CN105712822B - A kind of method by preparing ethylene by dehydrating ethanol - Google Patents
A kind of method by preparing ethylene by dehydrating ethanol Download PDFInfo
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Abstract
The invention discloses a kind of method by preparing ethylene by dehydrating ethanol.This method is catalyst A and catalyst B including at least two beds, and catalyst A compositions are as follows：Active component is heteropoly acid, and auxiliary agent is boron oxide, and carrier is the aluminum oxide of coated with silica, and catalyst B compositions are as follows：Active component is ammonium heteropoly acidses, and auxiliary agent is nickel oxide, and carrier is silica.The present invention is cooperated using above two catalyst, is given full play to respective advantage, is improved the combined reaction performance of reaction system, has higher activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of method by preparing ethylene by dehydrating ethanol, is used more particularly to one kind using combination catalyst
In the method for preparing ethylene by dehydrating ethanol.
Background technology
Ethene is as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products
It is prepared by raw material of ethene, therefore the size of ethylene yield has become one national oil development of chemical industry water of measurement
Flat important symbol.Traditional ethene mainly by light petroleum fraction crack made from, heavy dependence petroleum resources.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and it has been the task of top priority to develop new renewable alternative energy source.
Recently, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, and it has
Green, sustainable, reaction condition is gentle and many advantages such as product ethylene purity height.Bio-ethanol is mainly derived from agriculture
The fermentation of byproduct, the dependence to petroleum resources can be avoided, deficient in some petroleum resources such as Brazil, India, Pakistan
Country continues to use this method production ethene always, and this point more has realistic meaning to the country of oil-poor and few oil.Ethanol dehydration prepares second
Alkene, which has, partly or entirely replaces the great potential that ethene is obtained from oil.Therefore, research producing ethylene from dehydration of ethanol has great
Economic value and strategic importance.
Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..It is living
Property aluminum oxide is cheap as catalyst, and activity and selectivity is preferable, but reaction temperature is high, and reaction velocity is low, energy
Consumption is high, and utilization rate of equipment and installations is low.The catalytic activity and selectivity of molecular sieve are high, stable；Reaction temperature is low, and reaction velocity is big, but
Catalyst life is short, and multiplication factor is small, limits its industrialized production.Heteropoly acid is with one by central atom and coordination atom
The oxygen-containing polyacid that fixed structure is formed by oxygen atom ligand bridging, has the advantages that highly acid.In producing ethylene from dehydration of ethanol
In reaction, heteropolyacid catalyst has the characteristics of reaction temperature is low, selectivity height and high income.
[Chemical Engineering Technology and exploitation, 2010,5 (39) such as Li Benxiang:7-9] report entitled MCM-41 load silico-tungstic acid and urge
Change the article of producing ethylene from dehydration of ethanol, catalyst is prepared using infusion process.CN200910057539.X discloses a kind of ethanol and taken off
The catalyst of water ethene.For the catalyst using aluminum oxide as carrier, active component is heteropoly acid, is prepared using kneading method.It is above-mentioned
Catalyst shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but when using low-concentration ethanol as
During raw material, catalyst activity is decreased obviously, and stability is bad.
Producing ethylene from dehydration of ethanol is the endothermic reaction, and main reaction is that a molecules of ethanol catalytic reaction obtains a molecule ethene and one
Molecular water, with the progress of reaction, along reactor axis to dehydration content, which occurs, for the ethanol in raw material gradually reduces, water
Content gradually rises, and the larger temperature difference also occurs in catalyst bed interlayer, and the catalyst contact of bottom bed is containing big all the time
The low-concentration ethanol raw material of water is measured, and catalyst bottom bed temperature substantially reduces, and this can directly influence lower catalytic agent
Performance, cause the catalyst activity of reactor lower part substantially to reduce, so as to influence the activity of integer catalyzer, selectivity and steady
It is qualitative.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of method of preparing ethylene by dehydrating ethanol.
This method has the advantages that high ethanol conversion, selectivity and stability are good.
