CN111978171A - Process for preparing acrylic acid and methyl acrylate - Google Patents
Process for preparing acrylic acid and methyl acrylate Download PDFInfo
- Publication number
- CN111978171A CN111978171A CN201910430792.9A CN201910430792A CN111978171A CN 111978171 A CN111978171 A CN 111978171A CN 201910430792 A CN201910430792 A CN 201910430792A CN 111978171 A CN111978171 A CN 111978171A
- Authority
- CN
- China
- Prior art keywords
- raw material
- molecular sieve
- methanol
- catalyst
- zeolitic molecular
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a method for preparing acrylic acid and methyl acrylate, the method comprising the steps of: raw material gas containing methanol, formaldehyde compounds and carbon monoxide is contacted with a solid acid catalyst in a reactor to react to obtain acrylic acid and methyl acrylate. The method takes the solid acid as the catalyst, has high target product selection, simple process, strong practicability and strong industrial application prospect.
Description
Technical Field
The application relates to a method for preparing acrylic acid and methyl acrylate, belonging to the technical field of catalytic preparation of organic matters.
Background
Acrylic acid and its ester are fine chemical raw materials with wide application, and are mainly used as organic synthesis intermediates and high molecular monomers. The polymer synthesized by the method is widely used in the industries of coating, textile, leather, adhesive, papermaking, paint, pharmacy and the like. The synthesis method of the acrylic acid mainly comprises the following steps: 1) chlorohydrin method: using chloroethanol and sodium cyanide as raw materials, generating cyanoethanol under the action of an alkaline catalyst, and then dehydrating the cyanoethanol in the presence of sulfuric acid to obtain acrylonitrile. Hydrolyzing or alcoholyzing acrylonitrile to obtain acrylic acid or acrylic ester; 2) a cyanoethanol method: the method is developed from a chlorohydrin method, and only cyanoethanol is generated by the ring-opening reaction of ethylene oxide under the action of hydrocyanic acid; 3) high-voltage Reppe and modified Reppe methods: acetylene, carbon monoxide and water generate esterification grade acrylic acid under the action of nickel salt or copper salt, and then the esterification grade acrylic acid and different alcohols generate esterification reaction to generate acrylic ester; 4) an ketene method: ketene (prepared by using acetone and acetic acid as raw materials) reacts with anhydrous formaldehyde to produce beta-propiolactone, and the beta-propiolactone is in contact with hot phosphoric acid to isomerize to produce acrylic acid; 5) formaldehyde-acetic acid process: formaldehyde and acetic acid are subjected to aldol condensation reaction to directly generate acrylic acid; 6) acrylonitrile hydrolysis method; 7) ethylene process: ethylene, carbon monoxide and oxygen are subjected to oxidation and carbonylation reaction in the presence of a noble metal catalyst to generate acrylic acid; 8) propylene direct oxidation process: wherein the method is divided into a one-step direct oxidation method and a two-step direct oxidation method. In the first step of the two-step oxidation process, propylene is oxidized to form acrolein, and in the second step, the acrolein is further oxidized to form acrylic acid; 9) propane oxidation method: propane is used as a raw material, metal oxide is used as a catalyst, and the propane is directly oxidized to obtain acrylic acid; 10) ethylene oxide process: the direct insertion of carbon monoxide into ethylene oxide, that is, the carbonylation of ethylene oxide, produces propionic acid. Among the above methods for producing acrylic acid, the chlorohydrin method, cyanoethanol method, Reppe method and ketene method have high industrial cost due to low efficiency and high toxicity, and have been gradually eliminated. The stability and selectivity of the catalyst and the catalyst process of the ethylene process, the propane process and the ethylene oxide process are not mature, and no large-scale production is reported at present, and only the propylene oxidation process becomes the only method adopted by the large-scale production of acrylic acid in the world today. These methods have the disadvantages of more or less serious pollution, high energy consumption, high toxicity of intermediate products, low yield and the like. Therefore, the development of the efficient green synthesis method of acrylic acid/methyl acrylate has very important practical significance and industrial application value.
Disclosure of Invention
According to one aspect of the application, the method for preparing acrylic acid and methyl acrylate is provided, solid acid is used as a catalyst, the target product is high in selection, the process is simple, the practicability is high, and the industrial application prospect is strong.
