CN105712824B - A kind of method by producing ethylene from dehydration of ethanol - Google Patents
A kind of method by producing ethylene from dehydration of ethanol Download PDFInfo
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Abstract
The invention discloses a kind of method by producing ethylene from dehydration of ethanol.This method is catalyst A and catalyst B including at least two beds, and catalyst A compositions are as follows：Active component is ammonium heteropoly acidses, and auxiliary agent boron oxide, alumina catalyst support, catalyst B forms as follows：Active component is ammonium heteropoly acidses, auxiliary agent nickel oxide, Support 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 producing ethylene from dehydration of ethanol, is used for more particularly to one kind using combination catalyst
The method of producing ethylene from dehydration of 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 producing ethylene from dehydration of ethanol.Should
When method is used for producing ethylene from dehydration of ethanol, have the advantages that high ethanol conversion, selectivity and stability are good.
The method of producing ethylene from dehydration of ethanol of the present invention, including two beds are catalyst A and catalyst B, wherein
Ethanol raw material first contacts with catalyst A, is then contacted again with catalyst B；
Catalyst A composition is as follows：Catalyst A includes active component, auxiliary agent and carrier, and active component is ammonium heteropoly acidses
See formula（1）, auxiliary agent is boron oxide, and carrier is aluminum oxide；On the basis of the weight of catalyst, the contents of ammonium heteropoly acidses for 3% ~
25%, preferably 8% ~ 20%, more preferably 12% ~ 20%, much further preferably from 15% ~ 20%, auxiliary agent containing in terms of oxide
Measure as 2% ~ 5%, the content of aluminum oxide is 70% ~ 95%, and preferably 75% ~ 90%, more preferably 75% ~ 86% are further excellent
Elect 75% ~ 83% as；
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 ~ 1.0；When Y represents P
When, m+n=3, n values are 0.1 ~ 1.0.
Catalyst B composition is as follows：
Catalyst B includes active component, auxiliary agent and carrier, and active component is that ammonium heteropoly acidses are shown in formula（2）, auxiliary agent is oxidation
Nickel, carrier are silica；On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 8% ~ 35%, preferably 12% ~ 30%,
More preferably 18% ~ 30%, for auxiliary agent using the content that oxide is counted as 3% ~ 18%, preferably 5% ~ 15%, the content of carrier is 47%
~ 89%, preferably 55% ~ 83%, more preferably 55% ~ 77%；
Hu(NH4)vBA12O40（2）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, u+v=4, v values are 0.1 ~ 1.0；When B represents P
When, u+v=3, v values are 0.1 ~ 1.0.
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 described catalyst A, ammonium heteropoly acidses are distributed for uniform type on the alumina support, i.e., ammonium heteropoly acidses are uniform
It is distributed on the surfaces externally and internally of alumina support, in described catalyst B, ammonium heteropoly acidses are eggshell type on silica support
Distribution, i.e. ammonium heteropoly acidses are distributed in the outer surface of silica support, and do not have ammonium heteropoly acidses substantially in catalyst duct.
In the present invention, the weight content of ammonium heteropoly acidses is not less than ammonium heteropoly acidses in catalyst A in the catalyst B
Weight content.
In the present invention, catalyst A preparation method, including：
I, the presoma of auxiliary agent is added in the aqueous solution containing organic acid, obtains solution A；
II, alumina support is added in solution A, stirring to solution is evaporated at 50 DEG C ~ 80 DEG C；
III, the obtained solids of step II be added in the alkaline solution containing ammonium impregnated, then filtered, 50 DEG C ~
Dried at 90 DEG C, or the solid that step II is obtained is adsorbed into ammonia at 50 DEG C ~ 90 DEG C；
IV, the solid for obtaining step III, are added in the aqueous solution of heteropoly acid, are stirred at 50 DEG C ~ 80 DEG C to solution
It is evaporated；
V, the solid for obtaining step IV, through drying, the h of 2 h ~ 6 is then calcined at 300 DEG C ~ 550 DEG C, produces catalyst
A。
In step I, described auxiliary agent presoma is boric acid；The organic acid can be in citric acid, tartaric acid, malic acid
The mol ratio of one or more, described organic acid and aluminum oxide in alumina support used in step II is 0.05 ~ 0.50.
In step II, 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 III, the obtained solids of step II are added in the alkaline solution containing ammonia and impregnated, dip time one
As for the min of 5 min ~ 30.The solid absorption ammonia that step II is obtained, adsorption time are generally the min of 5 min ~ 30.
In step III, the alkaline solution containing ammonium is one kind in ammoniacal liquor, sal volatile, ammonium bicarbonate soln
It is or a variety of.
In step III, 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.
In step IV, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step IV, solid that step III is obtained is added in the aqueous solution of heteropoly acid and impregnated, dip time
The min of generally 5 min ~ 30.
In step V, described drying condition is as follows：The h of 90 DEG C ~ 120 DEG C 5 h of drying ~ 12.