The method of preparing ethylene by dehydrating ethanol of the present invention, including at least two beds are catalyst A and catalyst
B, wherein ethanol raw material first contact with catalyst A, are then contacted again with catalyst B；
Catalyst A composition is as follows：Using alumina support, using heteropoly acid as active component, auxiliary agent is boron oxide, wherein
Alumina carrier surface coated silica, the weight of silica account for the carrying alumina body weight of coated with silica 5% ~
20%, preferably 8% ~ 18%, on the basis of the weight of catalyst, the content of heteropoly acid is 3% ~ 25%, preferably 5% ~ 20%, enters one
Step is preferably 10% ~ 18%, and using the content that oxide is counted as 2% ~ 8%, the content of the alumina support of coated with silica is auxiliary agent
67% ~ 95%, preferably 72% ~ 93%；
Catalyst B composition is as follows：
Active component is that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier is silica；With the weight of catalyst
On the basis of, the contents of ammonium heteropoly acidses is 8% ~ 35%, preferably 12% ~ 30%, more preferably 18% ~ 30%, and auxiliary agent is to aoxidize
The content of thing meter is 3% ~ 18%, preferably 5% ~ 15%, and the content of carrier is 47% ~ 89%, preferably 55% ~ 83%, further preferably
For 55% ~ 77%；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 0.5；When Y represents P
When, m+n=3, n values are 0.1 ~ 0.5.
The property of the silica support is as follows：Specific surface area is 500 ~ 820 m2/ g, pore volume are 0.62 ~ 0.92 mL/g,
Average pore diameter is 4.6 ~ 6.6 nm.
In catalyst A of the present invention, heteropoly acid is distributed on the alumina support of coated with silica in uniform type, i.e., miscellaneous more
Acid is evenly distributed on the surfaces externally and internally of the alumina support of coated with silica.In catalyst B of the present invention, heteropoly acid ammonium salinity
Cloth is distributed on silica support in eggshell type, that is to say, that and ammonium heteropoly acidses are distributed on the outer surface of silica support, and
There is no ammonium heteropoly acidses substantially in catalyst duct.
In the inventive method, the weight content of ammonium heteropoly acidses is not less than the weight of heteropoly acid in catalyst A in catalyst B
Content.
In the present invention, catalyst A preparation method, including：
I, alumina support is prepared；
II, the alumina support for preparing coated with silica；
III, carrier made from step II is added in the mixed solution of heteropoly acid and auxiliary agent presoma, 50 DEG C ~ 90
Stirring to solution is evaporated at DEG C；
IV, the solid for obtaining step III, in the h of 90 DEG C ~ 120 DEG C 5 h of drying ~ 12, then at 300 DEG C ~ 450 DEG C
The h of 2 h ~ 6 is calcined, produces catalyst A.
In step I, described alumina support be by boehmite through being molded, dry and roasting and obtain.Described plan
Boehmite can be made using conventional method, such as：Alchlor process, aluminum sulfate method, carbonizatin method etc..Described roasting condition：Roasting
It is 400 DEG C ~ 700 DEG C to burn temperature, and roasting time is the h of 2 h ~ 10.
In step II, the method for preparing the alumina support of coated with silica is as follows：By organic acid, dispersion aids and water
Mixing is made into mixed solution, and silicon source is added in mixed solution, after being well mixed, alumina support is added, at 50 DEG C ~ 90 DEG C
The h of 2 h of lower stirring ~ 6, then stirring is into gel at 50 DEG C ~ 90 DEG C, the h of the h of aging 5 ~ 12 at 20 DEG C ~ 50 DEG C, 90 DEG C ~
The h of 120 DEG C of 5 h of drying ~ 12, the h of 2 h ~ 6 is calcined at 300 DEG C ~ 600 DEG C, obtains the alumina support of coated with silica.It is described
Organic acid be one or more in citric acid, tartaric acid and malic acid, organic acid and mole of the silicon source in terms of silica
Than for 0.05 ~ 0.25；Dispersion aids is the one or more in the polyethylene glycol that molecular weight is 200 ~ 2000, polyethylene glycol and silicon
Source is using the mol ratio that silica is counted as 0.05 ~ 0.20.Silicon source is the one or more in tetraethyl orthosilicate, Ludox.Using
The silica particles that the above method can coat carrier surface are suitable and uniform, are uniformly dispersed.
In step III, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Auxiliary agent forerunner
Body is boric acid.
