CN111517936B - Method for preparing ketone organic matter - Google Patents
Method for preparing ketone organic matter Download PDFInfo
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- CN111517936B CN111517936B CN201910107123.8A CN201910107123A CN111517936B CN 111517936 B CN111517936 B CN 111517936B CN 201910107123 A CN201910107123 A CN 201910107123A CN 111517936 B CN111517936 B CN 111517936B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
Abstract
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 is1Is selected from C1～C10One of the hydrocarbon groups; r2Selected from H, C1～C10One of the hydrocarbyl groups in formula I contains an alpha-hydrogen atom on a carbon adjacent to the carbonyl group. Compared with the traditional simple substance type/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, and has good industrial application prospect.
Description
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 the hydrocarbyl group is present, the starting material for the reaction is a compound having 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 in arylSeed growing; 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
Example 1
1g of No. 1 catalyst was packed in a fixed bed reactor having an inner diameter of 8 mm, and the No. 1 catalyst was preactivated under the condition of N2The flow rate was 30ml/min and increased to 50 deg.C/min at a rate of 2 deg.C/min0 ℃ and keeping the temperature at 500 ℃ for 1 hour, then reducing the temperature to 320 ℃ in the nitrogen atmosphere, increasing the pressure of the reaction system to 20bar by using nitrogen, and the mass space velocity of the raw material methyl acetate is 0.3h-1The dilution gas is N2The dilution gas was 80% by volume of the feed gas, and the results of the ketonization reaction under these conditions are shown in Table 1.
Examples 2 to 10
The reaction conditions were the same as in example 1 except that the catalysts were # 2 to # 10, respectively, and the reaction results are shown in Table 1.
TABLE 1 results of methyl acetate ketonization in different catalysts
As can be seen from table 1: the acidic molecular sieves and the metal-modified molecular sieves listed can convert methyl acetate into acetone.
2.2 ketonization results at different reaction temperatures
Example 11
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate was 30ml/min, the temperature was raised to 500 ℃ at a rate of 2 ℃/min under a nitrogen atmosphere, the temperature was maintained for 1 hour, the temperature was then lowered to the desired reaction temperature of 240 ℃ under a nitrogen atmosphere, and the pressure of the reaction system was raised to 20bar with nitrogen. The reaction raw materials are fed into a reactor from top to bottom, and the mass space velocity of the raw material methyl acetate is 0.3h-1The dilution gas is N2The dilution gas was 80% by volume in the feed gas, and the results of the ketonization reaction at 240 ℃ are shown in Table 2.
Examples 12 to 16
The other conditions were the same as in example 11 except that the reaction temperature was 260 deg.C, 280 deg.C and 330 deg.C, respectively. 350 ℃ and 400 ℃. The reaction results are shown in Table 2.
TABLE 2 results of the ketonization reaction at different reaction temperatures
As can be seen from Table 2, increasing the reaction temperature increased the conversion of methyl acetate and slightly increased the selectivity to acetone.
2.3 ketonization results at different reaction pressures
Example 17
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 1bar required by the reaction by using nitrogen. The reaction raw materials are fed into a reactor from top to bottom, and the mass space velocity of the raw material methyl acetate is 0.1h-1The dilution gas is N2The dilution gas was 80% by volume in the feed gas and the results of the ketonization reaction at 1bar are shown in Table 3.
Examples 18 to 21
The other conditions were the same as in example 17 except that the reaction pressure was 10bar, 20bar, 40bar and 50bar, respectively. The reaction results are shown in Table 3.
TABLE 3 results of the ketonization reaction at different reaction pressures
As can be seen from table 3, the reaction pressure did not significantly increase the conversion of methyl acetate and the acetone selectivity.
