CN104014363B - Method for preparing copper-containing mordenite catalyst - Google Patents
Method for preparing copper-containing mordenite catalyst Download PDFInfo
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- CN104014363B CN104014363B CN201310066821.0A CN201310066821A CN104014363B CN 104014363 B CN104014363 B CN 104014363B CN 201310066821 A CN201310066821 A CN 201310066821A CN 104014363 B CN104014363 B CN 104014363B
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Abstract
The invention relates to a method for preparing a copper-containing mordenite catalyst. The method comprises the following steps: (1) providing an aqueous solution of copper salt, and adjusting the pH value of the solution to be equal to or more than 7 by adding an alkaline compound to prepare a copper-containing dispersion liquid; (2) mixing mordenite and the copper-containing dispersion liquid to obtain a solid-liquid mixture; and (3) carrying out solid-liquid separation on the solid-liquid mixture prepared in the step (2) to obtain a needed solid crude product, and washing, drying and roasting the solid crude product to obtain the copper-containing mordenite catalyst. The invention also provides a method for preparing methyl acetate by carbonylation of dimethyl ether in the presence of the catalyst.
Description
Technical field
The present invention relates to catalytic field, more particularly, the present invention relates to being used for preparing the mordenite catalyst of cupric
Method.
Background technology
Methyl acetate also known as methyl acetate, are a kind of important Organic Ingredientss intermediate, are most widely used fatty acids
One of ester, is widely used in the industries such as the intermediate field of weaving, spice, coating, ink, adhesive, medicine and pesticide.By
Methyl acetate can produce numerous downstream product, and such as methyl acetate hydrolysis produce acetic acid, methyl acetate hydrogenation produces ethanol etc..
The demand of methyl acetate maintains sustained and rapid growth in recent years.
The traditional processing technology of methyl acetate is to be raw material using methanol and acetic acid, and concentrated sulphuric acid is catalyst.Concentrated sulphuric acid is urged
Change activity high, cheap and easy to get, but etching apparatus is serious, and pollute environment, lead to product post processing difficult.
It is a more, noticeable new reaction of Recent study by dimethyl ether carbonylation reaction synthesis of acetic acid methyl ester
Route.This route selectivity of product height, process is simple, environment is not corroded and pollutes, be that a future is ideal
Methyl acetate production line.Dimethyl ether as a kind of important industrial chemicals, at present by the technology of producing dimethyl ether by dehydrating methanol
Technique is highly developed, and drug on the market to lead to the yield of dimethyl ether, is closed by carbonylation with dimethyl ether for raw material
Become the methyl acetate of high added value, be a kind of good approach of dimethyl ether effectively utilizes, have technically and economically substantially
Advantage.
The early stage research of Dimethyl ether carbonylation mainly uses the noble metal catalyst of loaded by heteropoly acid, but in order to reduce work
Skill cost, people are being devoted to exploitation inexpensively efficient new catalyst always.Iglesia group first reported within 2006
Modenite (8 yuan of rings and 12 yuan of rings) and ferrierite (8 yuan of rings and 10 yuan of rings) have very high dimethyl ether carbonylation reaction and live
Property, the selectivity of acetic acid product methyl ester is more than 90%(angew.chem.int.ed2006 (45): 1).Thus in molecular sieve catalytic
Achieve dimethyl ether carbonylation reaction on material it is achieved that dimethyl ether Halogen, base metal carbonylation course, have very
Important meaning.After this, people based on this, have carried out substantial amounts of improvement to catalyst and operating procedure.
One kind is described by, under substantially anhydrous conditions, urging having modenite or ferrierite in wo2006121778
In the presence of agent, with carbon monoxide carbonylation lower alkyl ether, to generate the lower alkyl esters of lower fatty acid as dimethyl ether
Method.
Us20070238897 reports the activity of the molecular sieve catalytic dimethyl ether carbonylation reaction of various different structures, sends out
The active highest of existing modenite, and the structure of molecular sieve, duct and acid bit distribution directly affect the activity of catalyst.
