CN105712824A - Method for preparation of ethylene by ethanol dehydration - Google Patents
Method for preparation of ethylene by ethanol dehydration Download PDFInfo
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Abstract
The invention discloses a method for preparation of ethylene by ethanol dehydration. The method involves at least two catalyst beds, i.e. a catalyst A and a catalyst B. The catalyst A is composed of: an active component heteropoly acid ammonium salt, an assistant boron oxide, and a carrier alumina, and the catalyst B consists of: an active component heteropoly acid ammonium salt, an assistant nickel oxide, and a carrier silicon oxide. According to the invention, the two catalysts are employed for mutual cooperation to give full play to respective advantages, so that the reaction system has improved comprehensive reaction performance, and has higher activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of by the method for producing ethylene from dehydration of ethanol, particularly relate to a kind of use combination catalyst for the method for producing ethylene from dehydration of ethanol.
Background technology
Ethylene is as the flagship product of basic Organic Chemicals and petro chemical industry, and the chemical products of about 75% prepare with ethylene for raw material, and therefore the size of ethylene yield has become as the important symbol weighing a national oil development of chemical industry level.Traditional ethylene obtains mainly by light petroleum fraction cracking, heavy dependence petroleum resources.Along with the day of international energy situation is becoming tight, petroleum resources are increasingly exhausted, and developing new renewable alternative energy source has been the task of top priority.
Many-sided advantages such as recently, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly subject to people's attention, and it has green, sustainable, reaction condition is gentle and product ethylene purity is high.Bio-ethanol is mainly derived from the fermentation of agricultural byproducts, can avoid the dependence to petroleum resources, continues to use this method in the country that some petroleum resources such as Brazil, India, Pakistan are deficient always and produces ethylene, and more there is realistic meaning in the country of oil-poor and few oil by this point.Preparing ethylene by dehydrating ethanol has the great potential partly or entirely replacing obtaining ethylene from oil.Therefore, research producing ethylene from dehydration of ethanol has great economic worth and strategic importance.
Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..Activated alumina is as catalyst low price, and activity and selectivity is better, but reaction temperature is high, and reaction velocity is low, and energy consumption is high, and utilization rate of equipment and installations is low.The catalysis activity and selectivity of molecular sieve is high, stable；Reaction temperature is low, and reaction velocity is big, but catalyst life is short, and amplification is little, limits its industrialized production.Heteropoly acid is with certain structure oxygen-containing polyprotic acid by oxygen atom ligand bridging by central atom and coordination atom, has the advantages such as highly acid.In producing ethylene from dehydration of ethanol reacts, it is low that heteropolyacid catalyst has reaction temperature, the feature that selectivity is high and yield is high.
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] report the article being entitled as MCM-41 load Catalyzed by Silicotungstic Acid producing ethylene from dehydration of ethanol, and catalyst adopts infusion process to prepare.CN200910057539.X discloses the catalyst of a kind of producing ethylene from dehydration of ethanol.This catalyst is with aluminium oxide for carrier, and active component is heteropoly acid, adopts kneading method to prepare.Above-mentioned catalyst, when with high concentration ethanol for raw material, shows higher catalysis activity and selectivity, but when with low-concentration ethanol for raw material, catalyst activity is decreased obviously, and stability is bad.
Producing ethylene from dehydration of ethanol is the endothermic reaction, primary response is that a part alcohol catalysis is obtained by reacting a part ethylene and a part water, carrying out along with reaction, axial along reactor, ethanol generation dehydration content in raw material is gradually lowered, the content of water gradually rises, catalyst bed interlayer also there will be the bigger temperature difference, the catalyst contact of bottom bed is the low-concentration ethanol raw material containing a large amount of water all the time, and catalyst bottom bed temperature substantially reduces, this can directly influence the performance of lower catalytic agent, the catalyst activity causing reactor lower part substantially reduces, thus affecting the activity of integer catalyzer, selectivity and stability.
Summary of the invention
In order to overcome weak point of the prior art, a kind of method that the invention provides producing ethylene from dehydration of ethanol.When the method is for producing ethylene from dehydration of ethanol, there is the advantages such as ethanol conversion height, selectivity and good stability.
