CN114618463B - Composite catalyst and preparation method and application thereof - Google Patents

Composite catalyst and preparation method and application thereof Download PDF

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CN114618463B
CN114618463B CN202011456763.9A CN202011456763A CN114618463B CN 114618463 B CN114618463 B CN 114618463B CN 202011456763 A CN202011456763 A CN 202011456763A CN 114618463 B CN114618463 B CN 114618463B
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catalyst
gallium
aluminum
acid
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CN114618463A (en
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赵银峰
刘中民
于政锡
袁翠峪
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The application discloses a composite catalyst and a preparation method and application thereof. The application provides a low-cost and environment-friendly catalyst for preparing propylene by dehydrogenating propane; the catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.

Description

Composite catalyst and preparation method and application thereof
Technical Field
The application relates to a composite catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts.
Background
Propylene is a basic chemical raw material and mainly comes from naphtha catalytic cracking, methanol-to-olefin, propane dehydrogenation and the like. Wherein the dehydrogenation of propane has been developed more rapidly due to the increase in the yield of propane and the reduction in cost.
At present, the propane dehydrogenation catalyst is mainly a Pt-based catalyst and a Cr-based catalyst. The propane dehydrogenation process is limited by thermomechanics, and the reaction temperature has serious influence on the conversion rate. To ensure the conversion of propane, the dehydrogenation reaction temperature of propane is between 580 and 630 ℃. At this temperature, deactivation of the catalyst by coking is difficult to avoid, and coking regeneration of the catalyst is a major means of restoring activity. The noble metal Pt is high in price, so that chromium oxide has great toxicity to the environment, and the problems of catalyst breakage and running loss are difficult to bear, so that a circulating fluidized bed process cannot be adopted. The Pt catalyst mainly adopts a moving bed process, while the chromium oxide catalyst adopts a multi-reactor fixed bed reactor which is connected in parallel, and the operation process is complex and tedious. Therefore, the development of a novel catalyst which is low in price and environment-friendly is a main development direction of a propane dehydrogenation catalyst.
Disclosure of Invention
Aiming at the problems, the application provides a low-cost and environment-friendly composite catalyst for preparing propylene by dehydrogenating propane, and a preparation method and application thereof.
According to a first aspect of the present application, there is provided a composite catalyst I prepared by subjecting a mixture of a gallium source, an aluminum source and a hydroxy acid to a reaction I, followed by heat treatment with zinc oxide and an inorganic acid water, and calcination.
Optionally, the composite catalyst I consists of four elements of zinc, aluminum, gallium and oxygen; the mol ratio of the zinc element, the gallium element and the aluminum element is 13.6-62.0: 0.6 to 7.8:30.2 to 85.8.
Optionally, the hydroxy acid is at least one of citric acid, tartaric acid, lactic acid and malic acid;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the inorganic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid.
Optionally, the composite catalyst I is prepared by a hydrothermal method.
Optionally, the hydroxy acid acts as a complexing agent.
Optionally, the concentration of the inorganic acid is 0.1-5 mol/L.
According to a second aspect of the present application, there is provided a method for preparing the above composite catalyst I, the method comprising:
(1) Reacting a mixture consisting of a gallium source, an aluminum source and a hydroxy acid to obtain a sol;
(2) Carrying out hydrothermal treatment on the mixture containing the sol, zinc oxide and inorganic acid to obtain an intermediate product;
(3) And drying and roasting the intermediate product to obtain the composite catalyst I.
Optionally, the mole ratio of the zinc oxide to the gallium source to the aluminum source is 13.6-62.0: 0.6 to 7.8:30.2 to 85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the number of moles of the aluminum source is calculated by the number of moles of metallic aluminum; the mole number of the zinc oxide is calculated by the mole number of the metallic zinc;
the molar ratio of the metal source to the hydroxy acid is 100:8.6 to 244;
the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source; the mole number of the hydroxy acid is calculated by the mole number of the hydroxy acid per se;
the molar ratio of the metal source to the inorganic acid is 100:2.7 to 62;
the mole number of the inorganic acid is calculated by the mole number of hydrogen ions; the mole number of the metal source is the sum of mole numbers of zinc oxide, gallium source and aluminum source.