A process for preparing acrylic acid and methyl acrylate includes such steps as contacting the raw material gas containing methanol, formaldehyde compound and CO with solid acid catalyst, and reacting to obtain acrylic acid and methyl acrylate.
In the present application, the skilled person can select suitable reaction conditions according to actual needs, and some preferred reaction conditions are described below.
Optionally, the reaction conditions are: the reaction temperature is 170-380 ℃; the reaction pressure is 0.1-20 MPa; the volume space velocity of the feed gas is 500-20000 h-1。
The upper limit of the reaction temperature is independently selected from 220 ℃, 250 ℃, 280 ℃, 320 ℃ and 380 ℃; the lower limit of the reaction temperature is independently selected from the group consisting of 170 deg.C, 220 deg.C, 250 deg.C, 280 deg.C, and 320 deg.C.
The upper limit of the reaction pressure is independently selected from 0.5MPa, 3MPa, 5MPa, 8MPa, 20 MPa; the lower limit of the reaction pressure is independently selected from 0.1MPa, 0.5MPa, 3MPa, 5MPa, 8 MPa.
Preferably, the reaction conditions are: the reaction temperature is 220-320 ℃; the reaction pressure is 1-10 MPa; the volume space velocity of the feed gas is 3000-10000 h -1。
Optionally, the formaldehyde-based compound comprises at least one of formaldehyde, methylal, trioxymethylene, and paraformaldehyde.
Optionally, the feed gas comprises a feed I and a feed II;
the raw material I contains a material A;
the material A is methanol and a formaldehyde compound;
the raw material II contains carbon monoxide.
Optionally, the feed gas comprises a feed I and a feed II; the raw material I contains a material A; the material A is methanol and a formaldehyde compound; the raw material II is carbon monoxide.
Optionally, the mass space velocity of the material A is 0.1-3 h-1。
The upper limit of the mass space velocity of the material A is selected from 0.4h-1、0.5h-1、0.7h-1、1h-1、2h-1、3h-1(ii) a The lower limit of the mass space velocity of the material A is selected from 0.1h-1、0.4h-1、0.5h-1、0.7h-1、1h-1、2h-1、。
Optionally, the molar percentage of the raw material I in the raw material gas is 1-70%; the molar percentage content of the raw material II in the raw material gas is 30-99%.
The upper limit of the molar percentage content of the raw material I in the raw material gas is selected from 2%, 3.6%, 6.2%, 7%, 13%, 23%, 30% and 70%; the lower limit of the molar percentage content of the raw material I in the raw material gas is selected from 1%, 2%, 3.6%, 6.2%, 7%, 13%, 23% and 30%.
The upper limit of the molar percentage content of the raw material II in the raw material gas is selected from 70%, 77%, 87%, 93%, 93.8%, 96.4%, 98% and 99%; the lower limit of the molar percentage content of the raw material II in the raw material gas is selected from 30%, 70%, 77%, 87%, 93%, 93.8%, 96.4% and 98%.
Preferably, the molar percentage content of the raw material I in the raw material gas is 2-30%; the molar percentage content of the raw material II in the raw material gas is 70-98%.
Optionally, the mass percentage of the methanol in the material A is 10-90%; the mass percentage of the formaldehyde compound in the material A is 10-90%.
The upper limit of the mass percentage of the methanol in the material A is independently selected from 42 percent, 52 percent and 90 percent; the lower limit of the mass percentage of the methanol in the material A is independently selected from 10%, 42% and 52%.
The upper limit of the mass percentage content of the formaldehyde compound in the material A is independently selected from 48%, 58% and 90%; the lower limit of the mass percentage of the formaldehyde compound in the material A is independently selected from 10%, 48% and 58%.
In the material A, the molar ratio of methanol to formaldehyde compounds is 1-5: 1.
preferably, the molar ratio of methanol to the formaldehyde compound is 2-3: 1.
in the raw material gas, the molar ratio of CO to methanol is 5-40: 1.
in a raw material gas, the molar ratio of CO to methanol to a formaldehyde compound is 10-120: 2-3: 1.
optionally, the mass percentage of the material A in the raw material I is 50-100%.