The method of producing ethylene from dehydration of ethanol of the present invention, including two beds and catalyst A and catalyst B, wherein ethanol raw material first contacts with catalyst A, then contacts with catalyst B again；
Catalyst A's is composed as follows: catalyst A includes active component, auxiliary agent and carrier, and active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is boron oxide, and carrier is aluminium oxide；With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 3% ~ 25%, it is preferably 8% ~ 20%, more preferably 12% ~ 20%, much further preferably from 15% ~ 20%, the content that auxiliary agent is counted with oxide is for 2% ~ 5%, the content of aluminium oxide is 70% ~ 95%, it is preferably 75% ~ 90%, more preferably 75% ~ 86%, much further preferably from 75% ~ 83%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, Y and represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P, m+n=3, n value is 0.1 ~ 1.0.
Catalyst B's is composed as follows:
Catalyst B includes active component, auxiliary agent and carrier, and active component is that ammonium heteropoly acids is shown in formula (2), and auxiliary agent is nickel oxide, and carrier is silicon oxide；With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 8% ~ 35%, it is preferred to 12% ~ 30%, more preferably 18% ~ 30%, the content that auxiliary agent is counted with oxide is for 3% ~ 18%, it is preferred to 5% ~ 15%, the content of carrier is 47% ~ 89%, it is preferred to 55% ~ 83%, more preferably 55% ~ 77%；
Hu(NH4)vAB12O40(2)
Wherein A represents W or Mo, B and represents Si or P；When B represents Si, u+v=4, v value is 0.1 ~ 1.0；When B represents P, u+v=3, v value is 0.1 ~ 1.0.
The character of described silica support is as follows: specific surface area is 500 ~ 820m2/ g, pore volume is 0.62 ~ 0.92mL/g, and average pore diameter is 4.6 ~ 6.6nm.
In described catalyst A, ammonium heteropoly acids is the distribution of uniform type on the alumina support, namely ammonium heteropoly acids is evenly distributed on the surfaces externally and internally of alumina support, in described catalyst B, ammonium heteropoly acids is distributed for eggshell type on silica support, namely ammonium heteropoly acids is distributed in the outer surface of silica support, and is substantially free of ammonium heteropoly acids in catalyst duct.
In the present invention, in described catalyst B, the weight content of ammonium heteropoly acids is not less than in catalyst A the weight content of ammonium heteropoly acids.
In the present invention, the preparation method of catalyst A, including:
I, the presoma of auxiliary agent is joined containing in organic aqueous acid, obtain solution A；
II, alumina support is joined in solution A, stir at 50 DEG C ~ 80 DEG C to solution and be evaporated；
III, the solid obtained by step II join in the alkaline solution containing ammonium and impregnate, and then filter, dry at 50 DEG C ~ 90 DEG C, or the solid obtained by step II adsorbs ammonia at 50 DEG C ~ 90 DEG C；
IV, the solid obtained by step III, join in the aqueous solution of heteropoly acid, stirs to solution and be evaporated at 50 DEG C ~ 80 DEG C；
V, the solid that step IV is obtained, drying, then at 300 DEG C ~ 550 DEG C roasting 2h ~ 6h, obtain catalyst A.
In step I, described auxiliary agent presoma is boric acid；Described organic acid can be one or more in citric acid, tartaric acid, malic acid, and in alumina support used by described organic acid and step II, the mol ratio of aluminium oxide is 0.05 ~ 0.50.
In step II, described alumina support is to be obtained through molding, dry and roasting by boehmite.Described boehmite can adopt conventional method to prepare, such as: Alchlor process, aluminum sulfate method, carbonizatin method etc..Described roasting condition: sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2h ~ 10h.
In step III, the solid obtained by step II joins in the alkaline solution containing ammonia and impregnates, and dip time is generally 5min ~ 30min.The solid absorption ammonia obtained by step II, adsorption time is generally 5min ~ 30min.
In step III, the described alkaline solution containing ammonium is one or more in ammonia, sal volatile, ammonium bicarbonate soln.
In step III, described ammonia can adopt pure ammonia, it would however also be possible to employ the gaseous mixture containing ammonia, and in mixing gas except ammonia, other is one or more in noble gas such as nitrogen, argon etc..
In step IV, described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step IV, the solid that step III is obtained, join in the aqueous solution of heteropoly acid and impregnate, dip time is generally 5min ~ 30min.
