阅读说明：本技术 一种制备酮类有机物的方法 (Method for preparing ketone organic matter ) 是由 周子乔 刘中民 朱文良 刘红超 刘勇 倪友明 于 2019-02-02 设计创作，主要内容包括：本申请公开了一种制备酮类有机物的方法,原料气通过载有酸性分子筛催化剂的反应器,反应,获得酮类有机物；所述原料气中包括反应原料；所述反应原料选自具有式I所示结构式的化合物中的至少一种；其中,R<Sup>1</Sup>选自C<Sub>1</Sub>～C<Sub>10</Sub>烃基中的一种；R<Sup>2</Sup>选自H、C<Sub>1</Sub>～C<Sub>10</Sub>烃基中的一种,在式Ⅰ中,羰基的邻位碳上包含有α-氢原子。本发明提供的制备酮类有机物的方法,和传统的单质型/负载型金属催化剂相比,具有反应活性高、原料易得及制备过程简单等优点,具有良好的工业应用前景。(The application discloses a method for preparing ketone organic matters, wherein raw material gas passes through a reactor loaded with an acidic molecular sieve catalyst to react to obtain the ketone organic matters; the raw material gas comprises reaction raw materials; the reaction raw material is selected from at least one of compounds with a structural formula shown in a formula I; wherein R is 1 Is selected from C 1 ～C 10 One of the hydrocarbon groups; r 2 Selected from H, C 1 ～C 10 One of the hydrocarbon groups, in the formula I, the carbon adjacent to the carbonyl group contains α -hydrogen atoms, the method for preparing the ketone organic substance provided by the invention, and the traditional simple substance type/loadCompared with the metal catalyst, the metal catalyst has the advantages of high reaction activity, easily obtained raw materials, simple preparation process and the like, and has good industrial application prospect.)

1. A method for preparing a ketone organic material, comprising: the raw material gas passes through a reactor loaded with an acidic molecular sieve catalyst to react to obtain a ketone organic substance;

the raw material gas comprises reaction raw materials;

the reaction raw material is selected from at least one of compounds with a structural formula shown in a formula I;

wherein R is¹Is selected from C₁～C₁₀One of the hydrocarbon groups;

R²selected from H, C₁～C₁₀One of the hydrocarbon groups;

in formula I, the carbon adjacent to the carbonyl group contains an alpha-hydrogen atom.

2. The method of claim 1, wherein the acidic molecular sieve catalyst comprises at least one of an acidic molecular sieve catalyst having a CHA topology, an acidic molecular sieve catalyst having a FER topology, an acidic molecular sieve catalyst having a MFI topology, an acidic molecular sieve catalyst having a MOR topology, an acidic molecular sieve catalyst having a FAU topology, and an acidic molecular sieve catalyst having a BEA topology.

3. The method of claim 2, wherein the acidic molecular sieve catalyst comprises an acidic molecular sieve;

the acidic molecular sieve comprises at least one of an HSAPO-34 molecular sieve, an HZSM-35 molecular sieve, an HZSM-5 molecular sieve, an HMOR molecular sieve, an HY molecular sieve and an H beta eta molecular sieve;

preferably, the atomic silica-alumina ratio of the ZSM-35 molecular sieve, the ZSM-5 molecular sieve, the MOR molecular sieve, the Y molecular sieve and the beta eta molecular sieve is independently 1-70;

preferably, the atomic silica-alumina ratio of the ZSM-35 molecular sieve, the ZSM-5 molecular sieve, the MOR molecular sieve, the Y molecular sieve and the beta eta molecular sieve is independently 2.5-25.

4. The method of claim 3, wherein the acidic molecular sieve catalyst further comprises a promoter metal element;

the metal element is at least one of gallium, iron, copper and silver;

preferably, the mass percentage of the metal element in the acidic molecular sieve catalyst is 0.01-10.0 wt%;

wherein the metal element is calculated by the mass of a metal simple substance;

preferably, the metal element is supported in the acidic molecular sieve.

