CN105709825B - Heteropoly acid ammonium catalyst and preparation method thereof - Google Patents
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Abstract
The invention discloses a kind of heteropoly acid ammonium catalyst and preparation method thereof.The catalyst includes active component, auxiliary agent and carrier, active component is ammonium heteropoly acidses, auxiliary agent is boron oxide, carrier is silica, its preparation method is that silica support loads organic acid, heteropoly acid and auxiliary agent successively, then alkane, heteropoly acid and auxiliary agent, alkaline solution or ammonia containing ammonium are loaded successively again, through drying and being calcined, obtains catalyst.Catalyst prepared by the present invention, heteropoly acid exists with ammonium salts, and major part heteropolyacid salt is dispersed in carrier outer surface, and smaller portions are dispersed in carrier inner surfaces of pores, catalyst improves the stability of catalyst while with higher low temperature active, selectivity and coking resistivity.Catalyst of the present invention is ethylene reaction produced for the dehydration of raw material especially suitable for the low-concentration ethanol aqueous solution.
Description
Technical field
The present invention relates to a kind of heteropoly acid ammonium catalyst and its preparation side, is used for ethanol dehydration more particularly to one kind and produces
Carried heteropoly acid ammonium salt in catalysis agent of ethene and preparation method thereof.
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 and 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.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of heteropoly acid ammonium catalyst and its preparation side
Method.The catalyst not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and stability is good.
The preparation method of described heteropoly acid ammonium catalyst, including：
（1）Silica support is added in aqueous solutions of organic acids, stirring to solution is evaporated at 60 DEG C ~ 90 DEG C；
（2）By step（1）Obtained material is added in the mixed aqueous solution of auxiliary agent presoma and heteropoly acid, 60 DEG C ~ 90
Stirring to solution is evaporated at DEG C；
（3）By step（2）Obtained material is added in alkane solvent, is then filtered, 20 DEG C ~ 50 DEG C, preferably 30
DEG C ~ 50 DEG C at dry to carrier surface without liquid phase；
（4）The mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added to step（3）In obtained material, 60 DEG C ~
Stirring to solution is evaporated at 90 DEG C, in 90 ~ 120 DEG C of dry 3.0 ~ 8.0 h；
（5）By step（4）Obtained material is added in the alkaline solution containing ammonium, is filtered after dipping, or by step（4）
Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C；
（6）By step（5）Then obtained solid is calcined 2 in the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12 at 300 DEG C ~ 550 DEG C
The h of h ~ 6, produces catalyst.
In the inventive method, step（1）Obtained material can be charged first in the alkaline solution containing ammonium, filtered,
Step is carried out again after being dried at 50 DEG C ~ 90 DEG C（2）.It is added in the alkaline solution containing ammonium and is impregnated, dip time is generally 5
min~30 min.The described alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
In the inventive method, step（1）Obtained material carries out step again after can adsorbing ammonia at 50 DEG C ~ 90 DEG C
（2）.The time of absorption ammonia is generally the min of 5 min ~ 30.Described ammonia can use pure ammonia, can also use and contain ammonia
Gaseous mixture, in mixed gas in addition to ammonia, other is the one or more in inert gas such as nitrogen, argon gas.
Heteropoly acid ammonium catalyst of the present invention, including active component, auxiliary agent and carrier, active component are that ammonium heteropoly acidses are shown in formula
（1）, auxiliary agent is boron oxide, and carrier is silica；On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 5% ~ 45%,
Preferably 15% ~ 40%, more preferably 25% ~ 40%, using the content that oxide is counted as 3% ~ 10%, the content of carrier is auxiliary agent
45% ~ 92%, preferably 50% ~ 82%, more preferably 50% ~ 72%；
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.
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.
Step（1）Described silica support can be prepared as follows：
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, then in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, silica is made
Carrier.
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, wherein the condition being calcined is as follows：The h of 2 h ~ 6 is calcined at 300 DEG C ~ 800 DEG C.
Step（1）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 ~ 0.5.
Step（5）In, obtained material is added in the alkaline solution containing ammonium and impregnated, dip time is generally 5
min~30 min.The solid absorption ammonia that will be obtained, adsorption time are generally the min of 5 min ~ 30.Step（5）In, described contains
The alkaline solution of ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（5）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（2）And step（4）In, described auxiliary agent presoma is boric acid.