Cn200810011999.4 reports a kind of acid utilizing organic base-modified pore structures such as pyridine, adjusting modenite
The method of property, the method can make the stability of catalyst greatly improve.
Cn200880121584.0 reports a kind of modenite, copper-loaded modenite, carries modenite of silver etc. two
The renovation process of the carbonylation of dimethyl ether catalyst.The method pass through in 250-600 DEG C of temperature range to reactor in be passed through hydrogen
Or the gaseous mixture of hydrogen and carbon monoxide carrys out regenerated catalyst as regeneration gas.The method can make the activity of catalyst substantially extensive
Multiple even more high.
Cn201080021103.6 reports a kind of method improving modenite activity, and the method is to take off the silk of aluminum
Use alkali metal hydroxide or the aqueous solution of alkaline earth metal hydroxide to process modenite on geolyte again, can be obtained with this
Higher catalyst activity.
So far, in document, the catalyst of the Dimethyl ether carbonylation synthesis of acetic acid methyl ester of report focuses primarily upon mercerising boiling
Stone, ferrierite and the modenite with metals such as supported coppers etc..The modenite of supported copper is that report activity is higher at present
Catalyst.Basic research shows that metallic copper etc. increased the absorption of reactant co, thus leading to reaction rate to be accelerated, catalysis is lived
Property improve.
Ion exchange is the preferable method preparing loaded metal zeolite catalyst of current report, but the system of report
Standby process is all carried out under sour environment, is difficult to improve the exchange degree of metal and zeolite, generally requires to exchange for several times and can be only achieved
Certain load capacity.
In view of this, present applicant proposes a kind of preparation method carrying out ion exchange under alkaline environment, the method can
So that the exchange degree of metal greatly improves thus improve exchange efficiency, reducing exchange times, greatly reduce preparation process
Cost, the catalyst of preparation also show higher activity.Preparation process is simple, effective, has industrial applications prospect.
Content of the invention
The invention provides a kind of method of the mordenite catalyst for preparing cupric, the method includes following step
Rapid:
(1) aqueous solution of mantoquita is provided, and by add alkali compoundss by the ph value of this solution adjust to equal to or height
In 7, prepared cupric dispersion liquid；
(2) modenite is mixed with this cupric dispersion liquid, obtain solidliquid mixture；
(3) solidliquid mixture that step (2) is obtained carries out solid-liquid separation, obtains required solid crude product, and this is solid
Body crude product carries out washing, is dried and roasting, and the mordenite catalyst of described cupric is obtained.
In a preferred embodiment, when ph value is for 7-8.5, described cupric dispersion liquid is serosity form；When ph value
During more than 8.5, described cupric dispersion liquid is solution morphology.
In an embodiment of the invention, the aqueous solution of described mantoquita: copper nitrate, chlorine is prepared using following mantoquita
Change copper, copper bromide, copper chlorate, Schweinfurt green, Tubercuprose., copper sulfate and combinations thereof, the concentration of described copper salt solution is
0.01-0.5mol/l, preferably 0.03-0.3mol/l.
In yet another embodiment of the present invention, described alkali compoundss are selected from ammonia, urea, ethamine, propylamine, second two
Amine and combinations thereof, by adding alkali compoundss by the ph value of the aqueous solution of described mantoquita regulation to 7-10, preferably
7.5-9.
In yet another embodiment of the present invention, described modenite is h-mordenite, its framework silicon-aluminum mole
Than for nsio2:nal2o3=5:1-50:1, more preferably 5:1-30:1.
In yet another embodiment of the present invention, described step (2), at 0-100 DEG C, is entered at a temperature of preferably 10-50 DEG C
OK.In yet another embodiment of the present invention, the weight of described cupric dispersion liquid and modenite is than for 1:1 to 20:1, excellent
Elect 5:1 to 10:1 as.In yet another embodiment of the present invention, the persistent period of described step (2) is 1-10 hour, preferably
For 1-6 hour.