Optionally, in the step (1), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the conditions of the hydrothermal treatment are: the temperature is 100-200 ℃; the time is 24-96 h;
in the step (3), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
in the step (3), the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
According to a third aspect of the present application, there is provided a composite catalyst II consisting of a composite catalyst I and alumina;
the mass ratio of the composite catalyst I to the alumina is 1-9:9-1;
the composite catalyst I is at least one selected from the composite catalyst I and the composite catalyst I prepared by the method.
Alternatively, the compound catalyst II in the application has the chemical formula: x (aZnbGacAldO)/y (Al) 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The mass fractions of the components are as follows: x=10 to 90%, y=10 to 90%, a=20 to 69%, b=1 to 10%, c=30 to 70%.
Wherein, the upper limit of the value of x can be selected from 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25%, 20%, 15%, 12% or 10.5%, and the lower limit can be selected from 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 40%, 30%, 20%, 12% or 10%;
the upper limit of y can be selected from 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25%, 20%, 15%, 12% or 10.5%, and the lower limit can be selected from 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 40%, 30%, 20%, 12% or 10%;
the upper limit of the value of a can be selected from 20.5%, 25.0%, 30.0%, 35.0%, 40.0%, 45%, 50%, 55%, 60%, 65% or 69%, and the lower limit can be selected from 20.0%, 24.5%, 29.5%, 34.5%, 39.5%, 44.5%, 49.5%, 54.5%, 59.5%, 64.5% or 68.5%;
the upper limit of the value of b can be selected from 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, and the lower limit can be selected from 1.0%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.
The upper limit of the value of c can be selected from 31%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, and the lower limit can be selected from 30%, 31%, 35%, 40%, 45%, 50%, 55%, 60% or 65%.
Optionally, the method comprises: and mixing the composite catalyst I with alumina to obtain the composite catalyst II.
Specifically, the composite catalyst I is not obtained by simply and physically mixing zinc oxide, aluminum oxide and gallium oxide, but has a specific morphology and structure.
Specifically, zinc ions can be obtained by adding zinc oxide, zinc oxide and inorganic acid to slowly act, enter a catalyst to become one of active components, and part of zinc oxide acts with generated aluminum oxide to generate a spinel structure, so that the acidity of the catalyst is reduced, and the product composite catalyst I has high activity and high selectivity.
Optionally, the method for preparing the composite catalyst II comprises:
(1) Preparing dehydrogenation components aZnbGacAlO by a hydrothermal method and the like, wherein a=20-69%, b=1-10% and c=30-70%, preparing a stoichiometric precursor containing Ga and Al into a solution, adding hydroxy acid into the solution, and the molar ratio of the added hydroxy acid to Al is as follows: hydroxy acid/Al=0.1-5, stirring uniformly to obtain Ga-Al sol, adding zinc oxide into Ga-Al sol to obtain aZnbGacAldO precursor mixture, and adding an acid solution into the mixture solution, wherein the molar ratio of zinc oxide to hydrogen ions in the acid is; zinc oxide/hydrogen ion=5 to 1;
(2) Transferring the mixture obtained in the step (1) into a synthesis kettle, sealing, heating to 100-200 ℃, and performing self-pressure hydrothermal treatment for 24-94 hours to obtain a hydrothermal treatment product;
(3) Filtering and washing the product of the hydrothermal treatment, drying at 50-200 ℃ for 4-20 hours, and roasting for 4-20 hours in 300-700 ℃ air atmosphere to obtain the catalyst 1: aZnbGacAldO;
(4) aZnbGacAldO catalyst and Al 2 O 3 Mixing according to a proportion to x (aZnbGacAldO)/y (Al 2 O 3 ) The composite catalyst II is obtained, wherein x is 10-90%, and y is 10-90%.