5. The method of claim 3 or 4, wherein the acidic molecular sieve catalyst further comprises a binder;

the binder comprises at least one of alumina, silica, zirconia and magnesia;

the mass percentage of the binder in the acidic molecular sieve catalyst is 0-80 wt%;

preferably, the binder is mixed with the acidic molecular sieve for molding.

6. The method of claim 1, wherein R is¹Is selected from C₁～C₁₀Alkyl radical, C₇～C₁₀One of aryl groups;

R²selected from H, C₁～C₁₀Alkyl radical, C₆～C₁₀One of aryl groups;

preferably, R¹Is selected from C₁～C₇Alkyl radical, C₇One of aryl groups;

R²selected from H, C₁～C₇Alkyl radical, C₆～C₇One of aryl groups;

preferably, R¹Is selected from C₁～C₃Alkyl radical, C₇One of aryl groups;

R²selected from H, C₁～C₃Alkyl radical, C₆～C₇One of aryl groups.

7. The method of claim 1, wherein the ketone organic is at least one compound selected from the group consisting of compounds having the structural formula shown in formula II:

wherein R is³，R⁴Independently selected from C₁～C₁₀One of the hydrocarbon groups;

preferably, said R is³，R⁴Independently selected from C₁～C₁₀Alkyl radical, C₇～C₁₀One of aryl groups;

preferably, said R is³，R⁴Independently selected from C₁～C₇Alkyl radical, C₇One of aryl groups;

preferably, said R is³，R⁴Independently selected from C₁～C₃Alkyl radical, C₇One of aryl groups.

8. The process according to claim 1, characterized in that the reaction conditions are: the mass space velocity of the reaction raw materials is 0.1-2 h^-1The reaction temperature is 240-400 ℃, and the reaction pressure is 1-50 bar;

preferably, the reaction conditions are: the mass space velocity of the reaction raw materials is 0.1-1.0 h^-1The reaction temperature is 280-330 ℃, and the reaction pressure is 20-50 bar.

9. The method of claim 1, wherein the feed gas further comprises a diluent gas, and the diluent gas is an inactive gas;

the inert gas is selected from inert gas and N₂、CO、H₂At least one of;

the volume percentage of the diluent gas in the feed gas is 0-80%;

preferably, the inert gas comprises N₂、He、CO、H₂And Ar, or a mixture thereof.

10. The method of claim 1, wherein the reactor comprises any one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.

Technical Field

The application relates to a method for preparing ketone organic matters, and belongs to the technical field of organic matter preparation.

Background

Acetone is an important organic synthetic raw material and is used for producing epoxy resin, polycarbonate, organic glass, medicines, pesticides and the like; is also an important raw material for manufacturing acetic anhydride, diacetone alcohol, chloroform, iodoform, epoxy resin, polyisoprene rubber, methyl methacrylate and the like. Is also a good solvent, is used for paint, adhesive, steel cylinder acetylene and the like; it is also used in the industries of smokeless powder, acetate fiber, spray paint, etc. Also used as a diluent, a cleaning agent and an extracting agent, and used as an extracting agent in the industries of grease and the like.

The disclosure shows that acetone, also known as dimethyl ketone, is the most important ketone in the saturated aliphatic ketone series. It is one of the most important basic organic chemical raw materials. The demand of the market of China on acetone is very vigorous, and the acetone is in a situation of steadily and greatly rising year by year. In 1996, the apparent consumption of acetone in China is 16 ten thousand tons, and the consumption of acetone in the national market in 2013 reaches more than 120 ten thousand tons, which is increased by nearly 8 times than that in 1996.

Acetone prices have been on the rise, especially the fastest rise in 2016. According to the' 2016 report of economic data on bulk commodities in China, 2016, issued by business society, the 2016 price of acetone rises from 3516.67 yuan per ton at the beginning of the year to 7305.56 yuan per ton at the end of the year, and the annual rise reaches 107.74%.