In step V, described drying condition is as follows: 90 DEG C ~ 120 DEG C dry 5h ~ 12h.
In the present invention, the preparation method of catalyst B, including:
(1) auxiliary agent precursor water solution is joined in silica support, stir at 60 DEG C ~ 90 DEG C to solution and be evaporated；
(2) solid step (1) obtained is at 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then at 300 DEG C ~ 500 DEG C roasting 2h ~ 6h, prepares catalyst precarsor A；
(3) catalyst precarsor A is joined in autoclave, adopt hydrogen that it is carried out reduction treatment；
(4) polyhydric alcohol solutions is driven in autoclave, then regulates Hydrogen Vapor Pressure to 2～4MPa, at 200～300 DEG C, react 0.5～5.0h；
(5) catalyst precarsor A reacted in step (4) is filtered out, at 20 DEG C ~ 50 DEG C, it is preferred to be dried at 30 DEG C ~ 50 DEG C, until sample surfaces is without liquid phase, obtain catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is joined in aqueous solutions of organic acids, stir at 60 DEG C ~ 90 DEG C and be evaporated to solution, obtain catalyst precarsor C；
(7) the catalyst precarsor C that step (6) obtains is joined in the alkaline solution containing ammonium, through filtering, dry at 50 DEG C ~ 90 DEG C；Or material step (6) obtained adsorbs ammonia at 50 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
(8) aqueous solution of heteropoly acid is joined in the catalyst precarsor D that step (7) obtains, stir at 60 DEG C ~ 90 DEG C to solution and be evaporated；
(9) solid step (8) obtained is at 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then at 300 DEG C ~ 550 DEG C roasting 2h ~ 6h, obtains catalyst.
Silica support described in step (1) is adopted and is prepared with the following method:
A, template is joined containing in organic acid aqueous solution, obtain solution I；
B, silicon source is joined in solution I, obtain solution II, then stir to becoming gel at 60 DEG C ~ 90 DEG C；
C, by gel aging 8h ~ 24h, drying at 20 DEG C ~ 50 DEG C, make silica support.
In step A, described template is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, sodium lauryl sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be 1000 ~ 10000 Polyethylene Glycol in one or more, described template and SiO in carrier2Mol ratio be 0.01 ~ 1.2；Described organic acid is one or more in citric acid, tartaric acid, malic acid, SiO in described organic acid and carrier2Mol ratio be 0.1 ~ 1.2.
In step B, described silicon source is one or more in tetraethyl orthosilicate, Ludox.
In step C, described silica support can make the silica support of molding, it is also possible to being the silica support not needing molding, those skilled in the art determine according to selected technique.The silica support of molding, it is possible to adopt existing conventional molding techniques to carry out molding, such as extruded moulding, compression molding etc., shape can be bar shaped, spherical, lamellar etc..In forming process, it is possible to adding binding agent and shaping assistant as required, binding agent is generally adopted little porous aluminum oxide.Shaping assistant is peptizer, extrusion aid etc. such as.After step C dries, it is possible to through molding or without molding, obtain silica support then through high-temperature roasting.
In step C, described dry and roasting adopts usual manner to carry out, and the dry condition being generally adopted is as follows: 90 DEG C ~ 120 DEG C dry 3h ~ 12h, roasting is typically in 300 DEG C ~ 800 DEG C roasting 2h ~ 6h.
In step (1), the described nickel salt that auxiliary agent presoma is solubility, be generally in nickel nitrate, nickel acetate one or more.
In step (3), described reduction treatment process is as follows: catalyst precarsor is warming up under hydrogen atmosphere 300 DEG C～600 DEG C, processes 4h～8h under 0.1MPa～0.5MPa.Wherein reduction treatment can adopt pure hydrogen, it would however also be possible to employ the hydrogen containing noble gas, and hydrogen volume concentration is 30% ~ 100%.
In step (4), described polyhydric alcohol is one or more in C5～C10 polyhydric alcohol, it is preferable that one or more in xylitol, sorbitol, mannitol, arabitol；The mass concentration of polyhydric alcohol solutions is 5%～30%.The mass ratio of the addition of polyhydric alcohol and catalyst precarsor A is 3:1 ~ 10:1.