2.4 ketonization of different ester Compounds on acidic molecular sieves
Example 22
1g of No. 3 catalyst was chargedPre-activating the 3# catalyst in a fixed bed reactor with an inner diameter of 8 mm under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 20bar required by the reaction by using nitrogen. Introducing a reaction raw material methyl acetate into a reactor from top to bottom, wherein the mass space velocity of the raw material methyl acetate is 0.3h-1The dilution gas is N2The dilution gas was 80% by volume of the feed gas, and the results of the ketonization reaction are shown in Table 4.
Examples 23 to 26
The other conditions were the same as in example 22 except that the reaction materials were ethyl propionate, propyl butyrate, isopropyl isobutyrate and benzyl phenylacetate, respectively. The reaction results are shown in Table 4.
TABLE 4 ketonization results for different fatty acid esters
As can be seen from Table 4, as the number of carbon atoms of the ester branch chain increases, the conversion rate decreases and the selectivity to the ketone hardly changes.
2.5 ketonization results at different feedstock Mass space velocities
Example 27
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to the required reaction temperature of 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to the required reaction pressure of 20bar by using nitrogen. Introducing a reaction raw material methyl acetate into a reactor from top to bottom, wherein the mass space velocity of the raw material methyl acetate is 0.1h-1The dilution gas is N2The volume percentage of the diluent gas in the feed gas was 80%, and the reaction results are shown in Table 5.
Examples 28 to 32
All other conditions areThe same as in example 27, except that the mass space velocities of the feedstocks were each 0.5h-1，1.0h-1，1.4h-1，1.6h-1，2.0h-1The reaction results are shown in Table 5.
TABLE 5 results of the ketonization reaction at different mass airspeeds of the feedstock
As can be seen from table 5, even though the acidic molecular sieves have good catalytic properties, as with all catalysts, the throughput is limited and the feed conversion is inversely proportional to the feed space velocity. But the space velocity of the raw materials does not influence the reaction behavior of the catalyst, namely the selectivity of the product is not changed.
2.6 ketonization results for different reactor types
Example 33
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 20bar required by the reaction by using nitrogen. Introducing a reaction raw material methyl acetate into the reactor from bottom to top, wherein the mass space velocity of the raw material methyl acetate is 0.3h-1The dilution gas is N2The volume percentage of the diluent gas in the feed gas was 80%, and the reaction results are shown in Table 6.
Examples 34 to 36
The other conditions were the same as in example 33 except that the reactors were a fluidized bed reactor and a moving bed reactor, respectively, and the reaction results were as shown in Table 6.
TABLE 6 results of the ketonization reaction at different reactor types
As can be seen from Table 6, the ketonization reaction can take place in all three reactors, and the heterogeneous reaction characteristic avoids the subsequent catalyst-product separation process.
2.7 results of the reaction in different dilution gases
Example 36
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 20bar required by the reaction by using nitrogen. Introducing a reaction raw material methyl acetate into a reactor from top to bottom, wherein the mass space velocity of the raw material methyl acetate is 0.3h-1The dilution gas is N2The volume percentage of the diluent gas in the feed gas was 80%, and the reaction results are shown in Table 7.
Examples 37 to 40
The other conditions were the same as in example 36 except that the diluent gases were each H2He, CO and Ar, the reaction results are shown in table 7.
TABLE 7 results of ketonization on acidic molecular sieves under different reaction atmospheres
As can be seen from table 7, carbon monoxide significantly promoted the conversion of methyl acetate and the selectivity to acetone.
2.8 ketonization results of different Adhesives
EXAMPLE 41
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to the required reaction temperature of 330 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to the required reaction pressure of 20bar by using nitrogen. Introducing the reaction raw material methyl acetate into a reactor from top to bottom, wherein the mass space velocity of the raw material methyl acetateIs 0.3h-1The dilution gas is N2The volume percentage of the diluent gas in the feed gas was 80%, and the reaction results are shown in Table 8.
