CN106669686B - A kind of copper-based catalysts and preparation method thereof - Google Patents

A kind of copper-based catalysts and preparation method thereof Download PDF

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CN106669686B
CN106669686B CN201510755360.7A CN201510755360A CN106669686B CN 106669686 B CN106669686 B CN 106669686B CN 201510755360 A CN201510755360 A CN 201510755360A CN 106669686 B CN106669686 B CN 106669686B
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catalyst
copper
catalyst according
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CN106669686A (en
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张信伟
李�杰
倪向前
张舒冬
孙晓丹
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The present invention discloses a kind of copper-based catalysts and preparation method thereof.The catalyst with CuO feature crystal face { 110 },{111}、{202}、It is wherein maximum with X-ray diffraction intensityWhen crystal face is benchmark, the relative intensity of each crystal face is respectively as follows:For 11-20,For 80-88,For 17-22,For 7-9,For 11-14.The preparation method of the catalyst: (1) prepare containing alcohols, surfactant, triethanolamine aqueous solution, copper presoma, zirconium precursor body, lanthanum presoma are dissolved in the solution；(2) by carrier incipient impregnation in solution prepared by step (1), aging, drying；(3) material by step (2) preparation carries out hydro-thermal process；(4) catalyst is made after roasting to step (3) resulting material.The copper-based catalysts of this method preparation can be improved the conversion ratio of bromomethane and the selectivity of dimethyl ether.

Description

A kind of copper-based catalysts and preparation method thereof
Technical field
The present invention relates to a kind of copper-based catalysts and preparation method thereof.
Background technique
Dimethyl ether is a kind of important industrial chemicals, and purposes is main are as follows: (1) prepares low-carbon alkene (DTO)；(2) pass through Carbonylation, hydrocarbylation, oxidation reaction synthesize fine chemical product；(3) it can be used as propellant, the foaming agent etc. of aerosol；(4) generation For freon as refrigerant.It is current studies have shown that dimethyl ether also has excellent combustibility, the property class after liquefaction It is similar to liquefied petroleum gas；Since its Cetane number is higher than diesel oil, ideal substitute of diesel fuel also can be used as.Dimethyl ether small toxicity, Corrosivity is low, is a kind of clean fuel for being able to achieve efficient burning, has wide answer in the fields such as transport, power generation, civilian, combustion gas Use prospect.
The industrial process of dimethyl ether is to prepare methanol by raw material of synthesis gas at present, and then methanol is by dehydration system Obtain dimethyl ether.Wherein, the preparation process of synthesis gas there are severe reaction conditions, equipment investment is expensive, production cost and energy consumption compared with A series of problems, such as high, causes detrimental effect to the economy of entire process for preparing dimethyl ether.Therefore current main solution Certainly method are as follows: the dimethyl ether preparation process of exploitation non-synthetic gas approach widens the channel of raw material, gets rid of the dependence to synthesis gas.
Olah et al. (GeorgeA O, Balaram G, JeffD F et al., J.Am.Chem.Soc., 1985,107 (24), 7097-7105) disclosed in 1985 it is a kind of methane is replaced with halogen after the method reacted again: by methane with Halogen simple substance reacts on solid acid or noble metal catalyst generates halide, then with excessive on aluminium oxide catalyst Steam converts methanol, dimethyl ether, water and HBr/HCl by hydrolysis for halide.But the technique methane one way turns Rate is less than 20%, and the energy consumption of product separation is higher, and isolated HBr/HCl aqueous solution has extremely strong corrosivity, right Subsequent processing causes very big pressure.
Ivan M.Lorkovic et al. (Ivan M.Lorkovic, Aysen Yilmaz, GurkanA.Yilmaz, et Al.Catalysis Today, 2004,98,317-322) it is also proposed that bromo-hydrocarbons is generated with the alkane reaction in bromine and natural gas, Then dimethyl ether, methanol and metal bromide, metal bromide oxygen are converted by bromo-hydrocarbons on metal oxide catalyst Metal oxide is obtained after gas regeneration and releases simple substance bromine, completes the circulation of bromine.But above route require using Simple substance bromine, there is great security risks.