In step (6), described organic acid is one or more in citric acid, tartaric acid, malic acid.Described organic acid and SiO in carrier2Mol ratio be 0.05 ~ 0.50.
In step (7), being joined in the alkaline solution containing ammonium by the catalyst precarsor C that step (6) obtains and impregnate, dip time is generally 5min ~ 30min.Catalyst precarsor C step (6) obtained adsorbs ammonia, and adsorption time is generally 5min ~ 30min.In step (7), the described alkaline solution containing ammonium is one or more in ammonia, sal volatile, ammonium bicarbonate soln.
In step (7), described ammonia can adopt pure ammonia, it would however also be possible to employ the gaseous mixture containing ammonia, and in mixing gas except ammonia, other is one or more in noble gas such as nitrogen, argon etc..
In step (8), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Can also adding mesopore molecular sieve, one or more in such as SBA-15, SBA-3, MCM-41 etc. in described silica support, molecular sieve weight content in the carrier, below 10%, is generally 1% ~ 8%.Mesopore molecular sieve can introduce before silicon oxide plastic, it is also possible to introduces in plastic process, it is also possible to introduces after silicon oxide plastic, it is also possible in silica support forming process, kneading introduces.
Described catalyst A and the admission space of catalyst B are than for 4:1 ~ 1:4.
The method of producing ethylene by ethanol dehydration of the present invention, adopts fixed-bed process, and its reaction condition is as follows: mass space velocity 0.5h-1~10.0h-1, reaction temperature 280 DEG C ~ 400 DEG C.
Compared with prior art, the invention have the advantages that
In the inventive method, the catalyst B adopted, there is the advantage that low temperature active is high in low-concentration ethanol raw material dehydration is ethylene reaction produced, it is seated in the downstream of catalyst A, bed temperature can be obviously improved and reduce the negative effect that catalyst system is brought, make catalyst A and catalyst B cooperate and give full play to respective advantage, catalyst entirety is made to have higher activity, while selectivity and coking resistivity, improve the stability of catalyst, the service life of catalyst can be extended, the combined reaction performance making reaction system improves, there is higher product yield.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
1, catalyst is prepared
Prepared by catalyst A
Weigh 7.1g boric acid and 31.7g citric acid joins in deionized water, be made into mixed solution；84g is joined in mixed solution through the alumina support of compression molding, stirs at 70 DEG C to solution and be evaporated, wherein citric acid and Al2O3Mol ratio be 0.2；Gained solid is put into dipping 10min in sal volatile, dry at 70 DEG C after filtration；Being joined by gained solid in the aqueous solution containing 12.5g phosphotungstic acid, stir and be evaporated to solution at 70 DEG C, at 110 DEG C, dry 8h, roasting 3h at 470 DEG C, prepare (NH4)0.5H2.5PW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 4wt%, (NH4)0.5H2.5PW12O40Content is 12wt%.
Prepared by catalyst B
(1) preparation of carrier:
Weigh 200g cetyl trimethylammonium bromide and 105.7g citric acid is made into mixed solution, 250mL tetraethyl orthosilicate is joined in mixed solution, stirring 2h, then stirs to becoming gel, by gel aging 12h at 40 DEG C at 70 DEG C, then dry 8h at 110 DEG C, through compression molding, at 600 DEG C of roasting 3h, obtain silica support, wherein cetyl trimethylammonium bromide is 0.5 with the mol ratio of silicon oxide, and the mol ratio of citric acid and silicon oxide is 0.5.Support is: specific surface area is 570m2/ g, pore volume is 0.72mL/g, and average pore diameter is 5.1nm.
(2) preparation of catalyst:
35.0g nickel nitrate is dissolved in deionized water, join in 73g silica support, stir at 70 DEG C to solution and be evaporated, by the solid that obtains at 110 DEG C of dry 8.0h, then at 400 DEG C of roasting 3.0h, prepare catalyst precarsor A, it is then added in autoclave, 450 DEG C it are warming up under hydrogen atmosphere, 4h is processed under 0.3MPa, it is down to reaction temperature, adding 400g mass concentration is the sorbitol solution of 20%, then Hydrogen Vapor Pressure is regulated to 3MPa, 2h is reacted at 300 DEG C, after reaction terminates, by catalyst filtration out, carrier surface it is dried to without liquid phase at 40 DEG C；It is then added to containing in 58.4g Fructus Citri Limoniae aqueous acid, stirs at 70 DEG C to solution and be evaporated；The material obtained joins dipping 10min in sal volatile, dry at 60 DEG C after filtration；It is then added in the aqueous solution containing 18.7g phosphotungstic acid, stirs at 70 DEG C to solution and be evaporated；By the solid that obtains at 110 DEG C of dry 8.0h, then at 500 DEG C of roasting 3.0h, prepare (NH4)0.5H2.5PW12O40-NiO/SiO2Catalyst, wherein NiO content is 9wt%, (NH4)0.5H2.5PW12O40Content is 18wt%.