Examples 42 to 46
9g, 8g, 7g, 5g and 2g of the calcined HZSM-5 catalyst were taken, 1g, 2g, 3g, 5g and 8g of a binder comprising alumina and silica (mass ratio 1: 1) were added thereto, respectively, and after mixing uniformly, they were extruded, crushed and sieved to obtain 20 to 40 mesh particles, and 1g of each of the molded catalysts having a binder content of 10%, 20%, 30%, 50% and 80% was used for the reaction, and the other conditions were the same as in example 39. The reaction results are shown in Table 8.
TABLE 8 results of ketonization on acidic molecular sieves with different binder contents
As can be seen from Table 8, the increase in the binder content and the decrease in the raw catalyst powder content resulted in a decrease in the conversion of the raw materials, but the adverse effect was not significant.
3. Preparation of ketone organic from carboxylic acid compounds
Example 47
1g of No. 3 catalyst was charged into a fixed bed reactor having an inner diameter of 8 mm, and the No. 3 catalyst was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 320 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 20bar required by the reaction by using nitrogen. Introducing a reaction raw material acetic acid into a reactor from bottom to top, wherein the mass space velocity of the raw material acetic acid is 0.3h-1The dilution gas is N2The volume percentage of the dilution gas in the feed gas was 80%.
Examples 48 to 52
Reaction conditions example 47, but starting material was changed from acetic acid in example 47 to butyric acid, heptanoic acid, decanoic acid, phenylacetic acid and phenylpropionic acid. The reaction results are shown in Table 9.
TABLE 9 results of ketonization of different carboxylic acids on acidic molecular sieves
| Examples | Carboxylic acids | Reaction acid conversion (%) | Corresponding ketone selectivity (%) |
| 47 | Acetic acid | 40.8 | 12.5 |
| 48 | Butyric acid | 27.2 | 11.7 |
| 49 | Heptanoic acid | 19.4 | 9.3 |
| 50 | Capric acid | 5.6 | 5.1 |
| 51 | Phenylacetic acid | 15.8 | 16.4 |
| 52 | Phenylpropionic acid | 12.1 | 18.8 |
4. Preparation of ketone organic matter with acid mordenite molecular sieve (HMOR) as catalyst and carbon monoxide as diluent gas
4.1 reaction results at different reaction temperatures
Example 53
1g of catalyst # 4 (HMOR) was charged to a fixed bed reactor having an internal diameter of 8 mm and the catalyst # 4 was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 240 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 20bar required by the reaction by using carbon monoxide. Introducing a reaction raw material methyl acetate into the reactor from bottom to top, wherein the mass space velocity of the raw material methyl acetate is 0.1h-1The dilution gas is carbon monoxide, and the volume percentage of the dilution gas in the raw material gas is 80%.
Examples 54 to 58
The reaction conditions were the same as in example 53, but the reaction temperatures were changed to 260 deg.C, 280 deg.C, 330 deg.C, 350 deg.C and 400 deg.C, respectively. The reaction results are shown in Table 10.
TABLE 10 reaction results of methyl acetate to acetone at different temperatures
As can be seen from Table 10, the combination of mordenite and carbon monoxide is more favorable for the generation of acetone, the selectivity of acetone is far higher than that of the No. 3 catalyst, and the catalyst has better acetone selectivity at the reaction temperature of 280-330 ℃, wherein the optimal reaction temperature is 280 ℃.
4.2 reaction results at different reaction pressures
Example 59
1g of catalyst # 4 (HMOR) was charged to a fixed bed reactor having an internal diameter of 8 mm and the catalyst # 4 was preactivated under the condition of N2The flow rate is 30ml/min, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 280 ℃ under the nitrogen atmosphere, and the pressure of the reaction system is increased to 1bar required by the reaction by using carbon monoxide. Introducing a reaction raw material methyl acetate into the reactor from bottom to top, wherein the mass space velocity of the raw material methyl acetate is 0.1h-1The dilution gas is carbon monoxide, and the volume percentage of the dilution gas in the raw material gas is 80%.
