CN106955687A - A kind of preparation method and application for being used to prepare the catalyst of alkene - Google Patents
A kind of preparation method and application for being used to prepare the catalyst of alkene Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
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Abstract
The invention discloses a kind of multicomponent NiO/ SiO that high purity olefin is prepared for ether-splitting solution2 / F‑/ SO4 2‑/ Al2O3Type catalyst and preparation method thereof.According to this method, the component and percentage by weight of catalyst are：Al2O3 20 ~ 95%, NiO 1 ~ 50%, SiO2 0.1 ~ 20%, F‑ 0.1 ~ 10%, SO4 2‑ 0.5~35%.The catalyst of the present invention is prepared using infusion process, it is simple to operate, cheap, the reaction that ether-splitting solution prepares alkene can be carried out under than current similar catalyst lower temperature, while high alkene and methanol selectivity is ensured, ether-splitting solution has 2 ~ 10 times of raising than similar industrial catalyst close to complete conversion, the liquid air speed of reaction.
Description
Technical field
The preparation and application of the catalyst of alkene are prepared the present invention relates to a kind of ether-splitting solution.It is primarily related to metal oxidation
Thing, silica, halogen and sulfate are supported on the multicomponent NiO/ SiO on alundum (Al2O3)2/ F-/ SO4 2-/ Al2O3Type is urged
Agent.
Background technology
Iso-amylene is the mixture of 2- methyl-2-butenes and 2-methyl-1-butene alkene, and 2- methyl-2-butenes are most of anti-
The active component answered, therefore higher the included value of the content of 2- methyl-2-butenes is higher.Isobutene is used as a kind of important change
Work raw material, is widely used in production isoprene, pinacoline, tert-pentyl alcohol, spices and agricultural chemicals, wherein for producing agricultural chemicals and perfume (or spice)
Material accounts for the overwhelming majority.In particular with the disabling of domestic phosphorous agricultural chemicals, iso-amylene is given birth to as synthesis triazole bactericidal agent, plant
The base stock of the non-phosphorous agricultural chemicals such as long conditioning agent and herbicide is used widely, and demand is increased rapidly.
Production iso-amylene main method have oil gas separation, tert-pentyl alcohol dehydration, diolefin hydrogenation, pentane dehydrogenation, directly
Alkene hydrocarbon isomerization and TAME ether solutions.TAME cracking prepares the main method that iso-amylene is industrial production iso-amylene, with
Traditional method is compared, with product purity is high, reaction condition it is relative relax, high income the features such as be used widely.
Isobutene is a kind of important industrial chemicals, as synthesis butyl rubber, polyisobutene, methacrylate etc.
During chemical products, the requirement to its purity is at a relatively high, it is necessary to which a large amount of numerous and diverse separation processes or acid extraction, adsorbing separation etc. are able to
Realize.Because the downstream product of isobutene is a lot, isobutene is in great demand China, and the market competitiveness is also very fierce,
The C-4-fraction in steam cracking and catalytic cracking product is mostly come from, the traditional handicraft of industrial production isobutene has sulfuric acid
Extracting, molecular sieve adsorption, tert-butyl alcohol dehydration etc..Methyl tertiary butyl ether(MTBE) (MTBE) cracking prepare isobutene be a kind of advanced technology and
The technique that economically viable new development is got up, compared with traditional handicraft, with pollution-free, corrosion-free, product purity is high, one way turns
The features such as rate is high, device independence is strong.
Catalyst is the key that ether solution prepares alkene, and the performance of catalyst directly influences the conversion of ether cracking reaction
The important indicators such as rate, selectivity of product.
From the point of view of reaction in itself, ether-splitting solution is the endothermic reaction, improves reaction temperature and is conducive to ether to be cracked to form iso-amylene, temperature
When degree is higher, ether is close to complete conversion, it is to avoid the problems such as separation and recovery of ether is recycled, and reduces energy consumption.But cracking temperature
Gao Shi, side reaction increases, and such as iso-amylene oligomerisation causes the loss of iso-amylene；Crack obtained methanol dehydration generation dimethyl ether, two
The generation of methyl ether can reduce the rate of recovery of methanol, result in the need for adding substantial amounts of methanol again into initial etherification reaction system；
The water that dimethyl ether is produced when generating also is lost product with iso-amylene hydration, while separation of the generation of accessory substance to product
It is refined to add cost etc..The shortcoming of ion-exchange resin catalyst is that resistance to elevated temperatures is poor, when the temperature of reaction is too high, its
In active component easily decompose come off, due to being limited by reaction temperature, the conversion ratio of reaction is all relatively low.Therefore one is provided
Kind under relatively low reaction temperature, there is a high conversion ratio, high air speed, high alkene and methanol selectivity, and also it is cheap
Again environmental protection ether catalyst for cracking be related industry department it is highly desirable.
