CN106031876B - The catalyst and preparation method thereof of isobutene is prepared for ether-splitting solution - Google Patents
The catalyst and preparation method thereof of isobutene is prepared for ether-splitting solution Download PDFInfo
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Abstract
The invention discloses a kind of catalyst and preparation method thereof for preparing isobutene for ether-splitting solution, the mass ratio of each component is respectively as follows: SO in the catalyst4 2‑0.5~50%；X2O30.1~15%；CuO0.5~30%；Al2O320~99%；Wherein, X2O3For rare earth oxide.Compared with current same type catalyst, catalyst provided by the invention can make MTBE air speed with higher, in the case where not adding environmentally harmful halogen, the conversion ratio close to 100% MTBE and methanol and selective isobutene close to 100% can be possessed in lower reaction temperature.Halogen-free addition reduces pollution sources simultaneously, adds clean and environmental protection；It does not need to be passed through the inert substances such as water into reaction system, energy consumption can be reduced and improves utilization rate of equipment and installations.
Description
Technical field
The present invention relates to catalyst technical fields, prepare isobutene for methyl tertiary butyl ether(MTBE) cracking more particularly to one kind
Multiple active components SO4 2-/X2O3/CuO/Al2O3Type catalyst and preparation method thereof.
Background technique
Isobutene is a kind of very important industrial chemicals, is widely used in the neck such as light industry, oil refining, medicine, fragrance, building materials
Domain.After the fine chemical product for increasingly increasing and accelerating development high added value with demand of the various countries to clean gasoline, to isobutyl
The demand of alkene also increasingly increases.Different according to the purity of isobutene, the purposes of isobutene is also different, and the isobutene of low-purity can
To produce methyl tertiary butyl ether(MTBE), polyisobutene, C5 alcohol etc..The isobutene of high-purity can produce butyl rubber, tert-butylamine etc..It is special
It is not butyl rubber, is popularized comprehensively with the name of environmental protection and replace pitch.Therefore the demand of high-purity isobutylene is more next
It is bigger.
The method of industrial comparative maturity has adsorption separation method, tert-butyl alcohol dehydration method, Halcon conjugated oxidation, iso-butane de-
Hydrogen method, n-butene isomerization process, methyl tertiary butyl ether(MTBE) (MTBE) cracking process etc..Uop company, the adsorption separation method U.S., ucc company
Research was carried out respectively, and since the process is more complicated for this, Technological Economy is not so good as traditional sulfuric acid extraction, therefore without before too big
Scape.Halcon conjugated oxidation is also rarely employed at present since the unit scale by propylene oxide is limited.Dehydrogenation of isobutane method is
One, rich in emulative production process route, but in actual production, needs to face hydrogen environment again to inhibit coking and removing carbon deposit,
Therefore production has some difficulty.N-butene isomerization process is mainly reaction temperature height, and the yield of isobutene is not high.MTBE cracking process
It is compared with the traditional method, the technique is corrosion-free to equipment, and operating condition mitigates, and product purity is high, and unit scale activity is big, is
Current most widely used, most study, a kind of most attractive method.
The part of MTBE cracking process most critical is catalyst, and the activity of catalyst directly influences MTBE conversion ratio, methanol
Selectivity, selective isobutene and air speed.Catalyst used at present mainly has: alumina system, silica system, ion are handed over
Change some catalyst of resin system, sulfate system, molecular sieve system, Phosphoric Acid, heteropolyacid system and other systems.
But current catalyst more or less has some disadvantages.For MTBE cracking reaction, it is an endothermic reaction, is mentioned
High-temperature can significantly improve the conversion ratio of MTBE, but excessively high reaction temperature by the dehydration for causing methanol generate dimethyl ether,
The hydration of the dimerization of isobutene, isobutene, which generates side reactions, these side reactions such as the tert-butyl alcohol, reduces the purity of product isobutene,
Additional cost is increased to the separation and purification of product.It needs that the inertia such as a large amount of vapor are added while some catalyst reactions
Substance will substantially reduce the yield of methanol and isobutene, reduce utilization rate of equipment and installations.Therefore one kind is needed to gather around at low temperatures
There is the catalyst of high MTBE conversion ratio and high methanol and selective isobutene.