The production method of acetone mainly comprises an isopropanol method, an cumene method, a fermentation method, an acetylene hydration method and a propylene direct oxidation method. At present, the industrial production of acetone in the world is mainly based on the cumene method. Two thirds of the world's acetone is a by-product of phenol production and is one of the products of cumene oxidation. The major patent producers for this technology currently are Kellogg Brown & Root, Mitsui chemical, and UOP.

Solutia developed a technology for producing phenol by oxidizing benzene with nitrogen oxide, but the company cancelled the project of building a plant using the process in the last year because the gross profit level was too low using this technology. Japanese researchers have recently developed a one-step process for producing phenol and acetone from benzene using a europium-titanium catalyst.

The acetone production methods in the reports all use benzene and propylene in petrochemical industry as raw materials, and the cumene method does not accord with the actual national conditions in the environment of rich coal, little oil and little gas in China. And most of the catalysts used in the isopropyl benzene method are homogeneous catalysts, and the problems of difficult separation, equipment corrosion and the like exist in the use of the homogeneous catalysts, so that the production cost of the acetone is increased.

Disclosure of Invention

According to one aspect of the present application, there is provided a method of preparing a ketone-based organic material. Compared with the traditional simple substance type and/or supported metal catalyst, the method for preparing the ketone organic matter has the advantages of high reaction activity, easily obtained raw materials, simple preparation process and the like, reduces the production cost, and has good industrial application prospect.

A method of preparing a ketone-based organic substance, the method comprising: the raw material gas passes through a reactor loaded with an acidic molecular sieve catalyst to react to obtain a ketone organic substance;

the raw material gas comprises reaction raw materials;

the reaction raw material is selected from at least one of compounds with a structural formula shown in a formula I;

wherein R is¹Is selected from C₁～C₁₀One of the hydrocarbon groups;

R²selected from H, C₁～C₁₀One of the hydrocarbon groups;

in formula I, the carbon adjacent to the carbonyl group contains an alpha-hydrogen atom.

In this application, an alpha-hydrogen atom refers to a hydrogen on a carbon atom attached to a functional group, a carbonyl group.

In this application, when R is²When it is H, the reaction raw material is R¹Carboxylic acid compounds of the formula COOH; when R is²Is C₁～C₁₀When it is a hydrocarbon group, transThe raw material is provided with R¹COOR²Ester compounds of the structural formula.

The ester ketonization reaction may occur in a solid acid molecular sieve. The solid acid molecular sieve has the advantages of rich porous structure, simple preparation, wide source and the like, and has good industrial application prospect when used for catalyzing the ketonization reaction.

The purpose of the application is to provide a novel method for preparing ketone organic matters. The method comprises the step of reacting carboxylic acid compounds and/or ester compounds with a structural formula I in a reactor containing an acidic molecular sieve catalyst under certain reaction conditions to obtain corresponding ketone organic matters.

Optionally, the acidic molecular sieve catalyst comprises at least one of an acidic molecular sieve catalyst having CHA topology, an acidic molecular sieve catalyst having FER topology, an acidic molecular sieve catalyst having MFI topology, an acidic molecular sieve catalyst having MOR topology, an acidic molecular sieve catalyst having FAU topology, an acidic molecular sieve catalyst having BEA topology.

In the application, the acidic molecular sieve catalyst may be an acidic molecular sieve, or an acidic molecular sieve loaded with an auxiliary metal element, or a catalyst composed of an acidic molecular sieve and a binder, or a catalyst composed of an acidic molecular sieve loaded with an auxiliary metal element and a binder.

Optionally, the acidic molecular sieve catalyst comprises an acidic molecular sieve; the acidic molecular sieve comprises at least one of an HSAPO-34 molecular sieve, an HZSM-35 molecular sieve, an HZSM-5 molecular sieve, an HMOR molecular sieve, an HY molecular sieve and an H beta eta molecular sieve.