According to a final aspect of the present application, there is provided a process for the preparation of propylene, the process comprising: the raw material gas containing propane is reacted with II in the presence of a catalyst to obtain the propylene;
the catalyst is at least one of a composite catalyst I and a composite catalyst II;
the composite catalyst I is at least one selected from the composite catalyst I and the composite catalyst I prepared by the method;
the composite catalyst II is at least one selected from the composite catalyst II and the composite catalyst II prepared by the method.
Optionally, the method comprises: the raw material gas containing propane passes through a reactor to contact and react with a catalyst to generate propylene.
Alternatively, the conditions of reaction II are: the reaction temperature is 530-630 ℃; the reaction space velocity is 200-600L Kg - 1 h -1 。
Alternatively, the pressure of reaction II is atmospheric.
Alternatively, the upper limit of the reaction temperature is selected from 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃ or 630 ℃; the lower limit is selected from 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃ or 625 ℃.
Alternatively, the upper limit of the propane mass space velocity is selected from 220 Kg -1 h -1 、240L Kg -1 h -1 、260L Kg -1 h -1 、280L Kg -1 h -1 、300L Kg -1 h -1 、350L Kg -1 h -1 、400L Kg -1 h -1 、450L Kg -1 h -1 、500L Kg -1 h -1 、550L Kg -1 h -1 Or 600L Kg -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The lower limit is selected from 200L Kg -1 h -1 、220L Kg -1 h -1 、240L Kg -1 h -1 、260L Kg -1 h -1 、280L Kg - 1 h -1 、300L Kg -1 h -1 、350L Kg -1 h -1 、400L Kg -1 h -1 、450L Kg -1 h -1 、500L Kg -1 h -1 、550L Kg -1 h -1 Or 580L Kg -1 h -1 。
The application has the beneficial effects that:
(1) Provides a low-cost and environment-friendly catalyst for preparing propylene by dehydrogenating propane;
(2) The catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.
Drawings
FIG. 1 is an XRD pattern for catalyst 1;
fig. 2 is an XRD pattern of the mixed catalyst 1.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analysis method in the embodiment of the application is as follows:
the raw materials and the products were detected by Agilent 7890B gas chromatography from Agilent corporation using PLOT-Q capillary column from Agilent corporation.
In the examples of the present application, the propane conversion and propylene selectivity were calculated based on the number of moles of carbon.
In the embodiment of the application, the conversion rate and selectivity are calculated as follows:
propane conversion = [ (moles of propane in feed) - (moles of propane in discharge) ] +.f. (moles of propane in feed) × (100%)
Propylene selectivity = [ number of moles of propylene carbon in discharge ]/[ (number of moles of propane carbon in feed) - (number of moles of propane carbon in discharge) ]× (100%)
Example 1
Weigh 0.191gallium nitrate (g) and aluminum nitrate (1.5876 g) are added into 10mL of water, stirred at 80 ℃ until the mixture is completely dissolved, 1.3429g of lactic acid is added, stirring is continued for 30 minutes after the mixture is dissolved, then zinc oxide (0.55 g) is added into Ga-Al sol to obtain a precursor mixture, and then sulfuric acid solution (9.7 mL) with the concentration of 0.1mol/L is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 180 ℃, and performing self-pressure hydrothermal treatment for 48 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water and separated, dried at 80℃for 18 hours, and then calcined at 500℃in an air atmosphere for 12 hours to obtain catalyst 1. 0.6g of catalyst 1 and 0.4g of Al are taken 2 O 3 And uniformly mixing to obtain the catalyst 2. The XRD pattern of catalyst 1 is shown in FIG. 1.