In the present invention, catalyst B preparation method, including：
（1）Auxiliary agent precursor water solution is added in silica support, stirring to solution is evaporated at 60 DEG C ~ 90 DEG C；
（2）By step（1）Then obtained solid is calcined 2 h in 90 DEG C ~ 120 DEG C dry 3h ~ 12h at 300 DEG C ~ 500 DEG C
~ 6 h, catalyst precarsor A is made；
（3）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（4）Polyhydric alcohol solutions are driven into autoclave, Hydrogen Vapor Pressure are then adjusted to 2~4MPa, at 200~300 DEG C
0.5~5.0h of lower reaction；
（5）By step（4）In reacted catalyst precarsor A filter out, at 20 DEG C ~ 50 DEG C, preferably 30 DEG C ~ 50 DEG C
Under be dried, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（6）By step（5）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, stirred at 60 DEG C ~ 90 DEG C to
Solution is evaporated, and obtains catalyst precarsor C；
（7）By step（6）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, filtered, 50 DEG C ~ 90
Dried at DEG C；Or by step（6）Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（8）The aqueous solution of heteropoly acid is added to step（7）In obtained catalyst precarsor D, stirred at 60 DEG C ~ 90 DEG C
It is evaporated to solution；
（9）By step（8）Then obtained solid is calcined 2 in the h of 90 DEG C ~ 120 DEG C dry 3h ~ 12 at 300 DEG C ~ 550 DEG C
The h of h ~ 6, produces catalyst.
Step（1）Described silica support is prepared with the following method：
A, template is added in the aqueous solution containing organic acid, obtains solution I；
B, silicon source is added in solution I, obtains solution II, then stirred at 60 DEG C ~ 90 DEG C extremely into gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ 24h, through drying, silica support is made.
In step A, the template is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecane
Base sodium sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be 1000 ~
One or more in 10000 polyethylene glycol, SiO in described template and carrier2Mol ratio be 0.01 ~ 1.2；It is described
Organic acid is citric acid, the one or more in tartaric acid, malic acid, SiO in described organic acid and carrier2Mol ratio be
0.1~1.2。
In step B, described silicon source is the one or more in tetraethyl orthosilicate, Ludox.
In step C, described silica support can be made the silica support of shaping or be not required to the oxygen of shaping
SiClx carrier, those skilled in the art determine according to selected technique.The silica support of shaping, it can use existing
Conventional molding techniques are molded, such as extruded moulding, compression molding etc., and shape can be bar shaped, spherical, sheet etc..It is being molded
During, binding agent and shaping assistant can be added as needed, and binding agent typically uses small porous aluminum oxide.Shaping assistant is such as
Peptizing agent, extrusion aid etc..After step C dryings, silica can be obtained through shaping or without shaping, then through high-temperature roasting
Carrier.
In step C, described drying and roasting are carried out using usual manner, and it is as follows to dry the condition typically used: 90℃
~ 120 DEG C of dry 3h ~ 12h, roasting are typically calcined the h of 2 h ~ 6 at 300 DEG C ~ 800 DEG C.
Step（1）In, described auxiliary agent presoma is soluble nickel salt, generally one kind in nickel nitrate, nickel acetate
It is or a variety of.
Step（3）In, described reduction treatment process is as follows：Under hydrogen atmosphere by catalyst precarsor be warming up to 300 DEG C~
600 DEG C, 4h~8h is handled under 0.1MPa~0.5MPa.Wherein reduction treatment can use pure hydrogen, can also use containing lazy
Property gas hydrogen, hydrogen volume concentration be 30% ~ 100%.
Step（4）In, described polyalcohol is the one or more in C5~C10 polyalcohols, preferably xylitol, sorb
One or more in alcohol, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%~30%.The addition of polyalcohol
Mass ratio with catalyst precarsor A is 3:1~10:1.
Step（6）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid
With SiO in carrier2Mol ratio be 0.05 ~ 0.50.
Step（7）In, by step（6）Obtained catalyst precarsor C, which is added in the alkaline solution containing ammonium, to be impregnated, leaching
The stain time is generally the min of 5 min ~ 30.By step（6）Obtained catalyst precarsor C absorption ammonias, adsorption time are generally 5
min~30 min.Step（7）In, the alkaline solution containing ammonium is one in ammoniacal liquor, sal volatile, ammonium bicarbonate soln
Kind is a variety of.