Optionally, the atomic silica to alumina ratio of the ZSM-35 molecular sieve, the ZSM-5 molecular sieve, the MOR molecular sieve, the Y molecular sieve and the beta eta molecular sieve is independently 1-70.

Preferably, the atomic silica-alumina ratio of the ZSM-35 molecular sieve, the ZSM-5 molecular sieve, the MOR molecular sieve, the Y molecular sieve and the beta eta molecular sieve is independently 2.5-25.

In the present application, the upper limit of the silicon-aluminum atomic ratio of the acidic molecular sieve is selected from 2.5, 22, 25 and 70, and the lower limit of the silicon-aluminum atomic ratio of the acidic molecular sieve is selected from 1, 2.5, 22 and 25.

Optionally, the acidic molecular sieve catalyst further comprises an auxiliary metal element; the metal element is at least one selected from gallium, iron, copper and silver.

Optionally, the mass percentage of the metal element in the acidic molecular sieve catalyst is 0.01-10.0 wt%; wherein the metal element is calculated by the mass of a simple metal substance.

Optionally, the promoter metal element is supported in the acidic molecular sieve.

In the present application, the promoter metal element may be introduced into the acidic molecular sieve catalyst by in situ synthesis, metal ion exchange or impregnation, etc.

The following takes Fe-supported HMOR molecular sieve as an example, and specifically describes the method for introducing the metal element. The present application is not limited to the following modes, and the skilled person can select the modes and conditions for introduction according to actual needs. This application only introduces preferred modes and conditions.

When introduced by in situ synthesis, a metered amount of sodium aluminate is first dissolved in water and stirred to a clear solution, after which sodium hydroxide is added and stirring is continued. To the above solution was added a metered amount of silica sol (silica content 30%) under stirring, and after stirring was continued for 30 minutes, an aqueous ferric nitrate solution was added. And (3) filling the obtained uniform gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 20 hours in a constant-temperature oven at 180 ℃ in a rotating state. And filtering the crystallized sample, washing to be neutral, and drying overnight at 120 ℃ to obtain the in-situ synthesized FeNaMOR. The obtained FeNaMOR is treated with NH₄NO₃FeHMOR was obtained after exchange (see the description in section 1.2 of example 1 for details).

When introduced by metal ion exchange, 20g of HMOR and 2.41g of ferric nitrate were dissolved in 100ml of deionized water and stirred at 80 ℃ for 12 h. Then filtered, the catalyst was dried overnight at 100 ℃ and calcined at 550 ℃ for 4h to obtain FeHMOR by metal ion exchange.

When introduced by the dipping method, 2.41g of ferric nitrate was dissolved in 20ml of deionized water. 20g of HMOR were immersed in the ferric nitrate solution. And after the catalyst sufficiently adsorbs the ferric nitrate solution, drying the catalyst at 100 ℃ overnight, and roasting the catalyst at 550 ℃ for 4 hours to obtain FeHMOR introduced by an impregnation method.

Optionally, the acidic molecular sieve catalyst further comprises a binder;

the binder comprises at least one of alumina, silica, zirconia and magnesia;

the mass percentage of the binder in the acidic molecular sieve catalyst is 0-80 wt%.

Preferably, the mass percentage of the binder in the acidic molecular sieve catalyst is 0-50 wt%.

Optionally, the binder is mixed with the acidic molecular sieve for molding.

In the application, the acidic molecular sieve and the binder may be directly mixed to obtain the acidic molecular sieve catalyst containing the binder, or the acidic molecular sieve loaded with the promoter metal element may be mixed with the binder to obtain the acidic molecular sieve catalyst containing the binder and the promoter metal element.

For example, when the acidic molecular sieve catalyst comprises an acidic molecular sieve and a binder, the preparation method is as follows: and adding a binder into the acidic molecular sieve, uniformly mixing, extruding, crushing, and screening particles of 20-40 meshes to obtain the acidic molecular sieve catalyst containing the binder.