The upper limit of the mass percentage content of the material A in the raw material I is independently selected from 56%, 63% and 100%; the lower limit of the mass percentage of the material A in the raw material I is independently selected from 50%, 56% and 63%.
Optionally, the raw material I also contains a material B; the material B comprises at least one of dimethyl ether, methyl acetate and acetic acid.
Optionally, the mass percentage of the material B in the raw material I is 0-50%.
Specifically, the raw material I contains 50-100% of material A containing methanol and formaldehyde compounds by mass and 0-50% of material B containing at least one of dimethyl ether, methyl acetate and acetic acid by mass.
Optionally, the solid acid catalyst comprises a zeolitic molecular sieve.
Optionally, the zeolitic molecular sieve comprises at least one of a zeolitic molecular sieve having FER topology, a zeolitic molecular sieve having MFI topology, a zeolitic molecular sieve having MOR topology, a zeolitic molecular sieve having MFS topology, a zeolitic molecular sieve having MTF topology.
Optionally, the zeolite molecular sieve has a silica-alumina ratio of 8 to 100.
The upper limit of the silica to alumina ratio of the zeolite molecular sieve is selected from 15, 30, 50, 100; the lower limit of the silica to alumina ratio of the zeolite molecular sieve is selected from 8, 15, 30, 50.
Optionally, the zeolite molecular sieve is a hydrogen zeolite molecular sieve.
The hydrogen-form zeolite molecular sieve has the structure FER, MFI, MOR, MFS or MTF.
In the present application, the preparation of the hydrogen-type zeolite molecular sieve can adopt any suitable method in the prior art, and the present application is not limited strictly.
A preferred method of preparation is described below: adding Na-type zeolite molecular sieve powder into pre-prepared NH4NO3The solution was exchanged with stirring, filtered and washed. After continuous exchange for several times, drying and roasting to obtain the H-type zeolite molecular sieve.
Optionally, the zeolite molecular sieve is a metal-modified hydrogen-type zeolite molecular sieve;
the metal is at least one selected from copper, silver, iron, cobalt, nickel and gallium.
Optionally, the zeolite molecular sieve is a metal-modified hydrogen-type zeolite molecular sieve; the metal is at least one selected from copper, silver, iron, cobalt, nickel and gallium. That is, a metal element is introduced on the hydrogen type zeolite molecular sieve.
Optionally, the mass percentage of the metal element in the solid acid catalyst is 0.01-12 wt%.
The upper limit of the mass percentage content of the metal element in the solid acid catalyst is independently selected from 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 8 wt% and 12 wt%; the lower limit of the mass percentage content of the metal element in the solid acid catalyst is independently selected from 0.01 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 8 wt%.
Preferably, the mass percentage of the metal element in the solid acid catalyst is 0.1-8 wt%.
The metal modification method is selected from one of in-situ synthesis, ion exchange method and impregnation method. Namely, the metal elements are introduced into the hydrogen type zeolite molecular sieve by in-situ synthesis, an ion exchange method, an impregnation method or the like.
Specifically, the metal is introduced by adopting an impregnation method, and the method comprises the following steps: nitrate containing metal elements is dissolved in deionized water to prepare corresponding nitrate aqueous solution. And dropwise adding the aqueous solution of nitrate to the hydrogen-type zeolite molecular sieve, standing, drying the obtained sample, and roasting to introduce the metal elements into the hydrogen-type zeolite molecular sieve.
Introducing metal by adopting an ion exchange method, putting an aqueous solution containing nitrate of the metal element and the hydrogen-type zeolite molecular sieve into a flask, performing condensation reflux treatment under a stirring state, filtering and separating, washing with deionized water, repeating the steps, drying, and roasting to introduce the metal element into the hydrogen-type zeolite molecular sieve.
Introducing metal by in-situ synthesis, synthesizing metal-containing FER molecular sieve and MOR molecular sieve according to the methods in Chinese Journal of Catalysis 2010Vol.31P788-792 and Catalysis Science & Technology 2015Vol.5P1961-19681, respectively, roasting the synthesized sample, exchanging with ammonium nitrate, exchanging under stirring, filtering, washing, continuously exchanging for several times, drying, and roasting to obtain a metal-containing hydrogen type sample.