Chinese patent CN 1640864A replaces Br using HBr aqueous solution2, propose from methane and prepare acetic acid, methanol With the two-step process of dimethyl ether.Methane carries out oxygen bromination reaction, the CH of generation with HBr and oxygen first3Br, CO and H2O is into one Step is in RhCl3、RuCl3、FeCl3Or CoCl3Carbonyls catalyst action under generate acetic acid, wherein CH3The one way of Br turns Rate is 46%, and acetic acid is selectively 96%.In addition, CH3Br is in RuCl3It is hydrolyzed on catalyst and produces methanol and dimethyl ether, first The one-way yield of pure and mild dimethyl ether is 90%.But the process conversion ratio is lower, and while preparing dimethyl ether, there are also first Alcohol generates, and does not only result in dimethyl ether selectivity reduction, it is also necessary to separate to product, increase corresponding energy consumption.
GRT Inc. propose a kind of methane activation technology (US6462243, US6465696, US6472572, US2002198416), traditional methane synthetic gas production process can be avoided, to reduce cost.Main design thought are as follows: use Methane is converted bromomethane by continuous bromination reaction mode, and then bromomethane is converted into high-carbon on metal oxide catalyst Hydrocarbon or oxygen-containing organic chemicals, such as dimethyl ether.Wherein the metal oxide of catalysis bromomethane conversion is the key that the technology, GRT Company mainly uses sol-gel method to prepare copper zirconium mixed oxide as catalyst.But the bromomethane of the bulk phase catalyst turns Rate and dimethyl ether selectivity are lower, and stability is poor, begin to inactivate within half an hour.
Summary of the invention
In view of the deficiencies of the prior art, it is an advantage of the invention to provide one kind to be by bromomethane Efficient Conversion The copper-based catalysts of dimethyl ether；It is a further object of the invention to provide the preparation methods of the copper-based catalysts.
A kind of copper-based catalysts of the present invention, the copper-based catalysts are made of copper oxide, lanthana, zirconium oxide, carrier, institute Stating mass percent of the copper oxide in terms of Cu element in the catalyst is 5%-50%；Preferably 15%-30%, the zirconium oxide Mass percent in terms of Zr element in the catalyst is 0.5%-20%, preferably 0.5%-15%, further preferably 1%-10%, mass percent of the lanthana in terms of La element in the catalyst is 0.5%-20%, preferably 0.5%- 15%, further preferably 1%-10%, surplus are carrier, the carrier be aluminium oxide, silica, molecular sieve, active carbon or One or more of carbon nanotube, preferably aluminium oxide, the catalyst with CuO feature crystal face { 110 }, {111}、{202}、It is wherein maximum with X-ray diffraction intensityWhen crystal face is benchmark, each crystal face Relative intensity is respectively as follows:For 11-20,For 80-88,For 17- 22,For 7-9,For 11-14.
A kind of preparation method of copper-based catalysts of the present invention, includes the following steps:
(1) prepare containing alcohols, surfactant, triethanolamine aqueous solution, before copper presoma, zirconium precursor body, lanthanum Body is driven to be dissolved in the solution；
(2) by carrier incipient impregnation in solution prepared by step (1), aging, drying are carried out；
(3) material prepared by step (2) is placed in tube furnace and carries out hydro-thermal process；
(4) catalyst is made after roasting to step (3) resulting material.
The method of the present invention, copper presoma described in step (1) be one or more of nitrate, chloride, sulfate, Preferably copper nitrate.
The method of the present invention, zirconium precursor body described in step (1) are nitrate, chloride, oxychlorination things, one in sulfate Kind is several, preferably zirconium oxychloride.