In yet another embodiment of the present invention, in described step (3), carry out roasting: temperature under the following conditions
For 300-600 DEG C, preferably 400-550 DEG C；Calcination atmosphere is selected from air, nitrogen or argon；Roasting time is 1-80 hour.
In yet another embodiment of the present invention, on the basis of the gross weight of the mordenite catalyst of described cupric
Meter, in this catalyst, the content of copper is 1-12 weight %.
Present invention also offers a kind of for by the method for preparing methyl acetate by carbonylating dimethyl ether, the method include with
Lower step: so that gas in the reaction system that there is the mordenite catalyst of cupric prepared by the method for the present invention
Raw mixture reacts, and described gas material mixture is the mixture of co and dimethyl ether or comprises co and h2Synthesis
Gas and the mixture of dimethyl ether, in described gas material mixture, co and the volume ratio of dimethyl ether are 1-100, preferably 1-50, instead
Temperature is answered to be 100-350 DEG C, pressure is 0.1-10mpa, the volume space velocity of described gas material mixture is that 1000-10000 is little
When-1.
The method for preparing catalyst process of the present invention is simple, efficient, can be obtained by shirtsleeve operation needed for having
The mordenite catalyst of high-copper load capacity, this catalyst has very high dimethyl ether conversion rate and methyl acetate selectivity.
Specific embodiment
" scope " disclosed herein is in the form of lower limit and the upper limit.One or more lower limits can be respectively, and one
Or the multiple upper limit.Given range is defined by selecting a lower limit and a upper limit.Selected lower limit and upper limit limit
Determine the border of special scope.All scopes that can be defined by this way comprise and can be combined, i.e. any lower limit
One scope of formation can be combined with any upper limit.For example, list the scope of 60-120 and 80-110 for special parameter, reason
Solving the scope for 60-110,60-80,110-120 and 80-120 is also expect.If additionally, the minimum zone value 1 listed
With 2, and if listing maximum magnitude value 3,4 and 5, then following scope can all expect: 1-2,1-3,1-4,1-5,2-
3rd, 2-4,2-5,3-4 and 4-5.In the present invention, illustrate without special, all embodiments mentioned in this article and
Preferred implementation can be mutually combined and form new technical scheme.
In the present invention, illustrate without special, all technical characteristics mentioned in this article and preferred feature can
Form new technical scheme to be mutually combined.
In the present invention, illustrate without special, all steps mentioned in this article can sequentially carry out it is also possible to
Carry out at random, but preferably sequentially carry out.For example, methods described includes step (a) and (b), represents that methods described can be wrapped
Include the step (a) that carries out of order and (b) it is also possible to the step (b) that carries out of inclusion order and (a).For example, described mention described side
Method may also include step (c), represents that step (c) can be added to methods described with random order, for example, methods described can include
Step (a), (b) and (c), may also comprise step (a), (c) with (b) it is also possible to include step (c), (a) and (b) etc..
The modenite that the present invention uses can change the kind of the cation of combination thereon by modes such as ion exchanges
Class, for example, under the conditions of neutral or alkaline ph value, the modenite of preparation is often na type or K-type zeolite, i.e. modenite
The counter cation connecting on al-si skeleton is sodium or potassium, by being processed to it with acid solution, so that these ions
Exchanged by hydrion, thus obtaining h-mordenite.Similarly it is also possible to make modenite by way of ion exchange
On cation be mg, ca etc..One of the present invention preferred embodiment in, the modenite in catalyst of the present invention is excellent
Choosing is h-mordenite.For the modenite of natural origin, due to the difference of its place of production natural conditions, framework silicon therein
Al mole ratio is it may happen that than larger change.And the modenite for commercial synthesis, by adjusting sodium silicate, aluminum in raw material
The condition such as the mol ratio of the components such as salt and acid-base value is it is also possible to effectively adjust prepared zeolitic frameworks silica alumina ratio and micro-
See pore passage structure.In a preferred embodiment of the present invention, used in described catalyst modenite framework silicon-aluminum
Mol ratio is nsio2:nal2o3=5:1 to 50:1, more preferably 5:1 to 30:1.