Preferably, the solid acid catalyst comprises any one or more of metal modified hydrogen form zeolite molecular sieves having the structure FER, MFI, MOR, MFS or MTF.
Optionally, the solid acid catalyst further comprises a matrix;
the matrix comprises at least one of alumina, silica, kaolin and magnesia.
Optionally, the mass percentage of the matrix in the solid acid catalyst is 1-50%.
The solid acid catalyst contains 50-99% of zeolite molecular sieve.
For example, the solid acid catalyst contains 50-99% of hydrogen type zeolite molecular sieve or metal modified zeolite molecular sieve, and the rest is matrix; the matrix is any one or mixture of more of aluminum oxide, silicon oxide, kaolin and magnesium oxide.
The preparation method of the solid acid catalyst containing the matrix is a mixing and forming method in the prior art. The method specifically comprises the following steps: the hydrogen type zeolite molecular sieve catalyst or the hydrogen type zeolite molecular sieve catalyst containing metal elements is fully mixed with the matrix, and the mixture is extruded into strips for forming, so that the solid acid catalyst containing the matrix, namely the formed solid acid catalyst, can be obtained.
Optionally, the zeolite molecular sieve is a hydrogen form zeolite molecular sieve that adsorbs pyridine. Specifically, the hydrogen zeolite molecular sieve is pretreated with pyridine.
The preparation method of the pyridine modified solid acid catalyst at least comprises the following steps: and (2) treating the formed hydrogen type zeolite molecular sieve or the formed hydrogen type zeolite molecular sieve containing metal elements for 2-8h at 250-350 ℃ in an atmosphere containing pyridine, and then purging for 1-3 h in a nitrogen atmosphere to obtain the pyridine modified solid acid catalyst.
Optionally, the reactor is selected from any one of a fixed bed reactor, a fluidized bed reactor, a moving bed reactor.
The beneficial effects that this application can produce include:
1) according to the method provided by the application, acrylic acid and methyl acrylate can be prepared from cheap raw materials of methanol and formaldehyde compounds;
2) according to the method provided by the application, the target product is high in selection, simple in process, strong in practicability and extremely strong in industrial application background.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The analysis method in the examples of the present application is as follows:
the raw materials and products were detected by Agilent 7890A gas chromatography from Agilent, Inc. using FFAP capillary column from Agilent, Inc.
The conversion and selectivity in the examples of the present application were calculated as follows:
Methanol conversion rate ═ [ (moles of methanol in feed) - (moles of methanol in discharge) ]/(moles of methanol in feed) × (100%)
Dimethyl ether selectivity 2 × (moles of dimethyl ether in discharge) ÷ [ (moles of methanol in feed) - (moles of methanol in discharge) ] × (100%)
Acetic acid selectivity (moles of acetic acid in the output) ÷ [ (moles of methanol in the feed) - (moles of methanol in the output) ] × (100%)
Methyl acetate selectivity 2 × (moles of methyl acetate in the discharge) ÷ [ (moles of methanol in the feed) - (moles of methanol in the discharge) ] × (100%)
Acrylic acid selectivity (moles of acrylic acid in the output) ÷ [ (moles of methanol in the feed) - (moles of methanol in the output) ] × (100%)
Methyl acrylate selectivity 2 × (moles of methyl acrylate in the discharge) ÷ [ (moles of methanol in the feed) - (moles of methanol in the discharge) ] × (100%)
Unless otherwise specified, the starting materials and catalysts in the examples of the present application were purchased commercially, and for samples that were not commercialized, the information of the samples was synthesized according to the relevant literature, and is shown in table 1.