Step（2）And step（4）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（2）And step（4）The middle mol ratio for introducing auxiliary agent presoma is 3:1~1:3.
Step（2）And step（4）The middle mol ratio for introducing heteropoly acid is 3:1~1:3.
Step（3）In, described alkane solvent is C5~C10One or more in liquid n-alkane, solvent and oxidation
The volume ratio of silicon carrier is 1 ~ 3, and silica support adds in alkane solvent time for being impregnated as the min of 5 min ~ 20.
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.
Present invention also offers a kind of method of producing ethylene by ethanol dehydration, wherein the catalyst using the present invention.This hair
Bright heteropoly acid ammonium catalyst is ethylene reaction produced for the dehydration of raw material especially suitable for the low-concentration ethanol aqueous solution.Described ethanol takes off
The reaction condition that water prepares ethene is as follows：Ethanol water concentration is 5wt% ~ 40wt%, the h of mass space velocity 0.5-1~15.0 h-1,
180 DEG C ~ 400 DEG C of reaction temperature.
Catalyst of the present invention uses the silica support of bigger serface, passes through specific method carried heteropoly acid and auxiliary agent
Component, the heteropoly acid in catalyst is set to exist with ammonium salts, major part heteropolyacid salt is dispersed in carrier outer surface, smaller part
Carrier inner surfaces of pores is dispersed in, catalyst has high ammonium heteropoly acidses load capacity, on the premise of high conversion is ensured,
It can obtain compared with high selectivity, and stability is good.
Embodiment
With reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
（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, compression molding, 3 h is calcined at 580 DEG C, obtains silica support, wherein cetyl
The mol ratio of trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Compare table
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：
The silica support of preparation is added in the aqueous solution containing 38.4g citric acids, stirred at 70 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 5.9g boric acid and 10.4g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained material is added to C6
In alkane solvent, 10min is impregnated, is then filtered, dried at 40 DEG C to carrier surface without liquid phase；It is then added to containing 3.0g
In the mixed aqueous solution of boric acid and 5.2g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C, in 110 DEG C of dry 5.0 h；Obtain
Material is added to impregnate 10min in sal volatile after filter, by obtained solid in 110 DEG C of dry 8.0 h, then 500
DEG C roasting 3.0 h, be made (NH4)0.5H2.5PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is 5wt%, (NH4)0.5H2.5PW12O40Content is 15wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 6
h-1, 260 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts
After reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 2
（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, compression molding, 3 h is calcined at 600 DEG C, obtains silica support, wherein cetyl
The mol ratio of trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Compare table
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：
The silica support of preparation is added in the aqueous solution containing 44.2g citric acids, stirred at 70 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 5.3g boric acid and 13.0g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained material is added to C6
In alkane solvent, 10min is impregnated, is then filtered, dried at 40 DEG C to carrier surface without liquid phase；It is then added to containing 5.3g
In the mixed aqueous solution of boric acid and 13.0g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C, in 110 DEG C of dry 5.0 h；Obtain
Material be added in sal volatile impregnate 10min after filter, by obtained solid in 110 DEG C of dry 8.0 h, Ran Hou
470 DEG C of 3.0 h of roasting, are made (NH4)0.7H2.3PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is 6wt%, (NH4)0.7H2.3PW12O40Content is 25wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 7
h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts
After reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 3
（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, compression molding, 3 h is calcined at 600 DEG C, obtains silica support, wherein cetyl three
The mol ratio of methyl bromide ammonium and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Support is：Compare surface
Product is 630 m2/ g, pore volume are 0.81 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
The silica support of preparation is added in the aqueous solution containing 46.4g citric acids, stirred at 70 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 4.1g boric acid and 12.1g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained material is added to C6
In alkane solvent, 10min is impregnated, is then filtered, dried at 40 DEG C to carrier surface without liquid phase；It is then added to containing 8.3g
In the mixed aqueous solution of boric acid and 24.2g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C, in 110 DEG C of dry 5.0 h；Obtain
Material be added in sal volatile impregnate 10min after filter, by obtained solid in 110 DEG C of dry 8.0 h, Ran Hou
520 DEG C of 3.0 h of roasting, are made (NH4)0.2H2.8PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 35wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 10
h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts
After reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 628g P123, with embodiment 3, gained is urged for remaining
Agent is (NH4)0.2H2.8PW12O40-B2O3/SiO2, wherein B2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 35wt%,
P123 and SiO2Mol ratio be 0.1.Support is：Specific surface area is 610 m2/ g, pore volume are 0.84 mL/g, average Kong Zhi
Footpath is 5.5 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Embodiment 5
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, 10min is impregnated in sal volatile and is changed to inhale
Attached 10v% NH3/ Ar gaseous mixture 10min, with embodiment 3, gained catalyst is (NH for remaining4)0.2H3.8SiW12O40-
B2O3/SiO2, wherein B2O3Content is 7wt%, (NH4)0.2H3.8SiW12O40Content is 35wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Embodiment 6
Catalyst is made according to embodiment 3, has carried out 100 h stabilization to catalyst according to the appreciation condition of embodiment 3
Property evaluation experimental, ethanol conversion and ethylene selectivity the results are shown in Table 2.