The method of the present invention, lanthanum presoma described in step (1) be one or more of nitrate, chloride, sulfate, Preferably lanthanum nitrate.
The method of the present invention, alcohols described in step (1) be one or more of ethyl alcohol, isopropanol, normal propyl alcohol, preferably Isopropanol.
The method of the present invention, the mass fraction of alcohols in the solution described in step (1) are 1%-20%, preferably 1%- 10%, more preferably 1%-5%.
The method of the present invention, surfactant described in step (1) are polyethylene glycol, fatty alcohol polyoxyethylene ether, dodecane One or more of base benzene sulfonic acid sodium salt, Sodium Polyacrylate, Tween 80, preferably fatty alcohol polyoxyethylene ether, more preferably AEO-7。
The method of the present invention, the mass fraction of surfactant in the solution described in step (1) are 0.1%-10%, preferably For 0.1%-5%, more preferably 0.5%-2%.
The method of the present invention, the mass fraction of triethanolamine in the solution described in step (1) are 0.1%-10%, preferably 0.1%-5%, more preferably 0.5%-2%.
The method of the present invention, aging condition described in step (2) are as follows: aged at room temperature 2h-24h, preferably 6h-10h.
The method of the present invention, drying condition described in step (2) are as follows: drying temperature be 80 DEG C -200 DEG C, preferably 80 DEG C - 120℃；Drying time is 6h-48h, preferably 6h-36h, more preferably 6h-24h.It can be vacuum drying when dry, it can also Think dry under the conditions of inert gas shielding, can also dry in air atmosphere.
The method of the present invention, carrier is bar shaped, piece shape, cylindricality or spherical shape etc. in step (2).Carrier molding is by public in this field Know technical operation.
The method of the present invention, hydrothermal conditions in step (3) are as follows: 100 DEG C -200 DEG C are warming up under inert atmosphere, preferably 120℃-150℃；The gaseous mixture of vapor and inert gas is then passed to, vapor volumn concentration is in gaseous mixture 10%-90%, preferably 50%-90%, surplus are inert gas；The processing time is 1h-10h, preferably 1h-4h；Finally cut It is changed to inert gas, purges 0.5h-2h.
The method of the present invention, roasting condition in step (4) are as follows: maturing temperature is 500 DEG C -900 DEG C, preferably 500 DEG C -700 ℃；Calcining time is 4h-24h, preferably 4h-16h, more preferably 4h-10h.It can be inert gas shielding condition when roasting Lower roasting, can also roast in air atmosphere.
The present invention also provides application of the copper-based catalysts in bromomethane preparing dimethy ether, using bromomethane as raw material, Reaction temperature is 160 DEG C -420 DEG C, preferably 170 DEG C -320 DEG C；Reaction pressure is 0.1MPa-5MPa, preferably 0.1MPa- 1MPa；Volume space velocity is 50h-1-2000h-1, preferably 50h-1-1000h-1, more preferably 50h-1-280h-1, needed before charging pair Catalyst is activated.
In above-mentioned application, be activated condition it is as follows: under inert atmosphere by the material after hydro-thermal process be warming up to 200 DEG C- 600 DEG C, preferably 300 DEG C -450 DEG C；Then pass to air or containing air and inert gas gaseous mixture；Processing the time be 0.5h-10h, preferably 0.5h-4h.Gaseous mixture hollow gas product percentage composition is 5%-90%, preferably 5%-50%, More preferably 10%-30%, surplus are inert gas.
In above-mentioned application, suitable inert gas can be contained in bromomethane raw material, bromomethane raw material and inert gas The volumn concentration of bromomethane raw material is 1%-99%, preferably 10%-90% in gaseous mixture.Inert gas is nitrogen, argon The gas that gas, helium etc. do not chemically react under the conditions of involved in the present invention, preferably nitrogen.