The present invention is with the maximum difference of existing process, adjusts the ph value of copper solution to more than 7 first, then right again
Modenite carries out dip operation.The inventors discovered that, here neutral to alkalescence, copper can more easily with mercerising
Zeolite combines, thus obtain thering is more high-copper load capacity and higher active mordenite catalyst.By comparison, existing
Technique often carries out cation exchange under the conditions of relatively low ph value, generally requires to exchange the load needed for can be only achieved for several times
Amount.
In the step (ii) of the inventive method, the alkali compoundss that used can selected from ammonia, urea, ethamine, propylamine,
Ethylenediamine and combinations thereof, most preferably ammonia.These alkali compoundss can be in drying and roasting process afterwards
It is removed, detrimental effect will not be brought to the final composition of catalyst and performance.By adding alkali compoundss by described copper
The ph value of the aqueous solution of salt is adjusted to 7-10, preferably 7.5-9.During adding alkali compoundss, in described copper solution
Copper is combined with alkali compoundss, and with the rising of ph, the state of copper-containing compound is copper-bearing complex solution by precipitating gradually transition
State.When ph value is for 7-8.5, described cupric dispersion liquid is serosity form；When ph value is more than 8.5, described cupric dispersion liquid
For solution morphology.While not wishing to be limited by specifically theory, applicant thinks that Composite mechanism on modenite for the copper is as follows:
When cupric dispersion liquid is solution morphology, copper-amine complex can occur ion exchange with modenite, thus being supported on
On modenite；And when copper dispersion liquid is slurry condition, the copper of a part can be combined in the form of solid precipitation
On modenite, formation copper oxide of decomposing in high-temperature calcination process afterwards, and pass through solid phase at high operating temperatures
Ion exchange course is supported on modenite.
The catalyst that the method for the present invention is obtained is used for dimethyl ether (dme) to synthesize second with the carbonylation of carbon monoxide (co)
The reaction of sour methyl ester, reaction equation is shown below.
Specifically, this course of reaction can be carried out using any appropriate reaction system.It is, for example possible to use it is fixing
Bed reactor, the catalyst of the present invention is filled in the form of bed in the reactor, by dimethyl ether with former containing carbon monoxide
Material gas is passed through in described reactor so that the two reaction generates methyl acetate.The described unstripped gas containing carbon monoxide can be pure
Co gas or the gas containing co of any conventional from industrial source, such as key component are co and h2Synthesis gas.
In a preferred embodiment of the present invention, co and the mol ratio of dimethyl ether are co/dme=1-100, preferably co/dme=1-
50；Reaction temperature is 100-350 DEG C, preferably 150-250 DEG C, more preferably 180-220 DEG C；Reaction pressure is 0.1-10mpa；Institute
The cumulative volume air speed stating the unstripped gas comprising carbon monoxide with dimethyl ether is 1000-10000 hour-1.Those skilled in the art can
Require reaction process is carried out with further conventional tune with the actual conditions according to reaction and required conversion ratio, selectivity etc.
Whole.
Embodiment
Further illustrate the preferred embodiment of the present invention by following examples, but it is also possible to without departing substantially from this
On the premise of invention protection domain, various improvement are carried out to these preferred implementations of the present invention and combines, thus obtaining new
Embodiment.
In the examples below, unless other part, the water otherwise being used is deionized water, the various reagents being used
It is analysis pure.