Examples 60 to 63
The reaction conditions were the same as in example 59, but the reaction pressures were changed to the corresponding 10bar, 20bar, 40bar and 50 bar. The reaction results are shown in Table 10.
TABLE 11 reaction results of methyl acetate to acetone at different pressures
| Examples | Reaction pressure (bar) | Methyl acetate conversion (%) | Acetone selectivity (%) |
| 59 | 1 | 3 | 10 |
| 60 | 10 | 20 | 42 |
| 61 | 20 | 19 | 73 |
| 62 | 40 | 26 | 71 |
| 63 | 50 | 28 | 73 |
As can be seen from Table 11, the acetone production is facilitated by increasing the system pressure, preferably at a pressure of 20 to 50 bar. Wherein the optimal pressure is 20bar, and the yield of the acetone can be promoted by continuously increasing the pressure without changing the selectivity.
In summary, in examples 53-63, acetic acid and CO were reacted in the presence of HMOR as a catalyst, and CH3COOCH3+CO→CH3COCH3+CO2. The conditions under which this reaction takes place are: the temperature is 280-330 ℃, the pressure is 20-50 bar, and higher acetone yield (more than 67%) can be obtained under the conditions, wherein the best conditions are 280 ℃, 20bar and 73% of acetone yield.
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 (11)
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～C3Alkyl radical, C7One of aryl groups;
R2is selected from C1～C3Alkyl radical, C6～C7One of aryl groups;
in formula I, the carbon adjacent to the carbonyl group contains an alpha-hydrogen atom;
the ketone organic matter is at least one compound selected from the compounds in the structural formula shown in the formula II:
wherein R is3，R4Independently selected from C1～C3Alkyl radical, C7One of aryl groups;
the feed gas also comprises a diluent gas, and the diluent gas is an inactive gas;
the non-reactive gas comprises CO;
the volume percentage of the diluent gas in the feed gas is 20-80%;
the acidic molecular sieve catalyst is an acidic molecular sieve catalyst with an MOR topological structure;
said counterThe conditions are as follows: 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 10-50 bar.
2. The method of claim 1, wherein the acidic molecular sieve catalyst comprises an acidic molecular sieve;
the acidic molecular sieve comprises a HMOR molecular sieve.
3. The method of claim 2, wherein the HMOR molecular sieve has an atomic silicon to aluminum ratio of 1 to 70.
4. The method of claim 2, wherein the HMOR molecular sieve has an atomic silicon to aluminum ratio of 2.5 to 25.
5. The method of claim 2, wherein the acidic molecular sieve catalyst further comprises a promoter metal element;
the metal element is at least one selected from gallium, iron, copper and silver.
6. The method according to claim 5, wherein 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.
7. The method of claim 5, wherein the metallic element is supported in the acidic molecular sieve.
8. The method of claim 2 or 5, 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%.
9. The method of claim 8, wherein the binder is mixed with an acidic molecular sieve to form the mixture.
10. The process according to claim 1, characterized in that the reaction conditions are: the mass space velocity of the reaction raw materials is 0.1-1.0 h-1The reaction temperature is 280-330 ℃, and the reaction pressure is 20-50 bar.
11. 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.
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| CN102992984A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Methyl ethyl ketone preparation method |
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| CN106518646B (en) * | 2015-09-11 | 2019-02-01 | 中国科学院大连化学物理研究所 | A method of acetic acid is prepared by methyl formate isomerisation |
| CN108774130B (en) * | 2018-06-29 | 2020-11-03 | 厦门大学 | Method for preparing methyl acetate by synthesis gas one-step method |
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| CN101579636A (en) * | 2008-05-15 | 2009-11-18 | 湖南大学 | Catalyst and method for preparing 2, 3-pentanedione by lactic acid or lactate |
| CN102992984A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Methyl ethyl ketone preparation method |
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