Comparative example 1
In embodiment 3, carrier is added directly into the mixed aqueous solution containing 12.4g boric acid and 36.3g phosphotungstic acids,
Stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 350 DEG C, are made
H3PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is 7wt%, H3PW12O40Content is 35wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
Catalyst is made according to comparative example 1, has carried out 100 h stabilization to catalyst according to the appreciation condition of embodiment 3
Property evaluation experimental, ethanol conversion and ethylene selectivity the results are shown in Table 2.
The conversion ratio and selectivity of 1 each catalyst of table
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 98.4 | 98.0 |
| Embodiment 2 | 98.7 | 98.2 |
| Embodiment 3 | 98.8 | 98.3 |
| Embodiment 4 | 98.9 | 98.5 |
| Embodiment 5 | 98.6 | 98.1 |
| Comparative example 1 | 94.5 | 93.5 |
The stability test evaluation result of table 2
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 6 | 98.6 | 98.1 |
| Comparative example 2 | 81.1 | 79.3 |
From Tables 1 and 2 result, activity, selectivity and the stability of catalyst of the present invention are urged significantly better than comparative example
Agent.
Claims (21)
1. a kind of preparation method of heteropoly acid ammonium catalyst, including：
（1）Silica support is added in aqueous solutions of organic acids, stirs at 60 DEG C~90 DEG C and is evaporated to solution, described has
Machine 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；
（2）By step（1）Obtained material is added in the mixed aqueous solution of auxiliary agent presoma and heteropoly acid, at 60 DEG C~90 DEG C
Stirring to solution is evaporated；
（3）By step（2）Obtained material is added in alkane solvent, is then filtered, and is dried at 20 DEG C~50 DEG C to carrier
Without liquid phase, described alkane solvent is C on surface5~C10One or more in liquid n-alkane, alkane solvent and silica
The volume ratio of carrier is 1~3；
（4）The mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added to step（3）In obtained material, at 60 DEG C~90 DEG C
Lower stirring to solution is evaporated, in 90~120 DEG C of dry 3.0~8.0h；
（5）By step（4）Obtained material is added in the alkaline solution containing ammonium, is filtered after dipping, or by step（4）Obtain
Material adsorb ammonia at 50 DEG C~90 DEG C；
（6）By step（5）Obtained solid in 90 DEG C~120 DEG C dry 3h~12h, be then calcined at 300 DEG C~550 DEG C 2h~
6h, produce catalyst.
2. in accordance with the method for claim 1, it is characterised in that：By step（1）Obtained material is added to the alkalescence containing ammonium
It is filtered in solution, dried at 50 DEG C~90 DEG C, then carry out step（2）.
3. in accordance with the method for claim 1, it is characterised in that：By step（1）Obtained material is inhaled at 50 DEG C~90 DEG C
Attached ammonia, then carry out step（2）.