TABLE 1 sources and molecular Si/Al ratios of different samples
| Catalyst and process for preparing same | Origin of origin | Si/Al2 |
| Na-MOR | South China Kai catalyst plant | 8 |
| Na-MOR | Dalian Chemical Physics Inst. | 15 |
| Na-FER | SHANGHAI NOVEL CHEMICAL TECHNOLOGY Co.,Ltd. | 30 |
| Na-MFI | South China Kai catalyst plant | 50 |
| Na-ZSM-57 | Dalian Chemical Physics Inst. | 30 |
| Na-MCM-35 | Dalian Chemical Physics Inst. | 50 |
Catalyst preparation
Preparation of Hydrogen Zeolite molecular Sieve catalyst samples
Na type molecular sieve and NH4NO3And carrying out ion exchange on the solution, filtering, drying and roasting to obtain a hydrogen type sample. A typical hydrogen form sample is prepared as follows: adding Na-MOR powder into pre-prepared 1mol/L NH4NO3The solid-liquid mass ratio in the solution was 1/10, the solution was exchanged for 2 hours at 80 ℃ with stirring, and the filtrate was washed. After continuous exchange for 3 times, drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the H-MOR.
Other hydrogen-form zeolite molecular sieve samples, such as H-FER, H-MFI, H-ZSM-57, H-MCM-35, were prepared similarly to H-MOR, except that the sodium-form molecular sieves of Table 1 were replaced.
Preparation of Metal modified catalyst samples
The method comprises the following steps: the metal is introduced by an immersion method, and a proper amount of nitrate (namely nitrate containing metal elements, such as copper nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, silver nitrate and gallium nitrate) is dissolved in deionized water to prepare a corresponding nitrate aqueous solution. Dropwise adding a proper amount of nitrate aqueous solution to the hydrogen type zeolite molecular sieve, standing for 24h, drying the obtained sample at 120 ℃ for 12h, and then roasting at 550 ℃ for 4h to obtain a metal element-containing hydrogen type zeolite molecular sieve catalyst sample.
For the example of a 5% Cu supported H-MOR catalyst, 39.64g of Cu (NO) was weighed3)·3H2Dissolving O in 200mL of deionized water to prepare 0.82mol/L copper nitrate solution, taking 20mL of solution, dropwise adding the solution to 20g of H-MOR, standing at room temperature for 24H, drying the obtained sample at 120 ℃ for 12H, and then roasting at 550 ℃ for 4H to obtain the H-MOR catalyst containing 5% of Cu. Other catalysts obtained by impregnation were prepared by the same procedure as described above, except that the concentration of nitrate and the volume of the solution dropped onto the molecular sieve were different due to the difference in metal content and water absorption of the molecular sieve.
The second method comprises the following steps: introducing metal by an ion exchange method, putting 200mL of aqueous solution containing a proper amount of nitrate (such as copper nitrate and silver nitrate) and 20g of hydrogen-type zeolite molecular sieve into a flask, carrying out condensation reflux treatment for 2h at 80 ℃ under a stirring state, filtering and separating, washing with deionized water, repeating the steps for 2 times, drying for 12h at 120 ℃, and then roasting for 4h at 550 ℃ to obtain a hydrogen-type zeolite molecular sieve catalyst sample containing metal elements.
Taking an H-FER catalyst loaded with 1% of Ag as an example, 200mL of silver nitrate solution with the concentration of 0.0094mol/L and a 20g H-FER molecular sieve are placed into a flask, and are subjected to condensation reflux treatment for 2H at 80 ℃ under the stirring state, filtration separation, washing by deionized water, repeating the steps for 2 times, drying for 12H at 120 ℃, and then roasting for 4H at 550 ℃ to obtain the H-FER catalyst containing 1% of Ag. Catalysts obtained by other ion exchange processes were prepared using the same procedure as described above, except that the nitrate concentration was different due to the difference in metal content.
The third method comprises the following steps: introducing metal by adopting an in-situ synthesis method, synthesizing FER molecular sieves and MOR molecular sieves containing metal (such as copper and silver) respectively according to the methods in Chinese Journal of Catalysis 2010Vol.31P788-792 and Catalysis Science & Technology 2015Vol.5P1961-19681, roasting the synthesized samples (the roasting temperature is 580 ℃, the roasting time is 8h), exchanging by 1mol/L ammonium nitrate, the solid-liquid mass ratio is 1/10, exchanging at 80 ℃ for 2h under the stirring state, filtering, washing, continuously exchanging for 3 times, drying at 120 ℃, roasting at 550 ℃ for 4h, and obtaining hydrogen type zeolite molecular sieve catalyst samples containing metal elements.