Specifically, the binder may be any one of alumina, silica, zirconia, and magnesia, or a mixture of alumina and silica. Preferably, the binder comprises alumina and silica, the proportion of which can be selected by those skilled in the art according to actual needs, and the mass ratio of the alumina to the silica is preferably 1: 1.

in the present application, the upper limit of the mass percentage of the binder in the acidic molecular sieve catalyst is selected from 10%, 20%, 30%, 50%, 80%, and the lower limit of the mass percentage of the binder in the acidic molecular sieve catalyst is selected from 0%, 10%, 20%, 30%, 50%.

Alternatively, R¹Is selected from C₁～C₁₀Alkyl radical, C₇～C₁₀One of aryl groups; r²Selected from H, C₁～C₁₀Alkyl radical, C₆～C₁₀One of aryl groups.

Alternatively, R¹Is selected from C₁～C₇Alkyl radical, C₇One of aryl groups; r²Selected from H, C₁～C₇Alkyl radical, C₆～C₇One of aryl groups.

When the reaction raw material is an ester compound, the reaction raw material can be butyl butyrate, amyl valerate and hexyl hexanoate; phenethyl butyrate, phenethyl valerate; butyl phenylacetate, amyl phenylacetate, hexyl phenylacetate; phenyl ethyl phenylacetate.

When the raw material is carboxylic acid compounds, the carboxylic acid compounds can be valeric acid, caproic acid, heptanoic acid, phenylacetic acid and phenylpropionic acid.

Alternatively, R¹Is selected from C₁～C₃Alkyl radical, C₇One of aryl groups; r²Selected from H, C₁～C₃Alkyl radical, C₆～C₇One of aryl groups.

The reaction raw materials can be: benzyl phenylacetate, ethyl propionate, propyl butyrate, isopropyl isobutyrate; butyric acid, phenylacetic acid.

Preferably, R¹、R²Are all-CH₃When the reaction is carried out, the reaction raw material is methyl acetate.

Optionally, the ketone organic is selected from at least one compound having a formula shown in formula II:

wherein R is³，R⁴Independently selected from C₁～C₁₀One kind of hydrocarbyl.

Alternatively, the R is³，R⁴Independently selected from C₁～C₁₀Alkyl radical, C₇～C₁₀One of aryl groups.

Alternatively, the R is³，R⁴Independently selected from C₁～C₇Alkyl radical, C₇One of aryl groups.

Alternatively, the R is³，R⁴Independently selected from C₁～C₃Alkyl radical, C₇One of aryl groups.

In this application, for example, when the starting material for the reaction is a compound having R¹COOR²When the ester compound has the structural formula, the generated ketone organic matter has R³COR⁴Structural formula (I). (the specific chemical reaction formula is R)¹ ₁COOA₁+R¹ ₂COOA₂→R¹ ₁COR¹ ₂+A₁OA₂+CO₂And 2 molecules of carboxylate react to generate 1 molecule of ketone, 1 molecule of ether and 1 molecule of carbon dioxide).

As another example, when the reaction starting material is a compound having R¹When carboxylic acid compounds of the formula COOH are used, the organic ketone compound formed therefrom has R³COR⁴Structural formula (I). (the specific chemical reaction formula is R)¹ ₁COOH+R¹ ₂COOH→R¹ ₁COR¹ ₂+H₂O+CO₂2 molecules of carboxylic acid react to form 1 molecule of ketone, 1 molecule of water and 1 molecule of carbon dioxide).

Optionally, the reaction conditions are: the mass space velocity of the reaction raw materials is 0.1-2 h^-1The reaction temperature is 240-400 ℃, and the reaction pressure is 1-50 bar.

Preferably, the mass space velocity of the reaction raw materials is 0.1-1.0 h^-1The reaction temperature is 280-330 ℃, and the reaction pressure is 20-50 bar.