Step（7）In, described ammonia can use pure ammonia, can also use the gaseous mixture containing ammonia, in mixed gas
In addition to ammonia, other is the one or more in inert gas such as nitrogen, argon gas.
Step（8）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
It can also be added in described silica support in mesopore molecular sieve, such as SBA-15, SBA-3, MCM-41 etc.
One or more, the weight content of molecular sieve in the carrier is below 10%, and generally 1% ~ 8%.Mesopore molecular sieve can aoxidize
Introduce, can also be introduced during plastic before silicon plastic, can also be introduced after silica plastic, can be with silica support
Kneading introduces in forming process.
Described catalyst A and catalyst B admission space ratio are 4:1 ~1:4.
The method of preparing ethylene by dehydrating ethanol of the present invention is as follows using fixed-bed process, reaction condition：Mass space velocity 0.5
h-1~15.0 h-1, 260 DEG C ~ 400 DEG C of reaction temperature.
Compared with prior art, the present invention has advantages below：
In the inventive method, the catalyst B of use is ethylene reaction produced especially suitable for low-concentration ethanol raw material dehydration, and
And low temperature active is high, catalyst A downstream is seated in, can be obviously improved bed temperature reduces and water content increasing in raw material
Add the negative effect brought to catalyst system, catalyst A and catalyst B is cooperated and give full play to respective advantage, make
While catalyst integrally has higher activity, selectivity and coking resistivity, the stability of catalyst, Ke Yiyan are improved
The service life of long catalyst, the combined reaction performance of reaction system is improved, there is higher product yield.
Embodiment
With reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
1st, catalyst preparation：
It is prepared by catalyst A
（1）The preparation of carrier：
4.8g citric acids and 15.0g Macrogol 600s are added in deionized water, mixed solution is made into, then adds
37.8mL tetraethyl orthosilicates, after stirring, it is added in the aluminum oxide through compression molding prepared, 2 is stirred at 60 DEG C
H, then stirring into gel, the h of aging 8 at 40 DEG C, then in 110 DEG C of dry 8 h, 3 is calcined at 550 DEG C at 80 DEG C
H, obtains the alumina support of coated with silica, and wherein silica accounts for the 12% of vehicle weight, mole of citric acid and silica
Than for 0.15, the mol ratio of Macrogol 600 and silica is 0.15.
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
8.9g boric acid and 12.5g phosphotungstic acids are added in deionized water, are configured to mixed solution；The carrier that will be prepared
It is added in mixed solution, stirring to solution is evaporated at 60 DEG C；Then obtained solid is dried into 8 h at 110 DEG C,
3 h are calcined at 350 DEG C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 5wt%, H3PW12O40Content
For 12wt%, SiO2Content is the 12wt% of the alumina support of coated with silica.
It is prepared by catalyst B
（1）The preparation of carrier：
Weigh 145.8g cetyl trimethylammonium bromides and 205g citric acids are made into mixed solution, by the positive silicic acid of 302mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely into gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, 8 h are then dried at 110 DEG C, through compression molding, be calcined 3 h at 580 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Than
Surface area is 525 m2/ g, pore volume are 0.64 mL/g, and average pore diameter is 4.9 nm.
（2）The preparation of catalyst：
27.2 g nickel nitrates are dissolved in deionized water, are added in 81g silica supports, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of drys 8.0 h, 3.0 h are then calcined at 400 DEG C, obtained catalyst precarsor A, are then added
Into autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds 400g
Mass concentration is 20% sorbitol solution, then regulation Hydrogen Vapor Pressure to 3MPa, and 3h is reacted at 260 DEG C, after reaction terminates,
Catalyst filtration is come out, dried at 40 DEG C to carrier surface without liquid phase；It is then added to containing the water-soluble of 38.9g citric acids
In liquid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, 60 after filtering
Dried at DEG C；It is then added in the aqueous solution containing 12.4g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By what is obtained
Then solid is calcined 3.0 h in 110 DEG C of dry 8.0 h at 500 DEG C, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst,
Wherein NiO contents are 7wt%, (NH4)0.5H2.5PW12O40Content is 12wt%.