Compared with prior art, a kind of copper-based catalysts of the present invention and preparation method thereof have the advantage that
(1) synergistic effect of alcohols, surfactant, triethanolamine, hydrothermal treatment process, available each crystal face are opposite The copper-based catalysts of intensity controlled；Meanwhile copper-based catalysts prepared according to the methods of the invention are in the anti-of bromomethane preparing dimethy ether Activity with higher in answering.Conversion per pass > 99% of the bromomethane on catalyst of the invention, the selectivity of dimethyl ether > 90%.
(2) method for preparing catalyst of the invention is easy to operate controllable, function admirable, and the reaction of bromomethane preparing dimethy ether Mild condition, industrialization easy to accomplish, has broad application prospects.
Detailed description of the invention
Fig. 1 is catalyst XRD diffraction pattern prepared by the embodiment of the present invention 1.
Specific embodiment
Catalyst of the present invention and its preparation method and application is further illustrated below by embodiment, but it is not considered that originally Invention is limited only in example below.
Embodiment 1
According to isopropanol mass percent be 4.1%, AEO-7 mass percent is 0.8%, triethanolamine mass percent For 1.5% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 15.2%, Zr element accounts for that catalyst quality percentage is 3.2%, La element accounts for catalyst quality percentage For 1.5% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 8h, is dried for 24 hours at 120 DEG C.Resulting material is placed in tube furnace In be warming up to 130 DEG C under a nitrogen, be passed through -35% nitrogen mixture of 65% vapor processing 2.5h, be switched to nitrogen, purge 2h.Then by treated, material roasts 8h at 600 DEG C；Catalyst, XRD the result is shown in Figure 1 is made.With X-ray diffraction intensity It is maximumWhen crystal face is benchmark, the relative intensity of each crystal face is shown in Table 1.
Embodiment 2
According to isopropanol mass percent be 2.5%, AEO-7 mass percent is 1.9%, triethanolamine mass percent For 0.6% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 20.2%, Zr element accounts for that catalyst quality percentage is 1.1%, La element accounts for catalyst quality percentage For 0.8% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 10h, dry 48h at 80 DEG C.Resulting material is placed in tube furnace In be warming up to 145 DEG C under a nitrogen, be passed through -45% nitrogen mixture of 55% vapor processing 3h, be switched to nitrogen, purge 2h. Then by treated, material roasts 10h at 550 DEG C；Catalyst is made.
Embodiment 3
According to isopropanol mass percent be 4.8%, AEO-7 mass percent is 1.7%, triethanolamine mass percent For 1.1% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 15.5%, Zr element accounts for that catalyst quality percentage is 2.0%, La element accounts for catalyst quality percentage For 2.5% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 8h, is dried for 24 hours at 120 DEG C.Resulting material is placed in tube furnace In be warming up to 130 DEG C under a nitrogen, be passed through -50% nitrogen mixture of 50% vapor processing 4h, be switched to nitrogen, purge 2h. Then by treated, material roasts 8h at 700 DEG C；Catalyst is made.
Embodiment 4
According to isopropanol mass percent be 1.2%, AEO-7 mass percent is 1.5%, triethanolamine mass percent For 0.8% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 24.8%, Zr element accounts for that catalyst quality percentage is 6.1%, La element accounts for catalyst quality percentage For 5.2% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 6h, dry 32h at 110 DEG C.Resulting material is placed in tube furnace In be warming up to 135 DEG C under a nitrogen, be passed through -25% nitrogen mixture of 75% vapor processing 2.5h, be switched to nitrogen, purge 2h.Then by treated, material roasts 6h at 800 DEG C；Catalyst is made.