Example 2
0.1879g of gallium chloride and 0.9945g of aluminum chloride are weighed and added into 10mL of water, stirring is carried out at 30 ℃ until the mixture is completely dissolved, 2.7617g of malic acid is added, stirring is continued for 60 minutes after the mixture is dissolved, then 0.69g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 5mol/L of hydrochloric acid solution (1.7 mL) is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 100 ℃, and performing self-pressure hydrothermal treatment for 96 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water, and dried at 50℃for 20 hours, and then calcined at 300℃in an air atmosphere for 20 hours to obtain catalyst 3. 0.9g of catalyst 3 and 0.1g of Al are taken 2 O 3 And uniformly mixing to obtain the catalyst 4.
Example 3
0.2729g of gallium nitrate and 2.0889g of aluminum nitrate are weighed and added into 10mL of water, stirred at 30 ℃ until the mixture is completely dissolved, 1.0305g of citric acid is added, stirring is continued for 240 minutes after the mixture is dissolved, then 0.45g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 2mol/L of nitric acid solution (1.1 mL) is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 150 ℃, and performing self-pressure hydrothermal treatment for 72h to obtain a hydrothermal treatment product. Filtering the product of the hydrothermal treatment, washing and separating, and then heating at 150 DEG CDrying time was 10 hours, and then calcination time was 5 hours in an air atmosphere at 650℃to obtain catalyst 5. 0.7g of catalyst 5 and 0.3g of Al are taken 2 O 3 The mixture was uniformly mixed to obtain a catalyst 6.
Example 4
0.0238g of gallium sulfate and 5.1635g of aluminum sulfate are weighed and added into 10mL of water, stirring is carried out at 80 ℃ until the mixture is completely dissolved, 0.2326g of tartaric acid is added, stirring is continued for 30 minutes after the mixture is dissolved, then 0.2g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 0.1mol/L of sulfuric acid solution (9.7 mL) is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 200 ℃, and performing self-pressure hydrothermal treatment for 24 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water, and dried at 200℃for 4 hours, and then calcined at 700℃in an air atmosphere for 4 hours to obtain catalyst 7. 0.1g of catalyst 7 and 0.9g of Al are taken 2 O 3 Uniformly mixing to obtain the catalyst 8.
Example 5
0.0819g of gallium nitrate and 2.5067g of aluminum nitrate are weighed and added into 10mL of water, stirring is carried out at 50 ℃ until the mixture is completely dissolved, 7.4195g of citric acid is added, stirring is continued for 60 minutes after the mixture is dissolved, then 0.35g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 3mol/L of hydrochloric acid solution (1 mL) is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 120 ℃, and performing self-pressure hydrothermal treatment for 80 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water, and dried at 110℃for 12 hours, followed by calcination at 600℃in an air atmosphere for 6 hours to give catalyst 9. 0.5g of catalyst 9 and 0.5g of Al are taken 2 O 3 The catalyst 10 is obtained by uniformly mixing.
Example 6
Weighing 0.0546g of gallium nitrate and 3.0498g of aluminum nitrate, adding into 10ml of water, stirring at 60 ℃ until the mixture is completely dissolved, adding 7.4195g of citric acid, stirring until the mixture is dissolved, continuing stirring for 40 minutes to obtain a sol, adding 0.25g of zinc oxide into Ga-Al sol to obtain a precursor mixture, and adding 1mol/L of nitric acidThe solution (1.5 mL) was added to the mixture solution and stirred well. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 160 ℃, and performing self-pressure hydrothermal treatment for 72 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water, dried at 100℃for 12 hours, and then calcined at 550℃in an air atmosphere for 12 hours to obtain a catalyst 11. 0.8g of catalyst 11 and 0.2g of Al are taken 2 O 3 The mixture was uniformly mixed to obtain a catalyst 12.