Embodiment 1
Prepare 500 milliliters of 0.2m copper chloride solution, the ammonia of Deca 1m thereto, uses simultaneously under mechanical agitation
The ph value changes situation of ph meter detection solution.When solution ph reaches 7.5, stop Deca ammonia, continue stirring 0.5 hour, so
Weigh the h-mordenite (similarly hereinafter) that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its silica alumina ratio (n afterwardssio2:
nal2o3) it is 15, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange, then using cloth
Family name's funnel carries out sucking filtration to this mixture, and deionized water (20 milliliters × 3) is washed to solution, by the solid sample obtaining
It is dried 2 hours at 120 DEG C, be then transferred in Muffle furnace, roasting 8 hours, are drawn off under 550 DEG C of air atmosphere,
Tabletting, and grind the granule for 20-40 mesh for the screening.Copper content (weight %) in finished catalyst is by German Spike company
Icp Instrumental Analysis record (similarly hereinafter).
Embodiment 2
Prepare 500 milliliters of 0.3m copper nitrate solution, the ammonia of Deca 1m thereto, uses simultaneously under mechanical agitation
The ph value changes situation of ph meter detection solution.When solution ph reaches 8.0, stop Deca ammonia, continue stirring 0.5 hour, so
Weigh the h-mordenite that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its silica alumina ratio (n afterwardssio2:nal2o3) be
15, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange, then using buchner funnel pair
This mixture carries out sucking filtration, and deionized water (20 milliliters × 3) is washed to solution, by the solid sample obtaining in 120 DEG C
Lower drying 2 hours, is then transferred in Muffle furnace, and under 550 DEG C of air atmosphere, roasting 8 hours, are drawn off, tabletting, and
Grind the granule for 20-40 mesh for the screening.Copper content (weight %) in finished catalyst is by the icp instrument of German Spike company
Analysis records.
Embodiment 3
Prepare 500 milliliters of 0.3m copper acetate solution, the ammonia of Deca 1m thereto, uses simultaneously under mechanical agitation
The ph value changes situation of ph meter detection solution.When solution ph reaches 9.0, stop Deca ammonia, continue stirring 0.5 hour, so
Weigh the h-mordenite that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its silica alumina ratio (n afterwardssio2:nal2o3) be
15, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange, then using buchner funnel pair
This mixture carries out sucking filtration, and deionized water (20 milliliters × 3) is washed to solution, by the solid sample obtaining in 120 DEG C
Lower drying 2 hours, is then transferred in Muffle furnace, and under 550 DEG C of air atmosphere, roasting 8 hours, are drawn off, tabletting, and
Grind the granule for 20-40 mesh for the screening.Copper content (weight %) in finished catalyst is by the icp instrument of German Spike company
Analysis records.
Embodiment 4
Prepare 500 milliliters of 0.3m copper-bath, the ammonia of Deca 1m thereto, uses simultaneously under mechanical agitation
The ph value changes situation of ph meter detection solution.When solution ph reaches 8.3, stop Deca ammonia, continue stirring 0.5 hour, so
Weigh the h-mordenite that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its silica alumina ratio (n afterwardssio2:nal2o3) be
10, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange, then using buchner funnel pair
This mixture carries out sucking filtration, and deionized water (20 milliliters × 3) is washed to solution, by the solid sample obtaining in 120 DEG C
Lower drying 2 hours, is then transferred in Muffle furnace, and under 550 DEG C of air atmosphere, roasting 8 hours, are drawn off, tabletting, and
Grind the granule for 20-40 mesh for the screening.Copper content (weight %) in finished catalyst is by the icp instrument of German Spike company
Analysis records.
