liquid separation treatment, so as to obtain a gas phase and a liquid phase;
The liquid phase is output from a liquid phase outlet of the gas-liquid separator, enters the coarse-fraction rectifying tower through an inlet of the coarse-fraction rectifying tower to be subjected to coarse-fraction rectifying treatment to obtain methanol, and light components comprising methanol and methyl acrylate, wherein the reflux ratio of the coarse-fraction rectifying tower is 2.4;
the entrainer enters the azeotropic distillation tower from the tower top of the azeotropic distillation tower, the light component is output from the tower top of the crude distillation tower, enters the azeotropic distillation tower from the inlet of the azeotropic distillation tower for azeotropic distillation treatment, the azeotrope comprising methanol and the entrainer and the methyl acrylate are obtained, the obtained methyl acrylate is output from the tower bottom of the azeotropic distillation tower, and the molar ratio of the entrainer to the light component is 1:6.5.
Example 2
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(1) Preparation of modified molecular sieve catalysts
3.170G of nickel nitrate, 0.126g of palladium chloride and 2.850g of copper nitrate were each dissolved in 25ml of deionized water.
(2) Preparation of methyl acrylate
The modified molecular sieve catalyst in example 1 was replaced with the modified molecular sieve catalyst in this example.
Example 3
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(1) Preparation of modified molecular sieve catalysts
3.170G of nickel nitrate, 0.445g of palladium chloride and 0.668g of copper nitrate were each dissolved in 25ml of deionized water.
(2) Preparation of methyl acrylate
The modified molecular sieve catalyst in example 1 was replaced with the modified molecular sieve catalyst in this example.
Example 4
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(1) Preparation of modified molecular sieve catalysts
3.170G of nickel nitrate, 0.445g of palladium chloride and 2.182g of copper nitrate were each dissolved in 25ml of deionized water.
(2) Preparation of methyl acrylate
The modified molecular sieve catalyst in example 1 was replaced with the modified molecular sieve catalyst in this example.
Example 5
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
12Kg of acetylene, 15kg of carbon monoxide (CO), 95kg of methanol, and 3.3kg of modified molecular sieve catalyst were charged to the carbonylation reactor.
Example 6
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
12Kg of acetylene, 15kg of carbon monoxide (CO), 38kg of methanol, and 3.3kg of modified molecular sieve catalyst were charged to the carbonylation reactor.
Example 7
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 50℃and a pressure of 8MPa for 0.3h.
Example 8
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 150℃and a pressure of 2.5MPa for 0.3h.
Example 9
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 150℃and a pressure of 8MPa for 0.05h.
Example 10
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 250℃and a pressure of 8MPa for 0.3h.
Example 11
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 150℃and a pressure of 15MPa for 0.3h.
Example 12
The preparation method of methyl acrylate of this example is basically the same as that of example 1, except that:
(2) Preparation of methyl acrylate
The catalytic reaction was carried out at a temperature of 150℃and a pressure of 8MPa for 1.2h.
Comparative example 1
The preparation method of methyl acrylate of this comparative example is basically the same as that of example 1, except that:
(1) Preparation of modified molecular sieve catalysts
3.170G of nickel nitrate and 2.850g of copper nitrate were dissolved in 25ml of deionized water.
(2) Preparation of methyl acrylate
The modified molecular sieve catalyst in example 1 was replaced with the modified molecular sieve catalyst in this comparative example.
Comparative example 2
The preparation method of methyl acrylate of this comparative example is basically the same as that of example 1, except that:
(1) Preparation of modified molecular sieve catalysts
3.170G of nickel nitrate and 0.445g of palladium chloride were dissolved in 25ml of deionized water.
(2) Preparation of methyl acrylate
The modified molecular sieve catalyst in example 1 was replaced with the modified molecular sieve catalyst in this comparative example.