Preparation of shaped catalyst samples (containing matrix)
And (2) fully mixing 50-99% of hydrogen type zeolite molecular sieve catalyst sample or hydrogen type zeolite molecular sieve catalyst sample containing metal elements with 1-50% of matrix, and extruding and forming.
Preparation of pyridine Pre-adsorption samples
The molded hydrogen zeolite molecular sieve catalyst sample was treated at 300 ℃ for 3h in an atmosphere containing pyridine (100ml/min nitrogen passed through a vessel containing pyridine and carried pyridine to the catalyst) followed by 2h purging under nitrogen.
The molded hydrogen type sample is marked as H-zeolite molecular sieve type, and the molded hydrogen type sample is marked as H-zeolite molecular sieve type-Py after adsorbing pyridine; the molded metal-containing hydrogen type sample is marked as H-zeolite molecular sieve type-x% M, wherein M represents the contained metal elements, and x% represents the mass percentage content of the contained metal elements in the solid acid catalyst.
A series of catalysts were prepared according to the above procedure, as detailed in Table 2.
TABLE 2 information on the different catalysts
Example 1
5g of catalyst is loaded into a fixed bed reactor with the inner diameter of 26 mm, the catalyst is activated for 4h at 450 ℃ under the nitrogen atmosphere, then the temperature is adjusted to 280 ℃, the system pressure is increased to 5MPa by CO, then methanol and trioxymethylene are introduced, and the molar ratio of CO, methanol and trioxymethylene is 80: 2: 1, the total mass space velocity of the methanol and the trioxymethylene is 0.5h-1The volume space velocity of the feed gas is 4650h-1. The results of the reaction for 2h with different catalysts under these conditions are shown in Table 3.
TABLE 3 evaluation results of different catalysts
As can be seen from table 3: on the solid acid catalyst, the acrylic acid and methyl acrylate with higher added value can be obtained by taking cheap raw materials of methanol and formaldehyde compounds as raw materials.
Example 2
Loading 5g of No. 10 catalyst into a fixed bed reactor with the inner diameter of 26 mm, activating the catalyst for 4h at 450 ℃ in a nitrogen atmosphere, adjusting the temperature to 280 ℃, increasing the system pressure to 5MPa by using CO, introducing methanol and trioxymethylene, wherein the total mass space velocity of the methanol and the trioxymethylene is 0.5h-1The molar ratio of methanol to trioxymethylene is 2: 1, the reaction results when the molar ratios of CO and methanol were 5, 10, 20 and 40, respectively, are shown in Table 4, and the reaction time was 2 hours.
TABLE 4 reaction results without CO/methanol ratio
As can be seen from table 4: the increase in the CO/methanol ratio favours the formation of acrylic acid and methyl acrylate.
Example 3
Loading 5g of No. 10 catalyst into a fixed bed reactor with the inner diameter of 26 mm, activating the catalyst for 4h at 450 ℃ in a nitrogen atmosphere, adjusting the temperature to a corresponding reaction temperature, raising the system pressure to 5MPa by using CO, introducing methanol and trioxymethylene, wherein the molar ratio of the CO to the methanol to the trioxymethylene is 60: 3: 1, the mass space velocity of methanol and trioxymethylene is 1h-1The volume space velocity of the feed gas is 5900h-1. The reaction results at different reaction temperatures are shown in Table 5, and the reaction time is 2 h.
TABLE 5 reaction results at different reaction temperatures
As can be seen from table 5: the selectivity to acrylic acid and methyl acrylate increases and then decreases with increasing temperature, reaching a maximum around 280 ℃.
Example 4
5g of No. 10 catalyst is loaded into a fixed bed reactor with the inner diameter of 26 mm, the catalyst is activated for 4 hours at 450 ℃ in a nitrogen atmosphere, then the temperature is adjusted to 280 ℃, the system pressure is increased to different pressures by CO, then methanol and trioxymethylene are introduced, and the molar ratio of CO to methanol to trioxymethylene is 60: 3: 1, the mass space velocity of methanol and trioxymethylene is 0.7h -1The volume space velocity of the feed gas is 4100h-1. The results of the reaction at different reaction pressures are shown in Table 6, with a reaction time of 2 h.