Ion exchange resin system is maximum, and the disadvantage is that not tolerating high temperature, high temperature will lead to sulfonic acid group and fall off, and cause to urge
The inactivation of agent, so can only be in low-temp reaction, and temperature is too low will lead to the low of MTBE conversion ratio；Phosphoric Acid is maximum
The disadvantage is that being easy argillization agglomeration, the lost of life is caused；Heteropolyacid system leads to catalyst cost since the cost of heteropoly acid is excessively high
Height, while the air speed of heteropoly acid is too low；Sulfate system catalyst possesses 95% or so MTBE conversion ratio, 98% or so first
Alcohol selectivity and selective isobutene, halogen is added into sulfate system can make catalyst obtain higher MTBE conversion
Rate, methanol selectivity and selective isobutene.Similarly, niobic acid System Catalyst, Phosphoric Acid catalyst etc. also all pass through
A certain amount of halogen is added to obtain higher MTBE conversion ratio and higher methanol and selective isobutene.It is catalyzed containing halogen
Although agent is had excellent performance, but its low biological degradation rate will lead to the accumulation of halogen constantly in vivo, influence human health, is broken
Bad ecological environment；The presence of halogen will result directly in the growth of environmental protection of enterprise treatment cost simultaneously.
Summary of the invention
In view of this, it is an object of the invention to propose a kind of catalyst and its preparation for preparing isobutene for ether-splitting solution
Method to improve MTBE conversion ratio and selective isobutene, while being avoided using halogen.
Based on above-mentioned purpose, the mass ratio of each component in the catalyst of isobutene is prepared provided by the present invention for ether-splitting solution
It is respectively as follows:
Wherein, X2O3For rare earth oxide.
In yet another embodiment of the present invention, the matter that each component in the catalyst of isobutene is prepared for ether-splitting solution
Amount ratio is respectively as follows:
In yet another embodiment of the present invention, the Al2O3Selected from hydrated alumina, η-Al2O3、χ-Al2O3With γ-
Al2O3At least one of.
In yet another embodiment of the present invention, the X2O3Selected from CeO2、La2O3And Sm2O3At least one of.
The present invention also provides a kind of methods for preparing above-mentioned catalyst, comprising the following steps:
Copper salt solution and rare earth soluble salt solutions are mixed, mixed impregnant liquor is obtained；
Aluminium oxide is impregnated into the mixed impregnant liquor 1~8 hour, after filtering, by filter residue in 80 DEG C~150 DEG C conditions
Then lower drying 1~8 hour roasts 1~8 hour in 400 DEG C~700 DEG C, obtains X2O3/CuO/Al2O3；
By X2O3/CuO/Al2O3It is impregnated into sulfate solution 1~8 hour, after filtering, by filter residue 80 DEG C~150
It is 1~8 hour dry under the conditions of DEG C, it is then roasted 1~8 hour in 400 DEG C~700 DEG C, obtains SO4 2-/X2O3/CuO/Al2O3Type
Catalyst.
In yet another embodiment of the present invention, the mantoquita is in copper sulphate, copper chloride, copper nitrate, copper acetate
It is one or more of.
In yet another embodiment of the present invention, one of the rare earth soluble-salt selected from cerium, lanthanum, samarium soluble-salt
Or it is several.
In yet another embodiment of the present invention, the sulfate solution is selected from sodium sulphate, magnesium sulfate, sulfuric acid, sulfuric acid
The aqueous solution of one or more of ammonium, ammonium hydrogen sulfate, copper sulphate, cerous sulfate, ceric sulfate, aluminum sulfate, lanthanum sulfate sulfate.
In yet another embodiment of the present invention, the mass concentration of the copper salt solution is 0.1%~50%, rare-earth salts
The mass concentration of aqueous solution is 0.1%~50%, and the mass concentration of sulfate solution is 0.1%~40%.
In yet another embodiment of the present invention, the mass concentration of the copper salt solution is 1%~30%, rare earth salt water
The mass concentration of solution is 1%~30%, and the mass concentration of sulfate solution is 1%~25%.
In yet another embodiment of the present invention, the content of mantoquita and rare earth soluble-salt is distinguished in the mixed impregnant liquor
For 0.01~8g/ml and 0.01~8g/ml；Impregnate X2O3/CuO/Al2O3Afterwards, the X in the sulfate solution2O3/CuO/
Al2O3Content be 0.01~20g/ml, most preferably measure be 0.1~15g/ml.