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 producing ethylene by ethanol dehydration of the present invention is as follows using fixed-bed process, its reaction condition：Mass space velocity
0.5 h-1~10.0 h-1, 280 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, in low-concentration ethanol raw material dehydration is ethylene reaction produced there is low temperature to live
Property it is high the advantages of, be seated in catalyst A downstream, can be obviously improved bed temperature reduces what catalyst system was brought
Negative effect, catalyst A and catalyst B is cooperated and give full play to respective advantage, catalyst is integrally had higher
While activity, selectivity and coking resistivity, the stability of catalyst is improved, the service life of catalyst can be extended,
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 is prepared
It is prepared by catalyst A
Weigh 7.1g boric acid and 31.7g citric acids are added in deionized water, be made into mixed solution；By 84g through tabletting into
The alumina support of type is added in mixed solution, and stirring to solution is evaporated at 70 DEG C, wherein citric acid and Al2O3Mole
Than for 0.2；Gained solid is put into sal volatile and impregnates 10min, is dried after filtering at 70 DEG C；Gained solid is added
Enter into the aqueous solution containing 12.5g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C, 8 h is dried at 110 DEG C, 470
3 h are calcined at DEG C, (NH is made4)0.5H2.5PW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 4wt%, (NH4)0.5H2.5PW12O40Content is 12wt%.
It is prepared by catalyst B
（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%.
2nd, the evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 15wt% 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 5h-1, 330 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 5h-1, 320 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：
Weigh 8.9g boric acid and 45.2g citric acids are added in deionized water, be made into mixed solution；By 80g through tabletting into
Type alumina support is added in mixed solution, and stirring to solution is evaporated at 70 DEG C, wherein citric acid and Al2O3Mol ratio
For 0.3；Gained solid is put into sal volatile and impregnates 10min, is dried after filtering at 70 DEG C；Gained solid is added
Into the aqueous solution containing 15.6g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C, 8 h is dried at 110 DEG C, at 500 DEG C
3 h of lower roasting, (NH is made4)0.1H2.9PW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 5wt%, (NH4)0.1H2.9PW12O40Content is 15wt%.
Catalyst B preparation：
（1）The preparation of carrier：
Weigh 316g cetyl trimethylammonium bromides and 62.4g citric acids are made into mixed solution, by the positive silicic acid four of 246mL
Ethyl ester is added in mixed solution, stirs 2 h, then at 70 DEG C stirring into gel, by gel at 40 DEG C the h of aging 12,
Then 8 h are dried at 110 DEG C, through compression molding, 3 h is calcined at 600 DEG C, obtains silica support, wherein cetyl
The mol ratio of trimethylammonium bromide and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Support is：Compare table
Area is 630 m2/ g, pore volume are 0.81 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
46.7 g nickel nitrates are dissolved in deionized water, are added in 63g 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 70.6g 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 25.9g 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 520 DEG C, (NH is made4)0.2H2.8PW12O40-NiO/SiO2Catalyst,
Wherein NiO contents are 12wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
Catalyst A and B admission space ratio are 1:2, mass space velocity 8h-1, 310 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 (NH for remaining4)0.5H3.5SiW12O40-B2O3/Al2O3Catalyst, wherein B2O3Content is 4wt%, (NH4)0.5H3.5SiW12O40Content is 12wt%.Urge
Agent B is (NH4)0.5H3.5SiW12O40-NiO/SiO2Catalyst, wherein NiO contents are 9wt%, (NH4)0.5H3.5SiW12O40Content
For 18wt%.
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
| 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 (8)
1. a kind of method by producing ethylene from dehydration of 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 that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is boron oxide, and carrier is aluminum oxide；
On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 3% ~ 25%, and auxiliary agent is using the content that oxide is counted as 2% ~ 5%, oxygen
The content for changing aluminium is 70% ~ 95%；
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 ~ 1.0；When Y represents P, m
+ n=3, n value are 0.1 ~ 1.0；
Catalyst B composition is as follows：
Active component is that ammonium heteropoly acidses are shown in formula（2）, 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%；
Hu(NH4)vBA12O40（2）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, u+v=4, v values are 0.1 ~ 1.0；When B represents P, u+
V=3, v value are 0.1 ~ 1.0；
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, ammonium heteropoly acidses are distributed for uniform type on the alumina support, miscellaneous more in described catalyst B
Acid ammonium salt is distributed on silica support for 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 ammonium heteropoly acidses is 5% ~ 20%, and for auxiliary agent using the content that oxide is counted as 2% ~ 5%, the content of aluminum oxide is 75% ~ 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. 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%.
6. according to any described method of claim 1 ~ 5, it is characterised in that：The weight of ammonium heteropoly acidses in the catalyst B
Content is not less than the weight content of ammonium heteropoly acidses in catalyst A.
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, producing ethylene by ethanol dehydration it is anti-
Answer condition as follows：Mass space velocity 0.5h-1~10.0 h-1, 280 DEG C ~ 400 DEG C of reaction temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410713854.4A CN105712824B (en) | 2014-12-02 | 2014-12-02 | A kind of method by producing ethylene from dehydration of ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410713854.4A CN105712824B (en) | 2014-12-02 | 2014-12-02 | A kind of method by producing ethylene from dehydration of ethanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105712824A CN105712824A (en) | 2016-06-29 |
| CN105712824B true CN105712824B (en) | 2018-02-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104591978A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether through methanol dehydration |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104591978A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether through methanol dehydration |
Non-Patent Citations (1)
| Title |
|---|
| Efficient dehydration of ethanol on the self-organized surface layer ofH3PW12O40formed in the acidic potassium tungstophosphates;L.Matachowski,et al.;《Applied Catalysis A: General》;20131014(第469期);290-299 * |
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