Embodiment 5
Prepare 500 milliliters of 0.3m formic acid copper solution, the ammonia of Deca 1m thereto, uses simultaneously under mechanical agitation
The ph value changes situation of ph meter detection solution.When solution ph reaches 8.8, stop Deca ammonia, continue stirring 0.5 hour, so
Weigh the h-mordenite that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its silica alumina ratio (n afterwardssio2:nal2o3) be
25, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange, then using buchner funnel pair
This mixture carries out sucking filtration, and deionized water (20 milliliters × 3) is washed to solution, by the solid sample obtaining in 120 DEG C
Lower drying 2 hours, is then transferred in Muffle furnace, and under 550 DEG C of air atmosphere, roasting 8 hours, are drawn off, tabletting, and
Grind the granule for 20-40 mesh for the screening.Copper content (weight %) in finished catalyst is by the icp instrument of German Spike company
Analysis records.
Comparative example 1
Prepare 500 milliliters of 0.3m copper nitrate aqueous solution, do not carry out the regulation of ph value, measured using ph, this copper nitrate
The ph value of solution is 3.1.Then weigh the h-mordenite that 50 grams of Tianjin Nan Hua catalyst company limiteies produce, its sial rubs
You are than (nsio2:nal2o3) it is 15, it is added in above-mentioned solution, this mixture stirs 1 hour at 20 DEG C, to carry out ion exchange,
Then using buchner funnel, this mixture is carried out with sucking filtration, deionized water (20 milliliters × 3) is washed to solution, Ran Houzai
In the copper nitrate solution of the 0.3m that the solid after washing is rejoined 500 milliliters, repeat aforesaid operations.Carry out altogether
Three secondary ions exchange.Third time ion exchange after washing, the solid sample obtaining is dried at 120 DEG C 2 hours, then
It is transferred in Muffle furnace, roasting 8 hours, are drawn off under 550 DEG C of air atmosphere, tabletting, and grind screening for 20-40 mesh
Granule.Copper content (weight %) in finished catalyst is recorded by the icp Instrumental Analysis of German Spike company.
Carry out dimethyl ether carbonylation reaction with the catalyst sample of above example 1-5 and comparative example 1.
This reaction uses micro fixed-bed reactor, and reactor is the stainless steel tube of 12 millimeters of internal diameter, loads 8 grams wherein
Catalyst, reactor feed gas are co and dme, and the mol ratio both this is co/dme=9/1, and the total reaction volume air speed of the two is
3600 hours-1.Reaction temperature is respectively 190 and 200 DEG C, and reaction pressure is 1mpa.
Using gas chromatograph, on-line analyses are carried out to product, analyze inorganic component using tdx post, examined with conductance cell
Survey device to be detected；Analyze organic component using parapok r post, detected with hydrogen flame detector.
The icp measurement result of catalyst that embodiment 1-5 and comparative example 1 are obtained and being carried out using these catalyst
The test result of dimethyl ether carbonylation reaction product collects and is listed in the table below in 1 and table 2.
Table 1
Table 2
Can see from the experimental result of Tables 1 and 2, the present invention, by heightening the ph value of copper solution, significantly promotes cu
Load effect on mordenite catalyst for the ion.The catalyst of embodiments of the invention 1-5 only carries out primary ions friendship
Change operation, just can obtain the copper load capacity of 7.6-9.2 weight %.And in comparative example 1, due to not adding alkali in copper solution
Property material, the ph value of solution is acidity, and in the case, hydrion present in solution can cause to the ion exchange of copper ion
Significantly disturb.Can see from the data of table 1, in the case of the raw material copper solution using same concentrations, even if repeating
After having carried out three secondary ion swap operations, copper load capacity in final catalyst is still only 4 weight %.This can be notable
Extend the process time and improve process costs, bring adverse effect to the commercialization of method for preparing catalyst.
From the data of Tables 1 and 2 it will be appreciated also that ground is seen, carry out under the conditions of acid ph value with shown in comparative example 1
The practice of ion exchange is compared, and the present invention passes through to be equal to or more than carry out the copper load of catalyst under conditions of 7 in ph value, significantly
Improve the catalytic performance of catalyst, obtain higher feed stock conversion and product yield.