From the above it can be seen that catalyst provided by the invention can make compared with current same type catalyst
MTBE air speed with higher can possess in the case where not adding environmentally harmful halogen in lower reaction temperature
Conversion ratio close to 100% MTBE and methanol and selective isobutene close to 100%.Halogen-free addition reduces simultaneously
Pollution sources add clean and environmental protection；It does not need to be passed through the inert substances such as water into reaction system, energy consumption can be reduced and improves equipment utilization
Rate.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
1) cerous nitrate that the copper sulphate of mass concentration 20% and mass concentration are 30% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper sulphate is 0.25g/ml in the mixed impregnant liquor, and the amount of cerous nitrate is 0.16g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 8 hours (excessive to impregnate), filtering takes filter residue, dries at 80 DEG C
It is 8 hours dry in case, it is then roasted 8 hours in 500 DEG C, obtains CeO2/CuO/Al2O3.Wherein, the aluminium oxide can be water
Close aluminium oxide, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by CeO2/CuO/Al2O3It is immersed in the aqueous sodium persulfate solution of mass concentration 20% 7 hours, obtains CeO2/
CuO/Al2O3Amount be 10g/ml mixture；Then it filters, takes filter residue, it is 8 hours dry in 120 DEG C of baking ovens, then at 550 DEG C
7 hours are roasted to get multiple active components SO is arrived4 2-/CeO2/CuO/Al2O3Type catalyst.
The quality of each component compares range in the catalyst are as follows: SO4 2-For 8~12%, CeO2For 3~8%, CuO be 3~
8%, Al2O3It is 72~86%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 3h-1, reaction temperature is 180 DEG C, MTBE conversion ratio 98.7%, isobutene selection
Property 99.9%, methanol selectivity 99.3%.
Embodiment 2
1) lanthanum nitrate that the copper chloride of mass concentration 30% and mass concentration are 15% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper chloride is 1.7g/ml in the mixed impregnant liquor, and the amount of lanthanum nitrate is 1.2g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 5 hours (excessive to impregnate), filtering takes filter residue, dries at 110 DEG C
It is 3 hours dry in case, it is then roasted 6 hours in 600 DEG C, obtains La2O3/CuO/Al2O3.Wherein, the aluminium oxide can be water
Close aluminium oxide, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by La2O3/CuO/Al2O3It is immersed in the magnesium sulfate solution of mass concentration 25% 6 hours, obtains La2O3/
CuO/Al2O3Amount be 8g/ml solution；Then it filters, takes filter residue, it is 7 hours dry in 90 DEG C of baking ovens, it is roasted then at 450 DEG C
4 hours to get arrive multiple active components SO4 2-/La2O3/CuO/Al2O3Type catalyst.
The quality of each component compares range in the catalyst are as follows: SO4 2-For 8~12%, La2O3For 2~6%, CuO be 3~
8%, Al2O3It is 74~87%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 2h-1, reaction temperature is 160 DEG C, MTBE conversion ratio 98.5%, isobutene selection
Property 99.9%, methanol selectivity 99.6%.
Embodiment 3
1) lanthanum sulfate that the copper nitrate of mass concentration 25% and mass concentration are 20% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper nitrate is 2.5g/ml in the mixed impregnant liquor, and the amount of lanthanum sulfate is 2.0g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 4 hours (excessive to impregnate), filtering takes filter residue, dries at 130 DEG C
It is 5 hours dry in case, it is then roasted 5 hours in 700 DEG C, obtains La2O3/CuO/Al2O3.Wherein, the aluminium oxide can be water
Close aluminium oxide, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by La2O3/CuO/Al2O3It is immersed in the sulfuric acid solution of mass concentration 33% 8 hours, obtains La2O3/CuO/
Al2O3Amount be 7g/ml solution；Then it filters, takes filter residue, it is 3 hours dry in 100 DEG C of baking ovens, it is small then at 520 DEG C of roastings 6
When to get arrive multiple active components SO4 2-/La2O3/CuO/Al2O3Type catalyst.
The quality of each component compares range in the catalyst are as follows: SO4 2-For 5~10%, La2O3For 4~10%, CuO be 4~
7%, Al2O3It is 70~85%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 2h-1, reaction temperature is 170 DEG C, MTBE conversion ratio 99.1%, isobutene selection
Property 99.8%, methanol selectivity 99.6%.