2, the evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol water, first contacts with catalyst A, then contacts with catalyst B again, and wherein the admission space of catalyst A and catalyst B ratio is for 3:1, common 20mL, mass space velocity 5h-1, reaction temperature 330 DEG C.Before reaction, catalyst is at N2Activating 2h in 400 DEG C under protection, be then down to after reaction temperature starts to react 200 hours, product is analyzed by gas chromatogram, calculates ethanol conversion and ethylene selectivity, and result is in Table 1.
Embodiment 2
Select in embodiment 1 catalyst A and B admission space ratio for 1:1, mass space velocity 5h-1, reaction temperature 320 DEG C, other appreciation condition is constant, and ethanol conversion and ethylene selectivity result are in Table 1.
Embodiment 3
The preparation of catalyst A:
Weigh 8.9g boric acid and 45.2g citric acid joins in deionized water, be made into mixed solution；80g is joined in mixed solution through compression molding alumina support, stirs at 70 DEG C to solution and be evaporated, wherein citric acid and Al2O3Mol ratio be 0.3；Gained solid is put into dipping 10min in sal volatile, dry at 70 DEG C after filtration；Being joined by gained solid in the aqueous solution containing 15.6g phosphotungstic acid, stir and be evaporated to solution at 70 DEG C, at 110 DEG C, dry 8h, roasting 3h at 500 DEG C, prepare (NH4)0.1H2.9PW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 5wt%, (NH4)0.1H2.9PW12O40Content is 15wt%.
The preparation of catalyst B:
(1) preparation of carrier:
Weigh 316g cetyl trimethylammonium bromide and 62.4g citric acid is made into mixed solution, 246mL tetraethyl orthosilicate is joined in mixed solution, stirring 2h, then stirs to becoming gel, by gel aging 12h at 40 DEG C at 70 DEG C, then dry 8h at 110 DEG C, through compression molding, at 600 DEG C of roasting 3h, obtain silica support, wherein cetyl trimethylammonium bromide is 0.8 with the mol ratio of silicon oxide, and the mol ratio of citric acid and silicon oxide is 0.3.Support is: specific surface area is 630m2/ g, pore volume is 0.81mL/g, and average pore diameter is 5.1nm.
(2) preparation of catalyst:
46.7g nickel nitrate is dissolved in deionized water, join in 63g silica support, stir at 70 DEG C to solution and be evaporated, by the solid that obtains at 110 DEG C of dry 8.0h, then at 400 DEG C of roasting 3.0h, prepare catalyst precarsor A, it is then added in autoclave, 450 DEG C it are warming up under hydrogen atmosphere, 4h is processed under 0.3MPa, it is down to reaction temperature, adding 400g mass concentration is the sorbitol solution of 20%, then Hydrogen Vapor Pressure is regulated to 3MPa, 2h is reacted at 300 DEG C, after reaction terminates, by catalyst filtration out, carrier surface it is dried to without liquid phase at 40 DEG C；It is then added to containing in 70.6g Fructus Citri Limoniae aqueous acid, stirs at 70 DEG C to solution and be evaporated；The material obtained joins dipping 10min in sal volatile, dry at 60 DEG C after filtration；It is then added in the aqueous solution containing 25.9g phosphotungstic acid, stirs at 70 DEG C to solution and be evaporated；By the solid that obtains at 110 DEG C of dry 8.0h, then at 520 DEG C of roasting 3.0h, prepare (NH4)0.2H2.8PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
Catalyst A and B admission space are than for 1:2, mass space velocity 8h-1, reaction temperature 310 DEG C, other appreciation condition is constant, and ethanol conversion and ethylene selectivity result are in Table 1.