Performance testing
The modified molecular sieve catalysts of the examples and comparative examples were each subjected to the following performance test, the results of which are shown in table 1;
(1) Specific surface area measurement the specific surface area of the modified molecular sieve catalyst of example 1 was measured using the BET method to evaluate the pore structure characteristics thereof;
(2) Measuring the contents of palladium simple substance, nickel simple substance and copper simple substance in the modified molecular sieve catalyst by adopting an inductively coupled plasma mass spectrometry (ICP-MS) method to obtain the mass ratio of the palladium simple substance, the nickel simple substance and the copper simple substance;
(3) And (3) testing the dispersity, namely observing the distribution and the size of the palladium simple substance, the nickel simple substance and the copper simple substance in the modified molecular sieve catalyst by a Transmission Electron Microscope (TEM), and evaluating the dispersity of the metal simple substance in the molecular sieve.
Table 1 test results
As can be seen from Table 1, the modified molecular sieve catalyst obtained in the examples of the present invention has a larger specific surface area and a higher dispersity. When the modified molecular sieve is used for catalytic reaction, the larger specific surface area can provide more active sites, promote the reactant to fully contact with the modified molecular sieve, and the higher dispersity can increase the available sites of active components, reduce the aggregation of the active components and further improve the catalytic efficiency of the modified analysis sieve catalyst.
The modified molecular sieve catalysts of examples and comparative examples were evaluated for catalytic performance, and acetylene conversion, methyl acrylate selectivity and yield were all calculated based on the number of moles of carbon of acetylene converted, and the results are shown in table 2;
table 2 catalytic performance of modified molecular sieve catalysts
As can be seen from table 2, the modified molecular sieve in the examples of the present invention can improve the efficiency of the catalytic reaction and the selectivity and yield of methyl acetate when used for the catalytic reaction of a raw material system comprising acetylene, carbon monoxide and methanol, and further, as can be seen from examples 1 to 4 and examples 5 to 10, by further selecting the parameters of the catalytic reaction, the conversion rate of acetylene can be improved while improving the selectivity and yield of methyl acetate.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments. The foregoing is merely illustrative of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (10)
1. A modified molecular sieve catalyst, characterized in that the modified molecular sieve catalyst comprises a molecular sieve and an active component supported on at least a portion of the pores and/or at least a portion of the surface of the molecular sieve;
the active component comprises a palladium simple substance, a nickel simple substance and a copper simple substance.
2. The modified molecular sieve catalyst of claim 1, wherein the molecular sieve comprises at least one of a ZSM-5 molecular sieve, a ZSM-35 molecular sieve, a MOR molecular sieve, and an EMT molecular sieve, and/or,
In the modified molecular sieve catalyst, the mass ratio of the palladium simple substance to the nickel simple substance to the copper simple substance is (0.35-1.42): 1.50-5.25): 0.85-2.35.
3. A method of preparing the modified molecular sieve catalyst of claim 1 or 2, comprising the steps of:
the method comprises the steps of carrying out impregnation treatment on a molecular sieve by using a mixed solution comprising a palladium source, a nickel source and a copper source to obtain a molecular sieve catalyst precursor, or respectively carrying out impregnation treatment on the molecular sieve by using a palladium source solution, a nickel source solution and a copper source solution to obtain a molecular sieve precursor;
and sequentially roasting and reducing the molecular sieve catalyst precursor to obtain the modified molecular sieve catalyst.
4. The method for producing a modified molecular sieve catalyst according to claim 3, wherein the calcination treatment comprises a pre-calcination treatment and a main calcination treatment in this order;
the temperature of the pre-firing treatment is less than the temperature of the main firing treatment.
5. The method for preparing a modified molecular sieve catalyst according to claim 4, wherein the pre-calcination treatment is performed at 320-460 ℃ for 0.5-4 hours and/or,
In the main roasting treatment, the temperature is 460-620 ℃ and the time is 3-5 h, and/or,
In the reduction treatment, the temperature is 330-380 ℃ and the time is 2-4 hours.
6. A method for synthesizing methyl acrylate by carbonylation of acetylene, which is characterized by comprising the step of carrying out catalytic reaction on a raw material system comprising acetylene, methanol and carbon monoxide by using the modified molecular sieve catalyst as claimed in claim 1 or 2 to obtain the methyl acrylate.