Embodiment 4
1) cerous sulfate that the copper acetate of mass concentration 15% and mass concentration are 10% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper acetate is 2.3g/ml in the mixed impregnant liquor, and the amount of cerous sulfate is 1.8g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 6.5 hours (excessive to impregnate), filtering takes filter residue, at 95 DEG C
It is 4 hours dry in baking oven, it is then roasted 4 hours in 440 DEG C, obtains CeO2/CuO/Al2O3.Wherein, the aluminium oxide can be
Hydrated alumina, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by CeO2/CuO/Al2O3It is immersed in the ammonium sulfate solution of mass concentration 12% 8 hours, obtains CeO2/
CuO/Al2O3Amount be 9.5g/ml solution；Then it filters, takes filter residue, it is 8 hours dry in 80 DEG C of baking ovens, it is roasted then at 660 DEG C
5.5 hours are burnt to get multiple active components SO is arrived4 2-/CeO2/CuO/Al2O3Type catalyst.
The mass ratio of each component is respectively as follows: SO in the catalyst4 2-For 3~9%, CeO2For 1.5~8%, CuO be 4~
15%, Al2O3It is 76~83%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 5h-1, reaction temperature is 190 DEG C, MTBE conversion ratio 99.2%, isobutene selection
Property 99.8%, methanol selectivity 99.7%.
Embodiment 5
1) cerous nitrate that the copper chloride of mass concentration 8% and mass concentration are 30% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper chloride is 1.7g/ml in the mixed impregnant liquor, and the amount of cerous nitrate is 3.3g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 2.8 hours (excessive to impregnate), filtering takes filter residue, at 105 DEG C
It is 3 hours dry in baking oven, it is then roasted 6 hours in 620 DEG C, obtains CeO2/CuO/Al2O3.Wherein, the aluminium oxide can be
Hydrated alumina, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by CeO2/CuO/Al2O3It is immersed in the ammonium hydrogen sulfate aqueous solution of mass concentration 18% 6.6 hours, obtains
CeO2/CuO/Al2O3Amount be 16g/ml solution；Then it filters, takes filter residue, it is 3.2 hours dry in 150 DEG C of baking ovens, then at
480 DEG C roast 6.5 hours to get multiple active components SO is arrived4 2-/CeO2/CuO/Al2O3Type catalyst.
The mass ratio of each component is respectively as follows: SO in the catalyst4 2-For 4~18%, CeO2For 0.5~6%, CuO be 1~
10%, Al2O3It is 65~75%.The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl- tert
Butyl ether is fed with micro-amounts of liquids sampling pump, and control liquid air speed is 4h-1, reaction temperature is 190 DEG C, MTBE conversion ratio
98.9%, selective isobutene 99.8%, methanol selectivity 99.7%.
Embodiment 6
1) cerous sulfate that the copper sulphate of mass concentration 50% and mass concentration are 8% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper sulphate is 3.1g/ml in the mixed impregnant liquor, and the amount of cerous sulfate is 1.2g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 5.2 hours (excessive to impregnate), filtering takes filter residue, at 140 DEG C
It is 2.2 hours dry in baking oven, it is then roasted 5.5 hours in 680 DEG C, obtains CeO2/CuO/Al2O3.Wherein, the aluminium oxide can
To be hydrated alumina, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by CeO2/CuO/Al2O3It is immersed in the ammonium hydrogen sulfate aqueous solution of mass concentration 30% 2.8 hours, obtains
CeO2/CuO/Al2O3Amount be 5g/ml solution；Then it filters, takes filter residue, it is 7 hours dry in 100 DEG C of baking ovens, then at 500
DEG C roasting 7 hours to get arrive multiple active components SO4 2-/CeO2/CuO/Al2O3Type catalyst.
The mass ratio of each component is respectively as follows: SO in the catalyst4 2-For 5~15%, CeO2For 2~5%, CuO be 0.5~
8%, Al2O3It is 70~82.5%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 3h-1, reaction temperature is 180 DEG C, MTBE conversion ratio 99.2%, isobutene selection
Property 99.9%, methanol selectivity 99.5%.