Claims (14)
1. a kind of for by the method for preparing methyl acetate by carbonylating dimethyl ether, the method comprises the following steps: in cupric
So that gas material mixture reacts in the reaction system of mordenite catalyst, described gas material mixture is co
With the mixture of dimethyl ether, in described gas material mixture, co and the volume ratio of dimethyl ether are 1-100, and reaction temperature is 100-
350 DEG C, pressure is 0.1-10mpa, and the volume space velocity of described gas material mixture is 1000-10000 hour-1, wherein, described
Prepared by the method that the mordenite catalyst of cupric passes through to comprise the following steps:
(1) aqueous solution of mantoquita is provided, and is adjusted the ph value of this solution to 8.0-8.3 by adding alkali compoundss, be obtained
Cupric dispersion liquid, described alkali compoundss are selected from ammonia, urea, ethamine, propylamine, ethylenediamine and combinations thereof；
(2) modenite is mixed with this cupric dispersion liquid, obtain solidliquid mixture；
(3) solidliquid mixture that step (2) is obtained carries out solid-liquid separation, obtains required solid crude product, by this solids crude
Product carries out washing, is dried and roasting, and the mordenite catalyst of described cupric is obtained.
2. the method for claim 1 it is characterised in that in described gas material mixture co and dimethyl ether volume ratio
For 1-50.
3. the method for claim 1 it is characterised in that prepare the aqueous solution of described mantoquita: nitre using following mantoquita
Sour copper, copper chloride, copper bromide, copper chlorate, Schweinfurt green, Tubercuprose., copper sulfate and combinations thereof, described copper salt solution
Concentration be 0.01-0.5mol/l.
4. method as claimed in claim 3 is it is characterised in that the concentration of described copper salt solution is 0.03-0.3mol/l.
5. the method for claim 1 it is characterised in that described modenite be h-mordenite, its framework silicon-aluminum
Mol ratio is nsio2:nal2o3=5:1-50:1.
6. the method for claim 1 it is characterised in that described modenite be h-mordenite, its framework silicon-aluminum
Mol ratio is nsio2:nal2o3=5:1-30:1.
7. the method for claim 1 it is characterised in that described step (2) be blended in enter at a temperature of 0-100 DEG C
OK；The persistent period of described step (2) is 1-10 hour.
8. the method for claim 1 it is characterised in that described step (2) be blended in enter at a temperature of 10-50 DEG C
OK；The persistent period of described step (2) is 1-6 hour.
9. the method for claim 1 is it is characterised in that in described step (2), described cupric dispersion liquid is boiled with mercerising
The weight of stone is than for 1:1 to 20:1.
10. the method for claim 1 is it is characterised in that in described step (2), described cupric dispersion liquid and mercerising
The weight of zeolite is than for 5:1 to 10:1.
11. methods as any one of claim 1-4 are it is characterised in that described cupric dispersion liquid is serosity form.
12. the method for claim 1 it is characterised in that in described step (3), carries out roasting under the following conditions:
Temperature is 300-600 DEG C；Calcination atmosphere is selected from air, nitrogen or argon；Roasting time is 1-80 hour.
13. the method for claim 1 it is characterised in that in described step (3), carry out roasting under the following conditions:
Temperature is 400-550 DEG C；Calcination atmosphere is selected from air, nitrogen or argon；Roasting time is 1-80 hour.
14. the method for claim 1 are it is characterised in that with the gross weight of the mordenite catalyst of described cupric be
Benchmark meter, in this catalyst, the content of copper is 1-12 weight %.
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| CN113955768B (en) * | 2021-11-24 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Preparation method of Cu/MOR molecular sieve and application of Cu/MOR molecular sieve in preparation of ethanol by direct oxidation of methane |
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| CN102247883A (en) * | 2011-08-03 | 2011-11-23 | 中国地质大学（武汉） | Method for preparing copper oxide hydrogenation catalyst loaded on silica gel-mordenite composite carrier |
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