The content of the invention
Ether-splitting solution is the back reaction of ether synthetic reaction, under catalyst action, is cracked into alkene and methanol.Such as methyl- tert
Amyl ether is cracked：
CH3CH2C(CH3)2OCH3 CH2=C(CH3)CH2CH3+CH3CH2(CH)=CHCH3+CH3OH
It may also happen that following main side reaction during tert amyl methyl ether(TAME) cracking：
1. the oligomerisation reaction of iso-amylene
nC5H10 —(—C5H10—)n— (n>1)
2. methanol dehydration generates dimethyl ether
2CH3OH CH3OCH3+H2O
3. tert-pentyl alcohol is dehydrated
2CH3CH2C(CH3)2OH H2C=C(CH3)CH2CH3+H3CHC(CH3)2+H2O
For example methyl tertiary butyl ether(MTBE) is cracked：
CH3-O-C(CH3)3 H2C=C(CH3)2+CH3OH
It may also happen that following main side reaction during methyl tertiary butyl ether(MTBE) cracking：
1. isobutene dimerization generates Diisobutylene
2H2C=C(CH3)2 H3C-C(CH3)2-CH=C(CH3)2
2. the isobutene hydration generation tert-butyl alcohol
H2C=C(CH3)2+H20 H2C-C(CH3)2OH
3. methanol dehydration generates dimethyl ether
2CH3OH CH3OCH3+H2O
Above-mentioned reaction is all reversible reaction, and growing amount and the reaction temperature of ether-splitting solution conversion ratio and accessory substance have close relationship,
The equilibrium constant of main reaction can be increased by improving reaction temperature, improve the conversion ratio of ether, but also accelerate the hair of side reaction simultaneously
It is raw, in order to improve main reaction thing（Alkene and alcohol）Selectivity, suppress side reaction generation, if under relatively low reaction temperature
Cracking ether prepares alkene, and above-mentioned side reaction is with regard to that can be effectively suppressed, and some reactions even no longer occur, to ensure having high
Alkene and methanol selectivity, while the activity of catalyst is improved, to ensure having high ether-splitting solution conversion ratio and reaction velocity.
Therefore the purpose of the present invention is that there is provided one under the premise of the conversion ratio of the high methanol of guarantee and olefine selective and ether
Plant in the case where other process conditions are basically unchanged, reaction temperature can be reduced, the volume space velocity of ether is significantly improved, prepare letter
Catalyst single, with low cost and environmentally friendly.
Therefore, inventor is studied the catalyst required for course of reaction, in patent CN2015101231188 base
Novel load is proposed on plinth in the multicomponent NiO/ SiO of alumina support2 /F-/ SO4 2-/ Al2O3Type catalyst, is used for
Ether-splitting solution course of reaction, this catalyst is applicable not only to tert amyl methyl ether(TAME) cracking, is applied equally to methyl tertbutyl ether-splitting
Solution, while high conversion is reached, selectivity is also very high, reduces the generation of accessory substance, mitigates and reduces subsequent treatment
Cost, gives full play to the performance of each catalytic active component, and on the premise of catalyst activity is not influenceed, air speed is significantly improved,
The consumption of expensive active component is reduced, catalyst cost is reduced.
Multicomponent NiO/ SiO2 /F-/ SO4 2-/ Al2O3Type catalyst, its constituent mass degree is：
Al2O3 20~95%
NiO 0.1~50%
SiO2 0.1~20%
F- 0.1~20%
SO4 2- 0.5~35%
Described Al2O3For alundum (Al2O3), from hydrated alumina, γ-Al2O3In one kind；NiO is nickel oxide, is come
Come from one kind in the water soluble salt containing W metal, such as nickel nitrate, the aqueous solution of nickel sulfate；SiO2For silica, come
Come from containing Si element water soluble salts, such as potassium silicate, sodium metasilicate, one kind in the aqueous solution of ammonium fluosilicate；F-For halogen
Fluorine, from soluble fluoride, such as hydrofluoric acid, ammonium fluoride, one kind in the aqueous solution of sodium fluoride；SO4 2-For sulfate radical, come
Come from one kind in water soluble sulfate class, such as aqueous solution of sulfuric acid, ammonium sulfate, ammonium hydrogen sulfate.