7. The method for synthesizing methyl acrylate by carbonylation of acetylene according to claim 6, wherein the molar ratio of acetylene, carbon monoxide and methanol in the raw material system is 1 (1.5-3.5): 3-10), and/or,
The weight ratio of the modified molecular sieve catalyst in the total weight of the raw material system is 0.001-6%.
8. The method for synthesizing methyl acrylate by carbonylation of acetylene according to claim 6 or 7, wherein in the catalytic reaction, the temperature is 80-220 ℃, the pressure is 3-12 mpa g, and the time is 0.1-1 h.
9. The process for the carbonylation of acetylene to methyl acrylate according to any one of claims 6 to 8, characterized in that it further comprises a post-treatment after the catalytic reaction,
The post-treatment comprises the steps of carrying out gas-liquid separation treatment on the mixed material obtained after the catalytic reaction to obtain a gas phase and a liquid phase;
Carrying out rough distillation treatment on the liquid phase to obtain a light component comprising methanol and methyl acrylate and methanol;
and under the action of an entrainer, carrying out azeotropic distillation treatment on the light component to obtain methyl acrylate.
10. The method for synthesizing methyl acrylate by carbonylation of acetylene according to claim 9, wherein the crude distillation treatment is performed by using a crude distillation column having a reflux ratio of (0.8-6): 1, and/or,
The molar ratio of the entrainer to the light component is 1 (5-15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411544328.XA CN119608224A (en) | 2024-10-31 | 2024-10-31 | A modified molecular sieve catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411544328.XA CN119608224A (en) | 2024-10-31 | 2024-10-31 | A modified molecular sieve catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN119608224A true CN119608224A (en) | 2025-03-14 |
Family
ID=94901277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411544328.XA Pending CN119608224A (en) | 2024-10-31 | 2024-10-31 | A modified molecular sieve catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119608224A (en) |
-
2024
- 2024-10-31 CN CN202411544328.XA patent/CN119608224A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9221685B2 (en) | Methods of capturing and sequestering carbon | |
| CN103880590A (en) | Process for preparing 1,3,3,3-tetrafluoropropene | |
| CN113816823A (en) | Process for synthesizing chloroethylene by using mercury-free catalyst | |
| WO2022028236A1 (en) | Method for synthesizing difluoromethane by means of gas phase catalysis | |
| CN101066955A (en) | A kind of synthetic method of N-methylmorpholine | |
| CN1120047C (en) | Catalyst for preparing propylene by dismutation reaction and its preparing process and application | |
| CN101530805B (en) | Catalyst for preparing tertiary olefin by cracking tertiary alkyl ether, preparation method and application thereof | |
| CN101279910A (en) | A kind of preparation method of acrylic acid | |
| CN1087656C (en) | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use | |
| CN101306990B (en) | Second-stage reaction process for preparing propenoic acid or ester from lactic acid or ester | |
| CN102240539B (en) | Preparation method of solid base catalyst and method for catalytically synthesizing propylene glycol phenyl ether | |
| CN119608224A (en) | A modified molecular sieve catalyst and its preparation method and application | |
| CN109761819B (en) | Continuous preparation method of N, N-dimethylpropylamine | |
| CN113828340B (en) | Palladium-based hydrogenation catalyst and preparation method and application thereof | |
| CN114870886A (en) | Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation | |
| CN1076631C (en) | Catalyst for conversion of methane to ethylene, preparation thereof, and process for manufacturing ethylene using said catalyst | |
| CN106475106A (en) | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst | |
| CN115536487B (en) | High-purity low-carbon alkane production process and equipment | |
| CN106866583B (en) | A kind of preparation method of two (2- ethoxy) piperazines | |
| CN106609156B (en) | The method of refinery gas removing alkene | |
| CN105727973B (en) | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst | |
| CN115368200B (en) | Method for preparing paraxylene by biomass conversion | |
| CN110152694B (en) | Heterogeneous acetylene carbonylation catalyst and preparation method and application thereof | |
| CN110304981A (en) | The method of chloromethanes conversion producing light olefins | |
| CN119638550A (en) | Green methanol production method based on controllable microchannel reactor with low-temperature plasma activation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |