阅读说明：本技术 生产丙酮的方法 (Method for producing acetone ) 是由 刘红超 朱文良 刘中民 文富利 刘勇 刘世平 周子乔 倪友明 马现刚 于 2019-02-02 设计创作，主要内容包括：本申请公开了一种生产丙酮的方法。该方法将含有有机化合物与一氧化碳的原料气通入载有固体酸催化剂的反应器中,反应,得到丙酮；其中,所述有机化合物包括甲醇、二甲醚中的至少一种；所述固体酸催化剂中包含酸性沸石分子筛。该方法由二甲醚一步生成丙酮,工艺过程简单,易分离,能耗低,摆脱了传统依赖于石油为原料的丙酮生产方法,具有广阔的应用前景。(The application discloses a method for producing acetone. Introducing raw material gas containing organic compounds and carbon monoxide into a reactor loaded with a solid acid catalyst, and reacting to obtain acetone; wherein the organic compound comprises at least one of methanol and dimethyl ether; the solid acid catalyst comprises an acidic zeolite molecular sieve. The method for producing acetone by dimethyl ether in one step has the advantages of simple process, easy separation and low energy consumption, gets rid of the traditional acetone production method which relies on petroleum as raw materials, and has wide application prospect.)

1. A method for producing acetone is characterized in that raw material gas containing organic compounds and carbon monoxide is introduced into a reactor loaded with a solid acid catalyst for reaction to obtain acetone;

wherein the organic compound comprises at least one of methanol and dimethyl ether;

the solid acid catalyst comprises an acidic zeolite molecular sieve.

2. The method according to claim 1, wherein the solid acid catalyst comprises 50-100% by mass of the acidic zeolite molecular sieve.

3. The method of claim 2, further comprising including a matrix in the solid acid catalyst;

the matrix comprises at least one of alumina, silica, kaolin and magnesia.

4. The method of claim 1, wherein the acidic zeolite molecular sieve comprises at least one of an acidic zeolite molecular sieve having a FER structure, an acidic zeolite molecular sieve having a MFI structure, an acidic zeolite molecular sieve having an ETL structure, an acidic zeolite molecular sieve having a MFS structure, an acidic zeolite molecular sieve having a MOR structure, an acidic zeolite molecular sieve having a MTF structure, an acidic zeolite molecular sieve having a BEA structure, an acidic zeolite molecular sieve having a FAU structure, an acidic zeolite molecular sieve having an EMT structure.

5. The method of claim 1, wherein the acidic zeolitic molecular sieve is modified with compound a;

the compound A is selected from any one of compounds with a structural formula shown in a formula I;

wherein R is₁、R₂、R₃、R₄、R₅Up to 3 of them are independently selected from F, Cl, Br, I, C₁～C₄Alkyl, CF₃、NO₂Any one of them, and the rest is H.

6. The method according to claim 5, wherein the compound A is selected from any one of 3-methylpyridine, 2, 6-dimethylpyridine, 2-ethylpyridine and 2-chloro-5-nitropyridine.

7. The method of claim 1, wherein the feed gas comprises feed gas I comprising the organic compound and feed gas II comprising the carbon monoxide;

the volume percentage of the organic compound in the feed gas I is 50-100%;

the volume percentage of the carbon monoxide in the feed gas II is 50-100%.

8. The method according to claim 7, wherein the raw material gas I further comprises a gas A, and the gas A is selected from at least one of acetic acid, methyl acetate, ethyl acetate and propyl acetate;

the feed gas II also comprises a gas B, and the gas B is at least one selected from hydrogen, nitrogen, helium, argon and carbon dioxide.

9. The process of claim 1, wherein the reaction in the reactor to produce acetone is carried out under the reaction conditions: the reaction temperature is 220-360 ℃, and the reaction pressure is 0.2-20MPa, and the mass space velocity of the organic compound is 0.001-2.0 h^-1The molar ratio of carbon monoxide to organic compound is 2-100: 1;

preferably, the reaction conditions for carrying out the reaction in the reactor to produce acetone are: the reaction temperature is 240-360 ℃, the reaction pressure is 2.0-15.0 MPa, and the mass space velocity of the organic compound is 0.1-2.0 h^-1The molar ratio of carbon monoxide to organic compound is 3-100: 1.

10. the method of claim 1, wherein the reactor is at least one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.

Technical Field

The application relates to a method for producing acetone, and belongs to the technical field of chemical product synthesis.

Background

In China, the demand of the market for acetone steadily and greatly rises year by year. The consumption reaches more than 120 ten thousand tons in 2013, and the consumption reaches 200 ten thousand tons in 2017. At present, the raw materials for producing acetone are mainly based on petroleum resources, and the production methods mainly comprise an isopropyl benzene method, an isopropyl alcohol dehydration method, a fermentation method, an acetylene hydration method and a propylene direct oxidation method. The acetone production by the cumene method is a common industrial production mode in the world at present. The cumene method is that benzene and propylene are used as raw materials, and the benzene and the propylene are subjected to Friede-Crafts acylation reaction to generate cumene; cumene and oxygen further react to generate cumene hydroperoxide; cumene hydroperoxide is hydrolyzed to phenol and acetone in the presence of liquid acid.

In the process of producing acetone by the isopropyl benzene method, three reactions are involved, so that the production process flow is long; inorganic acid is used as a catalyst, so that the corrosion is strong; in addition, the process is overly dependent on petroleum resources. The structure of rich coal, little gas and oil-deficient energy in China determines the development of a new acetone reaction process based on petroleum substitution, and becomes a technical problem to be solved urgently.

Disclosure of Invention

According to one aspect of the application, the method for producing acetone is provided, acetone is generated from dimethyl ether and/or methanol in one step, the process is simple, the separation is easy, the energy consumption is low, the traditional acetone production method which depends on petroleum as a raw material is eliminated, and the method has wide application prospect.

In the present application, a process for producing acetone, comprising the steps of: introducing a raw material gas containing an organic compound and carbon monoxide into a reactor carrying a solid acid catalyst, and reacting to obtain acetone;

wherein the organic compound comprises at least one of methanol and dimethyl ether;

the solid acid catalyst comprises an acidic zeolite molecular sieve.

The present inventors have found that acetone can be produced directly on a zeolite molecular sieve catalyst based on dimethyl ether and/or methanol as starting materials. The dimethyl ether in the method can be derived from synthesis gas, and the synthesis gas can be derived from coal, natural gas, shale gas and biomass, and the raw material source is wide. Dimethyl ether and carbon monoxide react to generate acetone under the condition of a zeolite molecular sieve catalyst, the traditional acetone production method which depends on petroleum as a raw material is avoided, and the preparation method provided by the application has the advantages of simple process, easiness in separation and low energy consumption, and can be widely applied to the chemical production process.

In the present application, when the organic compound includes methanol and dimethyl ether, the ratio of the two is not strictly limited, and those skilled in the art can select a suitable ratio according to actual needs. Preferably, the mole percentage of methanol to dimethyl ether is 1: 9-8: 2.

optionally, the mass percentage of the acidic zeolite molecular sieve in the solid acid catalyst is 50-100%.

Specifically, when the mass percentage of the acidic zeolite molecular sieve is 100%, only the acidic zeolite molecular sieve is contained in the solid acid catalyst.

The acidic zeolitic molecular sieve may be prepared by any suitable method known in the art and is not limited in its preparation herein. Preferably, the preparation method of the acidic zeolite molecular sieve comprises the following steps: passing Na-type molecular sieve through NH₄NO₃Ion exchange, drying and roasting to obtain the acid type zeolite molecular sieve.

Optionally, the solid acid catalyst further comprises a matrix; the matrix comprises at least one of alumina, silica, kaolin and magnesia.

The solid acid catalyst comprising the matrix can be prepared by any suitable method known in the art, and the preparation method is not limited herein. Preferably, the solid acid catalyst containing a matrix is prepared by: mixing Na-type zeolite molecular sieve with matrix, adding nitric acid, kneading, extruding to form, calcining, grinding, and making powder by NH₄NO₃And carrying out ion exchange, drying and roasting to obtain the solid acid catalyst containing the matrix.

Optionally, the acidic zeolite molecular sieve comprises at least one of an acidic zeolite molecular sieve having a FER structure, an acidic zeolite molecular sieve having a MFI structure, an acidic zeolite molecular sieve having an ETL structure, an acidic zeolite molecular sieve having a MFS structure, an acidic zeolite molecular sieve having a MOR structure, an acidic zeolite molecular sieve having a MTF structure, an acidic zeolite molecular sieve having a BEA structure, an acidic zeolite molecular sieve having a FAU structure, an acidic zeolite molecular sieve having an EMT structure.

Optionally, the acidic zeolite molecular sieve is modified with compound a;

the compound A is selected from any one of compounds with a structural formula shown in a formula I;

wherein R is₁、R₂、R₃、R₄、R₅Up to 3 of them are independently selected from F, Cl, Br, I, C₁～C₄Alkyl of, CF₃、NO₂Any one of them, and the rest is H.

In this application, when R is₁、R₂、R₃、R₄、R₅When all the zeolite is H, the acidic zeolite molecular sieve is modified by pyridine. When R is₁、R₂、R₃、R₄、R₅At least one selected from F, Cl, Br, I, C₁～C₄Alkyl radical, NO₂The acidic zeolite molecular sieve is an acidic zeolite molecular sieve modified by a pyridine substituent.

The pyridine or pyridine substituent modified acidic zeolite molecular sieve can be prepared by any suitable method in the prior art by one skilled in the art, and the preparation method is not limited in the application. Preferably, the preparation method of the pyridine or pyridine substituent modified acidic zeolite molecular sieve comprises the following steps: and (3) treating the molecular sieve I at high temperature in an atmosphere containing pyridine or pyridine substitutes to obtain the pyridine or/and pyridine substitute modified acidic zeolite molecular sieve.