Embodiment 4
In embodiment 1, changing phosphotungstic acid into silico-tungstic acid, all the other are with embodiment 1, and gained catalyst A is (NH4)0.5H3.5SiW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 4wt%, (NH4)0.5H3.5SiW12O40Content is 12wt%.Catalyst B is (NH4)0.5H3.5SiW12O40-NiO/SiO2Catalyst, wherein NiO content is 9wt%, (NH4)0.5H3.5SiW12O40Content is 18wt%.
The evaluation of catalyst with embodiment 1, ethanol conversion and ethylene selectivity result in Table 1.
Comparative example 1
Be used alone in embodiment 1 catalyst A, the evaluation of catalyst with embodiment 1, ethanol conversion and ethylene selectivity result in Table 1.
The evaluation result of each example of table 1
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 98.2 | 97.4 |
| Embodiment 2 | 98.0 | 97.3 |
| Embodiment 3 | 98.6 | 98.7 |
| Embodiment 4 | 98.0 | 97.3 |
| Comparative example 1 | 92.0 | 90.5 |
Claims (10)
1., by a method for producing ethylene from dehydration of ethanol, including at least two beds and catalyst A and catalyst B, wherein ethanol raw material first contacts with catalyst A, then contacts with catalyst B again；
Catalyst A's is composed as follows: active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is boron oxide, and carrier is aluminium oxide；With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 3% ~ 25%, and the content that auxiliary agent is counted with oxide is for 2% ~ 5%, and the content of aluminium oxide is 70% ~ 95%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, Y and represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P, m+n=3, n value is 0.1 ~ 1.0；
Catalyst B's is composed as follows:
Active component is that ammonium heteropoly acids is shown in formula (2), and auxiliary agent is nickel oxide, and carrier is silicon oxide；With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 8% ~ 35%, and the content that auxiliary agent is counted with oxide is for 3% ~ 18%, and the content of carrier is 47% ~ 89%；
Hu(NH4)vAB12O40(2)
Wherein A represents W or Mo, B and represents Si or P；When B represents Si, u+v=4, v value is 0.1 ~ 1.0；When B represents P, u+v=3, v value is 0.1 ~ 1.0.
2. in accordance with the method for claim 1, it is characterised in that: described catalyst A, with the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 5% ~ 20%, and the content that auxiliary agent is counted with oxide is for 2% ~ 5%, and the content of aluminium oxide is 75% ~ 93%.
3. in accordance with the method for claim 1, it is characterised in that: described catalyst B, with the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 12% ~ 30%, and the content that auxiliary agent is counted with oxide is for 5% ~ 15%, and the content of carrier is 55% ~ 83%.
4. in accordance with the method for claim 1, it is characterised in that: described catalyst B, with the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 18% ~ 30%, and the content that auxiliary agent is counted with oxide is for 5% ~ 15%, and the content of carrier is 55% ~ 77%.
5. in accordance with the method for claim 1, it is characterised in that: in described catalyst B, the character of silica support is as follows: specific surface area is 500 ~ 820m2/ g, pore volume is 0.62 ~ 0.92mL/g, and average pore diameter is 4.6 ~ 6.6nm.
6. in accordance with the method for claim 1, it is characterised in that: in described catalyst B, adding one or more in mesoporous molecular sieve SBA-15, SBA-3, MCM-41 in silica support, molecular sieve weight content in the carrier is below 10%.
7. according to the arbitrary described method of claim 1 ~ 6, it is characterised in that: in described catalyst A, ammonium heteropoly acids is the distribution of uniform type on the alumina support, and in described catalyst B, ammonium heteropoly acids is distributed for eggshell type on silica support.
8. according to the arbitrary described method of claim 1 ~ 6, it is characterised in that: in described catalyst B, the weight content of ammonium heteropoly acids is not less than in catalyst A the weight content of ammonium heteropoly acids.
9. in accordance with the method for claim 1, it is characterised in that: described catalyst A and the admission space of catalyst B are than for 4:1 ~ 1:4.
10. in accordance with the method for claim 1, it is characterised in that: adopting fixed-bed process, the reaction condition of producing ethylene by ethanol dehydration is as follows: mass space velocity 0.5h-1~10.0h-1, reaction temperature 280 DEG C ~ 400 DEG C.
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