In the present application, the upper limit of the mass space velocity of the reaction feed is selected from 0.5h^-1、1.0h^-1、1.4h^-1、1.6h^-1、2.0h^-1The lower limit of the mass space velocity is selected from 0.1h^-1、0.5h^-1、1.0h^-1、1.4h^-1、1.6h^-1。

The upper limit of the reaction temperature is selected from 260 deg.C, 280 deg.C, 330 deg.C, 350 deg.C, 400 deg.C, and the lower limit of the reaction temperature is selected from 240 deg.C, 260 deg.C, 280 deg.C, 330 deg.C, 350 deg.C.

The upper limit of the reaction pressure is selected from 10bar, 20bar, 40bar, 50bar, and the lower limit of the reaction pressure is selected from 1bar, 10bar, 20bar, 40 bar.

Optionally, the raw material gas also comprises a diluent gas, and the diluent gas is an inactive gas;

the inert gas is selected from inert gas and N₂、CO、H₂At least one of;

the volume percentage of the diluent gas in the feed gas is 0-80%.

Optionally, the inert gas comprises N₂、He、CO、H₂And Ar, or a mixture thereof.

In the present application, the upper limit of the volume percentage of the diluent gas in the raw material gas is 10%, 20%, 30%, 50%, 80%, and the lower limit of the volume percentage of the diluent gas in the raw material gas is 0%, 10%, 20%, 30%, 50%.

In this application, when the diluent gas comprises CO, the CO has R with the reaction feed¹COOR²The ester compound of the structural formula reacts to generate the ketone compound. Taking methyl acetate as an example, methyl acetate and carbon monoxide are in contact reaction with a catalyst, namely a hydrogen mordenite molecular sieve, and acetone can be generated with high selectivity (the acetone yield is more than 67%) at the temperature of 280-330 ℃ and the pressure of 20-50 bar.

When the reaction conditions were 280 ℃ and 20bar, the acetone selectivity was the highest, which was 73% acetone yield.

Optionally, the reactor comprises any one of a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a tank reactor.

In the present application, "C₁～C₁₀”，“C₆～C₁₀"and the like" each refer to the number of carbon atoms contained in a group.

In the present application, "aryl" refers to a group formed by the loss of any hydrogen atom from an aromatic hydrocarbon compound molecule.

In the present application, "alkyl" refers to a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound.

The beneficial effects that this application can produce include:

(1) the present application provides a novel process for the preparation of organic ketones, in particular acetone.

(2) The method for preparing the ketone organic matter is carried out on the acidic molecular sieve catalyst, has the characteristics of high reaction activity, simple catalyst industrial preparation, difficult loss of catalytic active ingredients and the like, and has good industrial application prospect.

(3) Compared with the prior elemental catalyst and/or active carbon catalyst loaded with metal elements, the acidic molecular sieve catalyst used in the application has the advantages of environmental friendliness, low preparation cost, strong sintering resistance, stable chemical property and the like, and is a catalyst with wide application prospect.

(4) In the application, when the dilution gas comprises CO, the CO reacts with the ester compound under the catalysis of the catalyst hydrogen-type mercerized molecular sieve to generate the ketone compound, and the selectivity of acetone is higher than 67%.

Detailed Description

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

All molecular sieves and related feedstocks in the examples of this application were purchased commercially, unless otherwise specified.

The analysis methods and conditions in the examples of the present application are as follows:

the raw materials and the products are detected on line by an Aligent7890B gas chromatography of Agilent and an HP-PLOT/Q capillary column of Agilent.

Preparation of raw gas in this application: the raw material is fed into the reactor by the following method, for example, the raw material methyl acetate is kept at a constant temperature in a water bath, a diluent gas is introduced for bubbling, a mixed gas (namely, raw material gas) carrying raw material steam is introduced into the fixed bed reactor, and the amount of the raw material fed into the reactor can be adjusted according to the flow rate of the reaction gas. The saturated vapor pressure of the raw materials under different temperature conditions can be calculated by the following formula:

lgP*＝A–B/(t+C)

a, B, C are the physical parameters of the raw materials respectively, and can be obtained by inquiring the handbook of Lanzhou chemistry, and t represents the temperature. This allows calculation of the saturated vapor pressure of the feedstock at any temperature. The amount of material fed to the reactor per unit time can be calculated from the saturated vapor pressure.