In this application, C₁～C₄Refers to an alkyl group having 1 to 4 carbon atoms, such as CH₃-、C₂H₅-。

Optionally, the compound A is selected from any one of 3-methylpyridine, 2, 6-dimethylpyridine, 2-ethylpyridine and 2-chloro-5-nitropyridine.

Optionally, the feed gas comprises feed gas I containing the organic compound and feed gas II containing the carbon monoxide; the volume percentage of the organic compound in the feed gas I is 50-100%; the volume percentage of the carbon monoxide in the raw material II is 50-100%.

For example, the volume percentage of the dimethyl ether and the methanol in the raw material gas I is 50-100%.

The upper limit of the volume percentage of the organic compound in the raw material gas I is 80%, 95%, 97.4% or 100%, and the lower limit of the volume percentage of the organic compound in the raw material gas I is any one of 50%, 80%, 95% or 97.4%.

Preferably, the raw gas I also comprises a gas A, and the gas A is selected from at least one of methyl acetate, acetic acid, ethyl acetate and propyl acetate; the feed gas II also comprises a gas B, and the gas B is at least one selected from hydrogen, nitrogen, helium, argon and carbon dioxide.

In the present application, a higher acetone production rate can be achieved by adding gas A to feed gas I. Preferably, gas a is methyl acetate.

The upper limit of the volume percentage of the gas A in the raw material gas I is any one of 2.6%, 5%, 20% and 50%, and the lower limit of the volume percentage of the gas A in the raw material gas I is any one of 20%, 5%, 2.6% and 0%.

Optionally, the reaction conditions for performing the reaction in the reactor to produce acetone are: the reaction temperature is 220-360 ℃, the reaction pressure is 0.2-20 MPa, and the mass space velocity of the organic compound is 0.001-2.0 h^-1The molar ratio of carbon monoxide to organic compound is 2-100: 1.

the upper limit of the reaction temperature is selected from any one of 240 ℃, 280 ℃, 290 ℃, 300 ℃, 320 ℃, 340 ℃ and 360 ℃; the lower limit of the reaction temperature is selected from any one of 220 ℃, 240 ℃, 280 ℃, 290 ℃, 300 ℃, 320 ℃ and 340 ℃.

The upper limit of the reaction pressure is selected from any one of 1MPa, 5MPa, 8MPa, 12MPa, 15MPa and 20MPa, and the lower limit of the reaction pressure is selected from any one of 0.2MPa, 1MPa, 5MPa, 8MPa, 12MPa and 15 MPa.

The upper limit of the mass space velocity of the organic compound is selected from 0.1h^-1、0.3h^-1、0.5h^-1、1h^-1、1.5h^-1、2h^-1The lower limit of the mass space velocity of the organic compound is selected from 0.001h^-1、0.1h^-1、0.3h^-1、0.5h^-1、1h^-1、1.5h^-1Any one of them.

The upper limit of the molar ratio of carbon monoxide to organic compound is selected from 10: 1. 20: 1. 50: 1. 60: 1. 80: 1. 100, and (2) a step of: the lower limit of the molar ratio of carbon monoxide to organic compound is selected from 2: 1. 10: 1. 20: 1. 50: 1. 60: 1. 80: 1.

preferably, the reaction conditions for carrying out the reaction in the reactor to produce acetone are: the reaction temperature is 240-360 ℃, the reaction pressure is 2.0-15.0 MPa, and the mass space velocity of the organic compound is 0.1-2.0 h^-1The molar ratio of carbon monoxide to organic compound is 3-100: 1.

optionally, the reactor is at least one of a fixed bed reactor, a fluidized bed reactor, a moving bed reactor.

The beneficial effects that this application can produce include:

the method for producing acetone provided by the application has the advantages that acetone is generated from methanol and/or dimethyl ether and carbon monoxide in one step, the process is simple, the separation is easy, the energy consumption is low, the traditional acetone production method which depends on petroleum as a raw material is eliminated, and the acetone has higher selectivity and wide application prospect.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.

In the present application, the conversion of methanol, dimethyl ether and the selectivity to methyl acetate are both calculated based on the carbon moles of dimethyl ether:

conversion of dimethyl ether [ (mole number of dimethyl ether carbon in raw material gas) - (mole number of dimethyl ether carbon in product) ]/(mole number of dimethyl ether carbon in raw material gas) × (100%)

Conversion of methanol [ (mole number of methanol carbon in raw material gas) - (mole number of methanol carbon in product) ]/(mole number of methanol carbon in raw material gas) × (100%)

Selectivity to acetone ═ acetone moles ÷ molar sum of different organics of the product × 100%

Selectivity to methyl acetate-methyl acetate moles ÷ molar sum of different organics of the product × 100%

Selectivity to acetic acid ═ acetic acid moles ÷ sum of moles of different organics of the product × 100%

The selectivity to hydrocarbons is defined as the hydrocarbon mole number, the sum of the moles of the different organic compounds of the product x 100%