The preparation of above-mentioned catalyst comprises the following steps：
By Al2O31 ~ 8 hour in the aqueous solution of the configured good salt containing W metal is immersed in, is filtered, in 80 ~ 180 DEG C
Dry 2 ~ 10 hours, be then calcined 2 ~ 10 hours in 300 ~ 800 DEG C, obtain NiO/ Al2O3；
By obtained NiO/ Al2O3It is added to configured good element containing Si and F-Solution in impregnate 1 ~ 8 hour, filtering,
Dry, be then calcined 2 ~ 8 hours in 200 ~ 800 DEG C, obtain SiO2/ F-/NiO/ Al2O3；
By obtained SiO2/ F-/NiO/ Al2O3It is added to containing SO4 2-The aqueous solution in, filter, dry, 200 ~ 800 DEG C roasting 2
~ 10 hours, that is, obtain the NiO/ SiO for preparing iso-amylene2/ F-/ SO4 2-/ Al2O3Type catalyst.
According to the present invention, the concentration of the water-soluble salt solution containing W metal is 0.01 ~ 50%, optimum scope is 1 ~
30%.The solution concentration of the element containing Si is 0.01 ~ 10%, and optimum concentration is 0.5 ~ 7%.F-The concentration of solution is 0.05 ~ 20%,
Optimum concentration is 1 ~ 15%, SO4 2-The concentration of salting liquid is 0.01 ~ 50%, and optimum concentration is 1 ~ 25%.In NiO solution
The amount of alundum (Al2O3) is 0.1 ~ 35g/ml；SiO2/ F-NiO/Al in solution2O3Amount be 0.1 ~ 35 g/ml；SO4 2-Salting liquid
Middle NiO/SiO2/ F-/ Al2O3Content is 0.1 ~ 35 g/ml.
With multicomponent NiO/ SiO2/ F-/ SO4 2-/ Al2O3When type catalyst cracking ether prepares olefine reaction, institute
The reaction temperature needed is generally 100 ~ 400 DEG C, and optimal reaction temperature is 120 ~ 220 DEG C.The flow velocity of ether, with unit volume per hour
The liquid feed volume of catalyst（Liquid air speed）Represent, generally 0.1 ~ 20h-1, optimal liquid air speed is 1 ~ 15 h-1。
From technical scheme disclosed above, the advantage of the invention is that catalyst is widely used, can be in relatively low temperature
(120 ~ 220 DEG C) progress ether cracking reactions under degree, alkene is converted close to complete；The selectivity of alkene is 100%, the selectivity of alcohol
For more than 99.5%.
Embodiment
The following examples further will be described to the present invention, but be in no way intended to limit the scope of the present invention.
Embodiment 1
By 40g γ-Al2O3It is added in the nickel nitrate solutions of 50ml 15% and stands 6h at room temperature, then filters, 120 DEG C of dryings
2h, is calcined 6h at 400 DEG C and obtains NiO/ Al2O3。
Then in the ammonium fluoride that the sodium silicate solution and concentration for being 5% in 40ml concentration by product are 20%, 4h, mistake are impregnated
After filter, 160 DEG C of dry 6h are calcined 4h at 400 DEG C and obtain NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the sulfuric acid solution that 50ml concentration is 20%, filtering, 100 DEG C are done
Dry 4h, 5h is calcined at 600 DEG C.Obtain the NiO/ SiO of the present invention2/ F- SO4 2- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, tert amyl methyl ether(TAME) is entered with micro-amounts of liquids
Sample pump is fed, and it is 1h-1 to control liquid air speed, and reaction temperature is 120 DEG C, TAME conversion ratios 95.5%, iso-amylene selectivity
96.8%, methanol selectivity 97.8%.2-methyl-1-butene alkene account for iso-amylene (2- methyl-2-butenes and 2-methyl-1-butene alkene it is mixed
Compound) ratio be 36%.