TABLE 6 reaction results at different reaction pressures
As can be seen from table 6: the increase in reaction pressure facilitates the production of acrylic acid and methyl acrylate.
Example 5
5g of No. 10 catalyst is loaded into a fixed bed reactor with the inner diameter of 26 mm, the catalyst is activated for 4 hours at 450 ℃ under the nitrogen atmosphere, then the temperature is adjusted to 280 ℃, the system pressure is increased to 5MPa by CO, then methanol and formaldehyde compounds are introduced, and the molar ratio of CO to the methanol to the formaldehyde compounds is 60: 3: 1, the mass space velocity of the methanol and the formaldehyde compound is 0.7h-1,. Wherein the formaldehyde source is the reaction of formaldehyde solution (37 wt%), trioxymethylene and methylalThe results are shown in Table 7, with a reaction time of 2 h.
TABLE 7 results of the reaction when the formaldehyde source is formaldehyde solution, trioxymethylene and methylal
As can be seen from table 7: acrylic acid and methyl acrylate can be obtained when formaldehyde solution, trioxymethylene and methylal are taken as formaldehyde raw materials.
Example 6
Loading 5g of No. 10 catalyst into a fixed bed reactor with the inner diameter of 26 mm, activating the catalyst for 4h at 450 ℃ in a nitrogen atmosphere, adjusting the temperature to 280 ℃, raising the system pressure to 5MPa by using CO, introducing methanol and trioxymethylene, wherein the molar ratio of the CO to the methanol to the trioxymethylene is 60: 2: 1, the mass space velocity of the methanol and the trioxymethylene is 0.4h -1Further, dimethyl ether, acetic acid or methyl acetate was introduced into the system in such an amount ratio to methanol as 1:1, and the reaction results were as shown in Table 8, with a reaction time of 2 hours.
TABLE 8 reaction results with dimethyl ether, acetic acid and methyl acetate as raw materials
As can be seen from table 8: when the raw material I contains dimethyl ether, acetic acid and methyl acetate, acrylic acid and methyl acrylate can be obtained with high selectivity.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing acrylic acid and methyl acrylate is characterized in that raw material gas containing methanol, formaldehyde compounds and carbon monoxide is contacted with a solid acid catalyst in a reactor and reacts to obtain acrylic acid and methyl acrylate.
2. The method of claim 1, wherein the reaction conditions are: the reaction temperature is 170-380 ℃; the reaction pressure is 0.1-20 MPa; the volume space velocity of the feed gas is 500-20000 h -1；
Preferably, the reaction conditions are: the reaction temperature is 220-320 ℃; the reaction pressure is 1-10 MPa; the volume space velocity of the feed gas is 3000-10000 h-1。
3. The method of claim 1, wherein the formaldehyde-based compound comprises at least one of formaldehyde, methylal, trioxymethylene, and paraformaldehyde.
4. The method of claim 1, wherein the feed gas comprises feed i and feed ii;
the raw material I contains a material A;
the material A is methanol and a formaldehyde compound;
the raw material II contains carbon monoxide;
preferably, the molar percentage content of the raw material I in the raw material gas is 1-70%; the molar percentage content of the raw material II in the raw material gas is 30-99%;
further preferably, the molar percentage content of the raw material I in the raw material gas is 2-30%; the molar percentage content of the raw material II in the raw material gas is 70-98%.
5. The method according to claim 4, wherein the mass percentage of the methanol in the material A is 10-90%; the mass percentage of the formaldehyde compound in the material A is 10-90%.
6. The method according to claim 4, wherein the mass percentage of the material A in the raw material I is 50-100%;
Preferably, the raw material I also contains a material B;
the material B comprises at least one of dimethyl ether, methyl acetate and acetic acid.
7. The method of claim 1, wherein the solid acid catalyst comprises a zeolitic molecular sieve;
preferably, the zeolitic molecular sieve is selected from at least one of zeolitic molecular sieves having FER topology, zeolitic molecular sieves of MFI topology, zeolitic molecular sieves of MOR topology, zeolitic molecular sieves of MFS topology, zeolitic molecular sieves of MTF topology;
preferably, the silicon-aluminum oxide ratio of the zeolite molecular sieve is 8-100;
preferably, the zeolitic molecular sieve is a hydrogen-form zeolitic molecular sieve.
8. The method of claim 7, wherein the zeolitic molecular sieve is a metal-modified zeolite molecular sieve in the hydrogen form;
the metal is at least one of copper, silver, iron, cobalt, nickel and gallium;
preferably, the mass percentage of the metal element in the solid acid catalyst is 0.01-12 wt%;
further preferably, the mass percentage of the metal element in the solid acid catalyst is 0.1-8 wt%.
9. The method of claim 7, wherein the solid acid catalyst further comprises a substrate;
The matrix comprises at least one of alumina, silica, kaolin and magnesia;
preferably, the zeolite molecular sieve is a hydrogen-type zeolite molecular sieve that adsorbs pyridine.
10. The method according to claim 1, wherein the reactor is selected from any one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430792.9A CN111978171A (en) | 2019-05-22 | 2019-05-22 | Process for preparing acrylic acid and methyl acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430792.9A CN111978171A (en) | 2019-05-22 | 2019-05-22 | Process for preparing acrylic acid and methyl acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111978171A true CN111978171A (en) | 2020-11-24 |
Family
ID=73436637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910430792.9A Pending CN111978171A (en) | 2019-05-22 | 2019-05-22 | Process for preparing acrylic acid and methyl acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111978171A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097325A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof |
| CN108101767A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of acrylic acid and methyl acrylate |
-
2019
- 2019-05-22 CN CN201910430792.9A patent/CN111978171A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097325A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof |
| CN108101767A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of acrylic acid and methyl acrylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2013533798A (en) | Catalysts comprising platinum and gold nanoparticles and their use for the oxidation of glucose and methods for preparing such catalysts | |
| CN107445830B (en) | Method for producing glyoxylic ester by oxidative dehydrogenation of glycolate | |
| CN109574839B (en) | Method for directly producing methyl acetate and/or acetic acid by using synthesis gas | |
| CN108101767B (en) | Preparation method of acrylic acid and methyl acrylate | |
| RU2712277C1 (en) | Method of producing acrylic acid and methyl acrylate | |
| US20200239401A1 (en) | Method for directly producing methyl acetate and/or acetic acid from syngas | |
| CN112387268B (en) | Solid base catalyst for preparing 3-hydroxybutyraldehyde and preparation method thereof | |
| CN109180486B (en) | Catalyst for preparing dimethyl carbonate by selectively oxidizing methylal, preparation method and application thereof | |
| CN114950505B (en) | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof | |
| CN111978171A (en) | Process for preparing acrylic acid and methyl acrylate | |
| CN114522737A (en) | Method for preparing 3-acetoxy propanol with high selectivity | |
| CN111974442B (en) | Catalyst for producing acrylic acid and methyl acrylate, and preparation method and application thereof | |
| CN114425367A (en) | Catalyst system for preparing acrylate through acetylene carbonylation, preparation and application thereof | |
| CN114632543A (en) | Catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and preparation method and application thereof | |
| CN111974443A (en) | Catalyst for preparing acrylic acid and methyl acrylate, preparation method and application thereof | |
| CN109772331B (en) | CoFe catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof | |
| CN114409525B (en) | Preparation method of 1,4-cyclohexanedicarboxylic acid | |
| CN111250161B (en) | Preparation method of catalyst and application of catalyst in preparation of 6-methyl-3-heptylene-2-ketone | |
| CN113233949B (en) | Jiale musk tower kettle waste liquid treatment method | |
| CN117380252A (en) | Preparation method of catalyst for synthesizing pyridine from 3-methylpyridine | |
| CN111517956A (en) | Method for producing methyl acetate and co-producing methyl acrylate by dimethyl ether | |
| JPS6046096B2 (en) | Method for producing cyclohexylbenzene | |
| CN117777066A (en) | Continuous preparation method of 2, 5-tetramethyl tetrahydrofuran and catalyst used by same | |
| CN118045602A (en) | Catalyst for preparing octenal by condensing butyraldehyde, and preparation method and application thereof | |
| CN117945904A (en) | Method for preparing unsaturated carboxylic ester by utilizing multistage condensation reaction, reaction system and obtained product |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201124 |