Before the catalyst is extruded and formed, a binder with corresponding mass is added to assist the catalyst in forming.

Methyl acetate conversion rate ═ [ (moles of methyl acetate in feed) - (moles of methyl acetate in discharge) ]/(moles of methyl acetate in feed) × (100%)

Acetone selectivity (moles of acetone in the output) ÷ (moles of carbon for all products) × (100%).

In the present application, the calculation of the conversion of other raw materials is similar to that of methyl acetate and is not described in detail herein.

The raw material in the application refers to ester compounds and/or carboxylic acid compounds with a chemical formula shown in a formula I.

In the present application, SAPO-34 was purchased from Nankai catalyst plants;

NaZSM-35 molecular sieves were purchased from Nankai catalyst works;

NaZSM-5 molecular sieves were purchased from Nankai catalyst works;

NaMOR molecular sieves were purchased from south opening catalyst works;

NaY molecular sieves were purchased from south-opening catalyst works;

Na-Beta molecular sieves were purchased from Nankai catalyst works.

1. Preparation of acidic molecular sieve catalyst

1.1 silicoaluminophosphate molecular sieve catalysts

SAPO-34 with a silicon to aluminum atomic ratio of 20 is commercially available. The molecular sieve is roasted for 4 hours at 600 ℃, and is extruded and crushed to screen a No. 1 catalyst with 20-40 meshes for later use.

1.2 Hydrogen-type acidic silicon-aluminum molecular sieve catalyst

Exchanging 100 g of baked NaZSM-35 molecular sieve, NaZSM-5 molecular sieve, NaMOR molecular sieve, NaY molecular sieve and Na-Beta molecular sieve with the atomic ratio of 25, 2.5, 22, 1 and 70 respectively with 1L of ammonium nitrate water solution with the concentration of 1mol/L for three times, wherein each time is 2 hours, washing with deionized water, drying at 100 ℃ overnight, baking at 550 ℃ in a muffle furnace for 4 hours to obtain hydrogen type ZSM-35 molecular sieve (HZSM-35), hydrogen type ZSM-5 molecular sieve (HZSM-5), hydrogen type MOR molecular sieve (HMOR), hydrogen type Y molecular sieve (HY) and hydrogen type Beta molecular sieve (H Beta eta), and respectively preparing a 20-40-mesh 2# catalyst, a 3# catalyst, a 4# catalyst, a 5# catalyst and a 6# catalyst by extrusion.

1.3 Supported M/HZSM-5 catalyst (M is a supported metal element)

The load type M/HZSM-5 catalyst is prepared by an isometric impregnation method. 2.56g of Ga (NO) are added₃)₃、1.7gAgNO₃、1.88gCu(NO₃)₂And 2.41gFe (NO)₃)₃Dissolving in 20ml deionized water to prepare corresponding nitrate aqueous solution. And (2) respectively adding 20g of the No. 3 catalyst into the salt solution, standing for 24 hours, separating, washing with deionized water, drying the obtained sample in a 120 ℃ oven for 12 hours, placing the dried sample in a muffle furnace, raising the temperature to 600 ℃ at the rate of 2 ℃/min, and roasting for 4 hours to respectively prepare the No. 7 catalyst, the No. 8 catalyst, the No. 9 catalyst and the No. 10 catalyst.

In the 7# catalyst, the mass percentage of Ga in the 7# catalyst is 3.5 wt%;

in the 8# catalyst, the mass percentage of Ag in the 8# catalyst is 5.35 wt%;

in the 9# catalyst, the mass percentage of Cu in the 9# catalyst is 3.2 wt%;

in the 10# catalyst, the mass percentage of Fe in the 10# catalyst is 2.8 wt%.

2. Preparation of ketone organic compounds from ester compounds under different conditions

2.1 ketonization results under different molecular sieves