Embodiment 7
1) cerous nitrate that the copper sulphate of mass concentration 22% and mass concentration are 18% is uniformly mixed, is configured to mixing leaching
Stain liquid.The amount of copper sulphate is 1.8g/ml in the mixed impregnant liquor, and the amount of cerous nitrate is how many 1.5g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 4 hours (excessive to impregnate), filtering takes filter residue, dries at 120 DEG C
It is 8 hours dry in case, it is then roasted 7 hours in 680 DEG C, obtains CeO2/CuO/Al2O3.Wherein, the aluminium oxide can be water
Close aluminium oxide, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by CeO2/CuO/Al2O3It is immersed in the aluminum sulfate aqueous solution of mass concentration 30% 7 hours, obtains CeO2/
CuO/Al2O3Amount be 12g/ml solution；Then it filters, takes filter residue, it is 5 hours dry in 108 DEG C of baking ovens, it is roasted then at 630 DEG C
4.8 hours are burnt to get multiple active components SO is arrived4 2-/CeO2/CuO/Al2O3Type catalyst.
The mass ratio of each component is respectively as follows: SO in the catalyst4 2-For 2.6~11%, CeO2It is for 1.8~7.6%, CuO
4~18%, Al2O3It is 68~90%.
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 3h-1, reaction temperature is 180 DEG C, MTBE conversion ratio 99.2%, isobutene selection
Property 99.9%, methanol selectivity 99.5%.
Embodiment 8
1) samaric nitrate that the copper sulphate of mass concentration 0.8% and mass concentration are 1.5% is uniformly mixed, is configured to mix
Maceration extract.The amount of copper sulphate is 0.03g/ml in the mixed impregnant liquor, and the amount of samaric nitrate is 0.07g/ml.
2) aluminium oxide is immersed in the mixed impregnant liquor 7.8 hours (excessive to impregnate), filtering takes filter residue, at 95 DEG C
It is 6 hours dry in baking oven, it is then roasted 6.8 hours in 480 DEG C, obtains Sm2O3/CuO/Al2O3.Wherein, the aluminium oxide can be with
It is hydrated alumina, η-Al2O3、χ-Al2O3、γ-Al2O3At least one of.
3) by Sm2O3/CuO/Al2O3It is immersed in the copper sulfate solution of mass concentration 5.5% 5.8 hours, obtains
Sm2O3/CuO/Al2O3Amount be 0.5g/ml solution；Then it filters, takes filter residue, it is 7 hours dry in 80 DEG C of baking ovens, then at
690 DEG C roast 6.6 hours to get multiple active components SO is arrived4 2-/Sm2O3/CuO/Al2O3Type catalyst.
The mass ratio of each component is respectively as follows: SO in the catalyst4 2-For 4.5~15%, Sm2O3For 2~8%, CuO 3.5
~20%, Al2O3It is 77~88%
The above-mentioned catalyst of 20g is fitted into the micro fixed-bed reactor of Φ 20mm diameter, methyl tertiary butyl ether(MTBE) liquid
Micro-sampling pump charging, control liquid air speed are 2h-1, reaction temperature is 180 DEG C, MTBE conversion ratio 99.5%, isobutene selection
Property 99.9%, methanol selectivity 99.5%.
Therefore, catalyst provided by the invention is not only not necessarily to add halogen, and possesses the MTBE conversion ratio close to 100%
And close to 100% methanol and selective isobutene, while possessing higher reaction velocity.Halogen-free addition makes catalyst more
Add environment-protecting clean, the promotion of catalyst performance is so that reaction more low energy.It will be catalyzed disclosed in ZL200610030973.5
Agent and SO provided by the invention4 2-/Sm2O3/CuO/Al2O3The performance of type catalysis compares, and reaction condition is reaction under normal pressure
Temperature is
170 DEG C the results are shown in Table 1.
Table 1
It can be seen that it is higher that catalyst provided by the invention can be such that MTBE has compared with current same type catalyst
Air speed can possess in lower reaction temperature close to 100% in the case where not adding environmentally harmful halogen
The conversion ratio of MTBE and close to 100% methanol and selective isobutene.Halogen-free addition reduces pollution sources simultaneously, adds clear
Clean environmental protection；It does not need to be passed through the inert substances such as water into reaction system, energy consumption can be reduced and improves utilization rate of equipment and installations.
It should be understood by those ordinary skilled in the art that: the above is only a specific embodiment of the present invention, and
It is not used in the limitation present invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done,
It should be included within protection scope of the present invention.
Claims (10)
1. a kind of catalyst for preparing isobutene for ether-splitting solution, which is characterized in that the mass ratio of each component in the catalyst
It is respectively as follows:
Wherein, X2O3For rare earth oxide, the rare earth oxide is selected from CeO2、La2O3And Sm2O3At least one of.