Embodiment 5
According to isopropanol mass percent be 3.6%, AEO-7 mass percent is 1.2%, triethanolamine mass percent For 1.3% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 14.5%, Zr element accounts for that catalyst quality percentage is 3.7%, La element accounts for catalyst quality percentage For 4.5% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 8h, is dried for 24 hours at 120 DEG C.Resulting material is placed in tube furnace In be warming up to 140 DEG C under a nitrogen, be passed through -20% nitrogen mixture of 80% vapor processing 1h, be switched to nitrogen, purge 2h. Then by treated, material roasts 4h at 900 DEG C；Catalyst is made.
Embodiment 6
According to isopropanol mass percent be 4.2%, AEO-7 mass percent is 1.6%, triethanolamine mass percent For 1.2% ratio, isopropanol, AEO-7, triethanolamine are added in deionized water, solution is prepared；Catalysis is accounted for according to Cu element Agent mass percent is 14.8%, Zr element accounts for that catalyst quality percentage is 4.7%, La element accounts for catalyst quality percentage For 3.5% ratio, copper nitrate, zirconium oxychloride and lanthanum nitrate are added in solution, maceration extract is made in stirring and dissolving completely, then Incipient impregnation is carried out with 10g alumina support, at room temperature aging 6h, is dried for 24 hours at 120 DEG C.Resulting material is placed in tube furnace In be warming up to 130 DEG C under a nitrogen, be passed through -35% nitrogen mixture of 65% vapor processing 4h, be switched to nitrogen, purge 2h. Then by treated, material roasts 6h at 700 DEG C；Catalyst is made.
Embodiment 7
Catalyst preparation is the same as embodiment 1.Evaluating catalyst condition are as follows: gained catalyst is packed into continuous flow fixed bed reaction In device, it is warming up to 350 DEG C under nitrogen, is passed through -70% nitrogen mixture of 30% air, activates 2h.Then under a nitrogen by temperature 200 DEG C are down to be reacted；Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 150h-1, CH3Br conversion ratio, dimethyl ether selectivity are shown in Table 1.
Embodiment 8
Catalyst preparation is the same as embodiment 1.Gained catalyst is fitted into continuous fixed bed reactor, is warming up under nitrogen 350 DEG C, it is passed through -70% nitrogen mixture of 30% air, activates 2h.Then 250 DEG C are cooled the temperature under a nitrogen to be reacted； Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 150h-1, CH3Br conversion ratio, dimethyl ether Selectivity is shown in Table 1.
Embodiment 9
Catalyst preparation is the same as embodiment 1.Gained catalyst is fitted into continuous fixed bed reactor, is warming up under nitrogen 350 DEG C, it is passed through -70% nitrogen mixture of 30% air, activates 2h.Then 300 DEG C are cooled the temperature under a nitrogen to be reacted； Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 150h-1, CH3Br conversion ratio, dimethyl ether Selectivity is shown in Table 1.
Embodiment 10
Catalyst preparation is the same as embodiment 1.Gained catalyst is fitted into continuous fixed bed reactor, is warming up under nitrogen 350 DEG C, it is passed through -70% nitrogen mixture of 30% air, activates 2h.Then 200 DEG C are cooled the temperature under a nitrogen to be reacted； Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 100h-1, CH3Br conversion ratio, dimethyl ether Selectivity is shown in Table 1.
Embodiment 11
Catalyst preparation is the same as embodiment 1.Gained catalyst is fitted into continuous fixed bed reactor, is warming up under nitrogen 350 DEG C, it is passed through -70% nitrogen mixture of 30% air, activates 2h.Then 200 DEG C are cooled the temperature under a nitrogen to be reacted； Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 200h-1, CH3Br conversion ratio, dimethyl ether Selectivity is shown in Table 1.
Embodiment 12
Catalyst preparation is the same as embodiment 1.Gained catalyst is fitted into continuous fixed bed reactor, is warming up under nitrogen 350 DEG C, it is passed through -70% nitrogen mixture of 30% air, activates 2h.Then 200 DEG C are cooled the temperature under a nitrogen to be reacted； Reaction pressure is normal pressure；Feed gas molar group becomes CH3Br:N2=1:2.5, air speed 230h-1, CH3Br conversion ratio, dimethyl ether Selectivity is shown in Table 1.