2nd, the evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 95wt% ethanol waters, first with being catalyzed
Agent A is contacted, and is then contacted again with catalyst B, and wherein catalyst A and catalyst B admission space ratio is 3:1, totally 20 mL, matter
Measure air speed 3h-1, 360 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, are then down to reaction
After temperature starts reaction 200 hours, product is analyzed by gas-chromatography, calculates ethanol conversion and ethylene selectivity, as a result
It is shown in Table 1.
Embodiment 2
Catalyst A and B admission space ratio are 1 in selection example 1:1, mass space velocity 4h-1, 360 DEG C of reaction temperature, its
Its appreciation condition is constant, and ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 3
Catalyst A preparation：
（1）The preparation of carrier：
7.4g citric acids and 13.9g polyethylene glycol 400s are added in deionized water, mixed solution is made into, then adds
43.8mL tetraethyl orthosilicates, after stirring, it is added in the aluminum oxide through compression molding prepared, 2 is stirred at 60 DEG C
H, then stirring into gel, the aging 8h at 40 DEG C, then in 110 DEG C of dry 8 h, 3 is calcined at 550 DEG C at 80 DEG C
H, obtains the alumina support of coated with silica, and wherein silica accounts for the 15% of vehicle weight, mole of citric acid and silica
Than for 0.2, the mol ratio of polyethylene glycol 400 and silica is 0.18.
（2）The preparation of catalyst：Catalyst is prepared using supersaturated infusion process, and step is as follows：
10.6g boric acid and 15.6g phosphotungstic acids are added in deionized water, are configured to mixed solution；The load that will be prepared
Body is added in mixed solution, 60oStirring to solution is evaporated under C；Then by obtained solid 110o8 h are dried under C,
350o3 h are calcined under C, H is made3PW12O40-B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 6wt%, H3PW12O40
Content is 15wt%, SiO2Content is the 15wt% of the alumina support of coated with silica.
Catalyst B preparation：
（1）The preparation of carrier：
Weigh 200g cetyl trimethylammonium bromides and 105.7g citric acids are made into mixed solution, by the positive silicic acid of 250mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely into gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, 8 h are then dried at 110 DEG C, through compression molding, be calcined 3 h at 600 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Than
Surface area is 570 m2/ g, pore volume are 0.72 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
35.0 g nickel nitrates are dissolved in deionized water, are added in 73g silica supports, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of drys 8.0 h, 3.0 h are then calcined at 400 DEG C, obtained catalyst precarsor A, are then added
Into autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds 400g
Mass concentration is 20% sorbitol solution, then regulation Hydrogen Vapor Pressure to 3MPa, and 2h is reacted at 300 DEG C, after reaction terminates,
Catalyst filtration is come out, dried at 40 DEG C to carrier surface without liquid phase；It is then added to containing the water-soluble of 58.4g citric acids
In liquid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, 60 after filtering
Dried at DEG C；It is then added in the aqueous solution containing 18.7g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By what is obtained
Then solid is calcined 3.0 h in 110 DEG C of dry 8.0 h at 500 DEG C, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst,
Wherein NiO contents are 9wt%, (NH4)0.5H2.5PW12O40Content is 18wt%.
Catalyst A and B admission space ratio are 1:2, mass space velocity 6h-1, 350 DEG C of reaction temperature, other appreciation conditions are not
Become, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 4
In embodiment 1, phosphotungstic acid is changed to silico-tungstic acid, with embodiment 1, gained catalyst A is H for remaining4SiW12O40-
B2O3/Al2O3-SiO2Catalyst, wherein B2O3Content is 5wt%, H4SiW12O40Content is 10wt%.Catalyst B is (NH4)0.5H3.5SiW12O40-NiO/SiO2Catalyst, wherein NiO contents are 7wt%, (NH4)0.5H3.5SiW12O40Content is 12wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Comparative example 1
Catalyst A in embodiment 1 is used alone, the evaluation of catalyst is the same as embodiment 1, ethanol conversion and ethylene selectivity
It the results are shown in Table 1.