2. the catalyst according to claim 1 for preparing isobutene for ether-splitting solution, which is characterized in that the Al2O3It is selected from
Hydrated alumina, η-Al2O3、χ-Al2O3With γ-Al2O3At least one of.
3. a kind of prepare the method for preparing the catalyst of isobutene described in any one of claim 1~2 for ether-splitting solution,
Characterized by comprising the following steps:
Copper salt solution and rare earth soluble salt solutions are mixed, mixed impregnant liquor is obtained；
Aluminium oxide is impregnated into the mixed impregnant liquor 1~8 hour, after filtering, filter residue is done under the conditions of 80 DEG C~150 DEG C
It dry 1~8 hour, is then roasted 1~8 hour in 400 DEG C~700 DEG C, obtains X2O3/CuO/Al2O3；
By X2O3/CuO/Al2O3It is impregnated into sulfate solution 1~8 hour, after filtering, by filter residue in 80 DEG C~150 DEG C conditions
Then lower drying 1~8 hour roasts 1~8 hour in 400 DEG C~700 DEG C, obtains SO4 2-/X2O3/CuO/Al2O3Type catalyst.
4. the preparation method of the catalyst according to claim 3 for preparing isobutene for ether-splitting solution, which is characterized in that institute
It states mantoquita and is selected from one or more of copper sulphate, copper chloride, copper nitrate, copper acetate.
5. the preparation method of the catalyst according to claim 3 for preparing isobutene for ether-splitting solution, which is characterized in that dilute
One or more of native soluble-salt selected from cerium, lanthanum, samarium soluble-salt.
6. the preparation method of the catalyst according to claim 3 for preparing isobutene for ether-splitting solution, which is characterized in that institute
It states sulfate solution and is selected from sodium sulphate, magnesium sulfate, ammonium sulfate, ammonium hydrogen sulfate, copper sulphate, cerous sulfate, ceric sulfate, sulfuric acid
The aqueous solution of one or more of aluminium, lanthanum sulfate sulfate.
7. the preparation method of the catalyst according to claim 3 for preparing isobutene for ether-splitting solution, which is characterized in that institute
The mass concentration for stating copper salt solution is 0.1%~50%, and the mass concentration of rare earth salt aqueous solution is 0.1%~50%, sulfuric acid
The mass concentration of saline solution is 0.1%~40%.
8. the preparation method of the catalyst according to claim 7 for preparing isobutene for ether-splitting solution, which is characterized in that institute
The mass concentration for stating copper salt solution is 1%~30%, and the mass concentration of rare earth salt aqueous solution is 1%~30%, sulfuric acid salt water
The mass concentration of solution is 1%~25%.
9. the preparation method of the catalyst according to claim 3 for preparing isobutene for ether-splitting solution, which is characterized in that institute
Stating the content of mantoquita and rare earth soluble-salt in mixed impregnant liquor is respectively 0.01~8g/ml and 0.01~8g/ml；Impregnate X2O3/
CuO/Al2O3Afterwards, the X in the sulfate solution2O3/CuO/Al2O3Content be 0.01~20g/ml.
10. the preparation method of the catalyst according to claim 9 for preparing isobutene for ether-splitting solution, which is characterized in that
X in the sulfate solution2O3/CuO/Al2O3Content be 0.1~15g/ml.
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|---|---|---|---|---|
| CN1418729A (en) * | 2002-12-06 | 2003-05-21 | 华东理工大学 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
| CN101020142A (en) * | 2007-02-12 | 2007-08-22 | 浙江大学 | Catalyst for cracking methyl tert-butyl ether to prepare isobutylene and its prepn |
| CN103846098A (en) * | 2014-03-25 | 2014-06-11 | 华东理工大学 | Catalyst for preparing isopentene by cracking of tertiary amyl methyl ether, as well as preparation method and applications of catalyst |
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| US9334575B2 (en) * | 2012-05-03 | 2016-05-10 | Los Alamos National Security, Llc | Catalytic oxidation of dimethyl ether |
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| CN1418729A (en) * | 2002-12-06 | 2003-05-21 | 华东理工大学 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
| CN101020142A (en) * | 2007-02-12 | 2007-08-22 | 浙江大学 | Catalyst for cracking methyl tert-butyl ether to prepare isobutylene and its prepn |
| CN103846098A (en) * | 2014-03-25 | 2014-06-11 | 华东理工大学 | Catalyst for preparing isopentene by cracking of tertiary amyl methyl ether, as well as preparation method and applications of catalyst |
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