Comparative example 1
0.1804g of copper nitrate and 1.5876g of aluminum nitrate are weighed and added into 10mL of water, stirring is carried out at 80 ℃ until the copper nitrate and the aluminum nitrate are completely dissolved, 1.3429g of lactic acid are added, stirring is carried out until the lactic acid is dissolved, stirring is continued for 30 minutes to obtain a sol, then 0.55g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 0.1mol/L of sulfuric acid solution (9.7 mL) is added into the mixture solution, and stirring is uniform. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 180 ℃, and performing self-pressure hydrothermal treatment for 48 hours to obtain a hydrothermal treatment product. The product of the hydrothermal treatment was filtered, washed with water, and dried at 80℃for 18 hours, and then calcined at 500℃in an air atmosphere for 12 hours to give comparative catalyst 1. 0.6g of catalyst 3 and 0.4g of Al are taken 2 O 3 And uniformly mixing to obtain the comparative catalyst 2.
Comparative example 2
0.55g of zinc oxide powder, 0.07g of gallium oxide powder and 0.38g of aluminum oxide powder are weighed and physically mixed to obtain the mixed catalyst 1. Fig. 2 is an XRD pattern of the mixed catalyst 1. From the XRD results, it can be seen that the catalyst 1 of example 1 and the mixed catalyst 1 are completely different substances, i.e., the catalyst 1 obtained in example 1 is not obtained by physical mixing of oxides.
Example 7
The catalyst of the previous example was subjected to reaction evaluation: the catalyst is filled into a fixed bed reactor, the reaction temperature is 530-630 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 200-600L Kg -1 h -1 . The reaction results of the foregoing example catalyst 1 were regarded as comparative examples. Sampling after 6min of reaction, and the reaction results are shown in Table 1.
TABLE 1 catalyst reaction results
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (5)

1. A process for the preparation of propylene, said process comprising: the raw material gas containing propane is reacted with II in the presence of a catalyst to obtain the propylene;
the catalyst is at least one of a composite catalyst I and a composite catalyst II;
the preparation method of the composite catalyst II comprises the following steps: mixing the composite catalyst I with alumina to obtain the composite catalyst II;
the mass ratio of the composite catalyst I to the alumina is 1-9:1-9;
the preparation method of the composite catalyst I comprises the following steps:
(1) Reacting a mixture consisting of a gallium source, an aluminum source and a hydroxy acid to obtain a sol;
(2) Carrying out hydrothermal treatment on the mixture containing the sol, zinc oxide and inorganic acid to obtain an intermediate product;
(3) Drying and roasting the intermediate product to obtain the composite catalyst I;
the composite catalyst I consists of four elements of zinc, aluminum, gallium and oxygen; the mol ratio of the zinc element, the gallium element and the aluminum element is 13.6-62.0: 0.6 to 7.8:30.2 to 85.8.
2. The method according to claim 1, wherein the hydroxy acid is at least one selected from the group consisting of citric acid, tartaric acid, lactic acid, and malic acid;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the inorganic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid.
3. The preparation method according to claim 1, wherein the molar ratio of the zinc oxide, the gallium source and the aluminum source is 13.6-62.0: 0.6 to 7.8:30.2 to 85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the number of moles of the aluminum source is calculated by the number of moles of metallic aluminum; the mole number of the zinc oxide is calculated by the mole number of the metallic zinc;
the molar ratio of the metal source to the hydroxy acid is 100:8.6 to 244;
the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source; the mole number of the hydroxy acid is calculated by the mole number of the hydroxy acid per se;
the molar ratio of the metal source to the inorganic acid is 100:2.7 to 62;
the mole number of the inorganic acid is calculated by the mole number of hydrogen ions; the mole number of the metal source is the sum of mole numbers of zinc oxide, gallium source and aluminum source.
4. The process according to claim 1, wherein in step (1), the conditions of reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the conditions of the hydrothermal treatment are: the temperature is 100-200 ℃; the time is 24-96 h;
in the step (3), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
5. The process of claim 1, wherein the conditions for reaction II are: the reaction temperature is 530-630 ℃; the reaction space velocity is 200-600L Kg -1 h -1 。
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