Comparative example 1
It is added without triethanolamine, catalyst is made with embodiment 1 in remaining.It is maximum with X-ray diffraction intensityIt is brilliant When face is benchmark, the relative intensity of each crystal face is shown in Table 1.Evaluating catalyst condition is the same as embodiment 7, CH3Br conversion ratio, dimethyl ether choosing Selecting property is shown in Table 2.
Comparative example 2
Surfactant is not added, catalyst is made with embodiment 1 in remaining.It is maximum with X-ray diffraction intensityIt is brilliant When face is benchmark, the relative intensity of each crystal face is shown in Table 1.Evaluating catalyst condition is the same as embodiment 7, CH3Br conversion ratio, dimethyl ether choosing Selecting property is shown in Table 2.
Table 1
Table 2

Claims (27)

1. a kind of copper-based catalysts, the copper-based catalysts are made of copper oxide, lanthana, zirconium oxide, carrier, the copper oxide Mass percent in terms of Cu element in the catalyst is 5%-50%, matter of the zirconium oxide in terms of Zr element in the catalyst Amount percentage is 0.5%-20%, and mass percent of the lanthana in terms of La element in the catalyst is 0.5%-20%, Surplus is carrier, it is characterised in that: the catalyst with CuO feature crystal face { 110 },{111}、 {202}、It is wherein maximum with X-ray diffraction intensityWhen crystal face is benchmark, the relative intensity difference of each crystal face Are as follows:For 11-20,For 80-88,For 17-22,For 7-9,For 11-14；
The preparation method of the catalyst, includes the following steps:
(1) prepare containing alcohols, surfactant, triethanolamine aqueous solution, by copper presoma, zirconium precursor body, lanthanum presoma It is dissolved in the solution；
(2) by carrier incipient impregnation in solution prepared by step (1), aging, drying are carried out；
(3) material by step (2) preparation carries out hydro-thermal process；
(4) catalyst is made after roasting to step (3) resulting material.
2. copper-based catalysts according to claim 1, it is characterised in that: the copper oxide in terms of Cu element in the catalyst Mass percent be 15%-30%, mass percent of the zirconium oxide in terms of Zr element in the catalyst is 0.5%- 15%, mass percent of the lanthana in terms of La element in the catalyst is 0.5%-15%, the carrier be aluminium oxide, One or more of silica, molecular sieve, active carbon or carbon nanotube.
3. copper-based catalysts according to claim 1, it is characterised in that: the zirconium oxide in terms of Zr element in the catalyst Mass percent be 1%-10%, mass percent of the lanthana in terms of La element in the catalyst is 1%-10%, The carrier is aluminium oxide.
4. catalyst according to claim 1, it is characterised in that: copper presoma described in step (1) is nitrate, chlorination One or more of object, sulfate.
5. catalyst according to claim 1, it is characterised in that: zirconium precursor body described in step (1) is nitrate, chlorination One or more of object, oxychlorination things, sulfate.
6. catalyst according to claim 1, it is characterised in that: lanthanum presoma described in step (1) is nitrate, chlorination One or more of object, sulfate.
7. catalyst according to claim 1, it is characterised in that: copper presoma described in step (1) is copper nitrate, described Zirconium precursor body is zirconium oxychloride, and the lanthanum presoma is lanthanum nitrate.
8. catalyst according to claim 1, it is characterised in that: alcohols described in step (1) is ethyl alcohol, isopropanol, just One or more of propyl alcohol.
9. catalyst according to claim 1, it is characterised in that: alcohols described in step (1) is isopropanol, and alcohols is molten Mass fraction in liquid is 1%-20%.
10. catalyst according to claim 1, it is characterised in that: surfactant described in step (1) is poly- second two One or more of alcohol, fatty alcohol polyoxyethylene ether, neopelex, Sodium Polyacrylate, Tween 80, the surface The mass fraction of activating agent in the solution is 0.1%-10%.