4. in accordance with the method for claim 1, it is characterised in that described catalyst, including active component, auxiliary agent and carrier,
Active component is that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is boron oxide, and carrier is silica；It is miscellaneous on the basis of the weight of catalyst
The content of more acid ammonium salts is 5%~45%, and for auxiliary agent using the content that oxide is counted as 3%~10%, the content of carrier is 45%~92%；
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.
5. in accordance with the method for claim 1, it is characterised in that：On the basis of the weight of catalyst, ammonium heteropoly acidses contain
Measure as 15%~40%, for auxiliary agent using the content that oxide is counted as 3%~10%, the content of carrier is 50%~82%.
6. in accordance with the method for claim 1, it is characterised in that：The property of the silica support is as follows：Specific surface area is
500~820m2/ g, pore volume are 0.62~0.92mL/g, and average pore diameter is 4.6~6.6nm.
7. according to claim 1 or 6 or described method, it is characterised in that：Step（1）Described silica support is using as follows
It is prepared by 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, then in 90 DEG C~120 DEG C dry 3h~12h, silica is made
Carrier.
8. in accordance with the method for claim 7, it is characterised in that：In step A, the template is cetyl trimethyl bromine
Change ammonium, hexadecyltrimethylammonium chloride, lauryl sodium sulfate, triblock polymer P123, triblock polymer F127, three
One or more in block polymer F108, the polyethylene glycol that molecular weight is 1000~10000.
9. in accordance with the method for claim 7, it is characterised in that：SiO in described template and carrier2Mol ratio be
0.01~1.2.
10. in accordance with the method for claim 7, it is characterised in that：In step B, described silicon source is tetraethyl orthosilicate, silicon is molten
One or more in glue.
11. in accordance with the method for claim 7, it is characterised in that：After step C dryings, through shaping or without being molded,
Silica support is obtained through high-temperature roasting again, wherein the condition being calcined is as follows：2h~6h is calcined at 300 DEG C~800 DEG C.
12. in accordance with the method for claim 1, it is characterised in that：Step（1）In, the organic acid is citric acid, winestone
One or more in acid, malic acid；SiO in described organic acid and carrier2Mol ratio be 0.05~0.5.
13. according to the method described in claim 1 or 2, it is characterised in that：The described alkaline solution containing ammonium is ammoniacal liquor, carbonic acid
One or more in ammonium salt solution, ammonium bicarbonate soln.
14. according to the method described in claim 1 or 3, it is characterised in that：Described ammonia uses pure ammonia, or uses and contain
The gaseous mixture of ammonia, in mixed gas in addition to ammonia, other one or more in inert gas such as nitrogen, argon gas.
15. in accordance with the method for claim 1, it is characterised in that：Step（2）And step（4）In, auxiliary agent presoma is boron
Acid；Described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
16. in accordance with the method for claim 1, it is characterised in that：Step（2）And step（4）Before the middle auxiliary agent introduced respectively
The mol ratio for driving body is 3:1~1:3；Step（2）And step（4）The mol ratio of the middle heteropoly acid introduced respectively is 3:1~1:3.
17. in accordance with the method for claim 1, it is characterised in that：Mesopore molecular sieve is added in described silica support
One or more in SBA-15, SBA-3, MCM-41, the weight content of mesopore molecular sieve in the carrier is below 10%.
18. a kind of heteropoly acid ammonium catalyst, it is characterised in that prepared using claim 1~17 either method.
A kind of 19. method of preparing ethylene by dehydrating ethanol, it is characterised in that using the catalyst described in claim 18.
20. in accordance with the method for claim 19, it is characterised in that：Described feed ethanol concentration of aqueous solution be 5wt%~
40wt%。
21. according to the method described in claim 19 or 20, it is characterised in that：The reaction condition of preparing ethylene by dehydrating ethanol is such as
Under：Mass space velocity 0.5h-1~15.0h-1, 180 DEG C~400 DEG C of reaction temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410714005.0A CN105709825B (en) | 2014-12-02 | 2014-12-02 | Heteropoly acid ammonium catalyst and preparation method thereof |
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|---|---|---|---|
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| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
| CN101157019A (en) * | 2007-10-26 | 2008-04-09 | 太原理工大学 | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method |
| 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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| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
| CN101157019A (en) * | 2007-10-26 | 2008-04-09 | 太原理工大学 | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method |
| 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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