The evaluation result of 1 each example of table
Claims (8)
1. a kind of method of preparing ethylene by dehydrating ethanol, including at least two beds are catalyst A and catalyst B, its
Middle ethanol raw material first contacts with catalyst A, is then contacted again with catalyst B；
Catalyst A composition is as follows：Active component is heteropoly acid, and auxiliary agent is boron oxide, wherein alumina carrier surface cladding two
Silica, the weight of silica account for the 5% ~ 20% of the carrying alumina body weight of coated with silica, using the weight of catalyst as
Benchmark, the content of heteropoly acid are 3% ~ 25%, and auxiliary agent is using the content that oxide is counted as the % of 2 % ~ 8, the aluminum oxide of coated with silica
The content of carrier is the % of 67 % ~ 95；The weight of silica accounts for the alumina support of coated with silica in described catalyst A
The 8% ~ 18% of weight；Described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；
Catalyst B composition is as follows：
Active component is that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier is silica；Using the weight of catalyst as base
Standard, the content of ammonium heteropoly acidses is 8% ~ 35%, and for auxiliary agent using the content that oxide is counted as 3% ~ 18%, the content of carrier is 47% ~ 89%；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 0.5；When Y represents P, m
+ n=3, n value are 0.1 ~ 0.5；
In described catalyst B, the property of silica support is as follows：Specific surface area is 500 ~ 820 m2/ g, pore volume be 0.62 ~
0.92 mL/g, average pore diameter are 4.6 ~ 6.6 nm；
In described catalyst A, heteropoly acid is distributed on the alumina support of coated with silica in uniform type, described catalysis
In agent B, ammonium heteropoly acidses are distributed on silica support to be distributed in eggshell type.
2. in accordance with the method for claim 1, it is characterised in that：Described catalyst A, on the basis of the weight of catalyst,
The content of heteropoly acid is 5% ~ 20%, and using the content that oxide is counted as 2% ~ 8%, the alumina support of coated with silica contains auxiliary agent
Measure as 72% ~ 93%.
3. in accordance with the method for claim 1, it is characterised in that：Described catalyst B, on the basis of the weight of catalyst,
The content of ammonium heteropoly acidses is 12% ~ 30%, and for auxiliary agent using the content that oxide is counted as 5% ~ 15%, the content of carrier is 55% ~ 83%.
4. in accordance with the method for claim 1, it is characterised in that：Described catalyst B, on the basis of the weight of catalyst,
The content of ammonium heteropoly acidses is 18% ~ 30%, and for auxiliary agent using the content that oxide is counted as 5% ~ 15%, the content of carrier is 55% ~ 77%.
5. according to any described method of claim 1 ~ 4, it is characterised in that：The weight content of ammonium heteropoly acidses in catalyst B
Not less than the weight content of heteropoly acid in catalyst A.
6. in accordance with the method for claim 1, it is characterised in that：In described catalyst B, added in silica support mesoporous
One or more in molecular sieve SBA-15, SBA-3, MCM-41, the weight content of molecular sieve in the carrier is below 10%.
7. in accordance with the method for claim 1, it is characterised in that：Described catalyst A and catalyst B admission space ratio are
4:1~1:4。
8. in accordance with the method for claim 1, it is characterised in that：Using fixed-bed process, preparing ethylene by dehydrating ethanol it is anti-
Answer condition as follows：Mass space velocity 0.5h-1~15.0 h-1, 260 DEG C ~ 400 DEG C of reaction temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410713674.6A CN105712822B (en) | 2014-12-02 | 2014-12-02 | A kind of method by preparing ethylene by dehydrating ethanol |
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| CN101687724A (en) * | 2007-05-11 | 2010-03-31 | 英尼奥斯欧洲有限公司 | Dehydration of alcohols over tungstosilicic acid supported on silica |
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| CN104588102A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method of catalyst used for producing dimethyl ether through methanol dehydration |
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| EP1982761A1 (en) * | 2006-11-22 | 2008-10-22 | BP Chemicals Limited | Supported heteropolyacid catalysts |
| CN101687724A (en) * | 2007-05-11 | 2010-03-31 | 英尼奥斯欧洲有限公司 | Dehydration of alcohols over tungstosilicic acid supported on silica |
| CN101940938A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Heteropolyacid modified alumina ethanol dehydration catalyst and preparation method thereof |
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