11. catalyst according to claim 1, it is characterised in that: the surfactant is fatty alcohol polyoxyethylene ether, The mass fraction of surfactant in the solution is 0.1%-5%.
12. catalyst according to claim 1, it is characterised in that: the surfactant is AEO-7, surfactant Mass fraction in the solution is 0.5%-2%.
13. catalyst according to claim 1, it is characterised in that: the matter of triethanolamine in the solution described in step (1) Amount score is 0.1%-10%.
14. catalyst according to claim 1, it is characterised in that: aging condition described in step (2) are as follows: aged at room temperature 2h-24h。
15. catalyst according to claim 1, it is characterised in that: drying condition described in step (2) are as follows: drying temperature It is 80 DEG C -200 DEG C；Drying time is 6h-48h, and dry is dry under the conditions of vacuum drying or inert gas shielding, or in sky It is dry under gas atmosphere.
16. catalyst according to claim 15, it is characterised in that: drying condition described in step (2) are as follows: drying temperature It is 80 DEG C -120 DEG C；Drying time is 6h-36h.
17. catalyst according to claim 1, it is characterised in that: carrier is bar shaped, piece shape, cylindricality or ball in step (2) Shape.
18. catalyst according to claim 1, it is characterised in that: hydrothermal conditions in step (3) are as follows: inert atmosphere Under be warming up to 100 DEG C -200 DEG C；The gaseous mixture of vapor and inert gas is then passed to, vapor volume basis contains in gaseous mixture Amount is 10%-90%, and surplus is inert gas；The processing time is 1h-10h；It is finally switched to inert gas, purges 0.5h-2h.
19. catalyst according to claim 18, it is characterised in that: hydrothermal conditions in step (3) are as follows: inert atmosphere Under be warming up to 120 DEG C -150 DEG C；Vapor volumn concentration is 50%-90% in gaseous mixture；The processing time is 1h-4h.
20. catalyst according to claim 1, it is characterised in that: roasting condition in step (4) are as follows: maturing temperature 500 ℃-900℃；Calcining time is 4h-24h；To roast under the conditions of inert gas shielding or roast in air atmosphere when roasting.
21. catalyst according to claim 20, it is characterised in that: roasting condition in step (4) are as follows: maturing temperature is 500℃-700℃；Calcining time is 4h-16h.
22. application of any catalyst of claim 1-21 in bromomethane preparing dimethy ether, it is characterised in that: with bromomethane For raw material, reaction temperature is 160 DEG C -420 DEG C；Reaction pressure is 0.1MPa-5MPa；Volume space velocity is 50h-1-2000h-1。
23. application according to claim 22, it is characterised in that: reaction temperature is 170 DEG C -320 DEG C；Reaction pressure is 0.1MPa-1MPa；Volume space velocity is 50h-1-1000h-1。
24. application according to claim 22, it is characterised in that: need to be activated catalyst before charging, activate Treatment conditions are as follows: the material after hydro-thermal process being warming up to 200 DEG C -600 DEG C under inert atmosphere；It then passes to air or contains Air and inert gas gaseous mixture；The processing time is 0.5h-10h；The gaseous mixture hollow gas product percentage composition is 5%- 90%.
25. application according to claim 24, it is characterised in that: be warming up to the material after hydro-thermal process under inert atmosphere 300℃-450℃；The processing time is 0.5h-4h；The gaseous mixture hollow gas product percentage composition is 5%-50%.
26. application according to claim 22, it is characterised in that: contain suitable inert gas, bromine in bromomethane raw material The volumn concentration of bromomethane raw material is 1%-99% in the gaseous mixture of methane feed and inert gas.
27. application according to claim 26, it is characterised in that: inert gas be one of nitrogen, argon gas, helium or It is several.
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