Embodiment 2
By 40g γ-Al2O3It is added in the nickel nitrate solutions of 50ml 20% and stands 4h at room temperature, then filters, 100 DEG C of dryings
2h, is calcined 6h at 600 DEG C and obtains NiO/ Al2O3。
Then in the etching acid that the potassium silicate solution and concentration for being 3% in 40ml concentration by product are 4%, 5h, filtering are impregnated
Afterwards, 120 DEG C of dry 8h, are calcined 4h at 300 DEG C and obtain NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the ammonium sulfate that 30ml concentration is 20%, filtering, 160 DEG C
3h is dried, 5h is calcined at 500 DEG C.Obtain the NiO/ SiO of the present invention2/ F-/ SO4 2- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, methyl tertiary butyl ether(MTBE) is entered with micro-amounts of liquids
Sample pump is fed, and it is 2h-1 to control liquid air speed, and reaction temperature is 140 DEG C, MTBE conversion ratios 97.6%, selective isobutene
97.8%, methanol selectivity 96.5%.
Embodiment 3
By 40g γ-Al2O3It is added in the nickel sulfate solutions of 50ml 30% and stands 6h at room temperature, then filters, 100 DEG C of dryings
2h, is calcined 6h at 700 DEG C and obtains NiO/ Al2O3。
Then by product in the ammonium fluosilicate solution that 40ml concentration is 10%, 6h is impregnated, after filtering, 120 DEG C of dry 2h,
6h, which is calcined, at 400 DEG C obtains NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the ammonium bisulfate solution that 50ml concentration is 20%, filtering, 100
DEG C dry 6h, 500 DEG C be calcined 5h.Obtain the NiO/ SiO of the present invention2/ F-/ SO4 2- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, tert amyl methyl ether(TAME) is entered with micro-amounts of liquids
Sample pump is fed, and it is 3h-1 to control liquid air speed, and reaction temperature is 160 DEG C, TAME conversion ratios 97.5%, iso-amylene selectivity
97.6%, methanol selectivity 98.7%.2-methyl-1-butene alkene account for iso-amylene (2- methyl-2-butenes and 2-methyl-1-butene alkene it is mixed
Compound) ratio be 21%.
Embodiment 4
By 40g γ-Al2O3It is added in the nickel chloride solutions of 50ml 40% and stands 6h at room temperature, then filters, 120 DEG C of dryings
6h, is calcined 6h at 600 DEG C and obtains NiO/ Al2O3。
Then in the sodium fluoride that the sodium silicate solution and concentration for being 7% in 40ml concentration by product are 9%, 4h, filtering are impregnated
Afterwards, 140 DEG C of dry 4h, are calcined 6h at 300 DEG C and obtain NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the sulfuric acid solution that 40ml concentration is 20%, filtering, 100 DEG C are done
Dry 2h, 5h is calcined at 300 DEG C.Obtain the NiO/ SiO of the present invention2/ F-/ SO4 2- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, methyl tertiary butyl ether(MTBE) is entered with micro-amounts of liquids
Sample pump is fed, and it is 4h-1 to control liquid air speed, and reaction temperature is 180 DEG C, MTBE conversion ratios 98.8%, selective isobutene
98.7%, methanol selectivity 98.4%.
Embodiment 5
By 40g γ-Al2O3It is added in the nickel chloride solutions of 50ml 40% and stands 3h at room temperature, then filters, 100 DEG C of dryings
4h, is calcined 6h at 500 DEG C and obtains NiO/ Al2O3。
Then by product in the potassium silicate and 4% potassium fluoride solution that 30ml concentration is 2%, 6h, after filtering, 100 DEG C are impregnated
4h is dried, being calcined 6h at 500 DEG C obtains NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the sulfuric acid solution that 40ml concentration is 25%, filtering, 100 DEG C are done
Dry 2h, 5h is calcined at 600 DEG C.Obtain the NiO/ SiO of the present invention2/ F-/ SO4 2- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, tert amyl methyl ether(TAME) is entered with micro-amounts of liquids
Sample pump is fed, and it is 5h-1 to control liquid air speed, and reaction temperature is 200 DEG C, TAME conversion ratios 98.5%, iso-amylene selectivity
97.5%, methanol selectivity 95.6%.2-methyl-1-butene alkene account for iso-amylene (2- methyl-2-butenes and 2-methyl-1-butene alkene it is mixed
Compound) ratio be 26%.
Embodiment 6
By 40g γ-Al2O3It is added in the nickel sulfate solutions of 50ml 15% and stands 6h at room temperature, then filters, 120 DEG C of dryings
4h, is calcined 6h at 600 DEG C and obtains NiO/ Al2O3。
Then by product in the potassium fluosilicate solution that 40ml concentration is 2%, 6h is impregnated, after filtering, 150 DEG C of dry 4h,
5h, which is calcined, at 400 DEG C obtains NiO/ SiO2/ F-/ Al2O3。
Again by NiO/ SiO2/ F-/ Al2O3It is added in the sulfuric acid solution that 50ml concentration is 20%, filtering, 100 DEG C are done
Dry 2h, 6h is calcined at 600 DEG C.Obtain the NiO/ SiO of the present invention2/ F-/SO42- / Al2O3。
In the micro fixed-bed reactor that 9g catalyst is fitted into φ 16mm diameters, methyl tertiary butyl ether(MTBE) is entered with micro-amounts of liquids
Sample pump is fed, and it is 6h-1 to control liquid air speed, and reaction temperature is 220 DEG C, MTBE conversion ratios 98.4%, selective isobutene
95.5%, methanol selectivity 97.4%.
Therefore, the catalyst that provides of the present invention is ensureing the ether conversion ratio close to 100% and the methanol close to 100% and different
Under the premise of amylene selectivity, with higher reaction velocity.As can be seen here, compared with current same type catalyst, the present invention is carried
The catalyst of confession is widely used, and is ensureing the ether conversion ratio close to 100% and the alcohol and olefine selective premise close to 100%
Under, with higher reaction velocity；This catalyst that simultaneously prepared by infusion process has simple to operate, free of contamination advantage；Activity
Component is cheap, reduces cost.
Claims (4)
1. a kind of be used to prepare the NiO/ SiO that ether-splitting solution prepares alkene2/ F-/ SO4 2-/ Al2O3Type catalyst, it is characterised in that
Component and percentage by weight are：
Al2O3 20~95%
NiO 0.1~50%
SiO2 0.1~20%
F- 0.1~20%
SO4 2- 0.5~35%
Wherein Al2O3For alundum (Al2O3), from hydrated alumina, γ-Al2O3In one kind；NiO is nickel oxide, is derived from
One kind in water soluble salt containing W metal, such as nickel nitrate, the aqueous solution of nickel sulfate；SiO2 For silica, derive from
Containing Si element water soluble salts, such as potassium silicate, sodium metasilicate, one kind in the aqueous solution of ammonium fluosilicate；F- For halogens fluorine, source
In soluble fluoride, such as hydrofluoric acid, ammonium fluoride, one kind in the aqueous solution of sodium fluoride；SO4 2-For sulfate radical, from water-soluble
One kind in property Sulfates, such as aqueous solution of sulfuric acid, ammonium sulfate, ammonium hydrogen sulfate.
2. the preparation method of catalyst according to claim 1, its feature is as follows：
By Al2O31 ~ 8 hour in the aqueous solution of the configured good salt containing W metal is immersed in, is filtered, in 80 ~ 180 DEG C of dryings
2 ~ 10 hours, then with 300 ~ 800 DEG C of 2 ~ 10 hours of roasting, obtain NiO/Al2O3；
Add it to configured good element containing Si and F-Solution in impregnate 1 ~ 8 hour, filter, dry, then in 200 ~
800 DEG C of 2 ~ 8 hours of roasting, obtain SiO2/ F-/NiO/Al2O3；
By obtained SiO2/ F-/NiO/Al2O3It is added to containing SO4 2-The aqueous solution in, filter, dry, 200 ~ 800 DEG C roasting 2 ~
10 hours, that is, obtain the NiO/ SiO for preparing iso-amylene2/ F-/SO4 2-/ Al2O3Type catalyst.
3. method for preparing catalyst according to claim 1, it is characterised in that the water-soluble salt solution containing W metal
Concentration be that the amount of alundum (Al2O3) in 0.01 ~ 50%, NiO solution is 0.1 ~ 35g/ml；The solution concentration of the element containing Si is 0.01
~ 10%, F-The concentration of solution is 0.05 ~ 20%, SiO2/ F-NiO/Al in solution2O3Amount be 0.1 ~ 35 g/ml；SO4 2-Salting liquid
Concentration be 0.01 ~ 50%, SO4 2-NiO/ SiO in salting liquid2/ F-/ Al2O3Amount be 0.1 ~ 35g/ml.
4. the application of the catalyst described in claim 1, is mainly used in ether-splitting solution and prepares olefine reaction, it is characterised in that reaction
Temperature is 100 ~ 400 DEG C, and liquid air speed is 0.1 ~ 20h-1；Optimum process condition is：120 ~ 220 DEG C, liquid air speed is 1 ~ 15 h-1。
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