CN106944145A - The preparation method of heteropoly acid ammonium catalyst - Google Patents
The preparation method of heteropoly acid ammonium catalyst Download PDFInfo
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- CN106944145A CN106944145A CN201610003165.3A CN201610003165A CN106944145A CN 106944145 A CN106944145 A CN 106944145A CN 201610003165 A CN201610003165 A CN 201610003165A CN 106944145 A CN106944145 A CN 106944145A
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Abstract
The invention discloses a kind of preparation method of heteropoly acid ammonium catalyst.The catalyst includes active component, auxiliary agent and carrier component, and active component is ammonium heteropoly acidses, and auxiliary agent is nickel oxide, and carrier component is silica, and its preparation method is the silica support for preparing the nickel containing auxiliary agent；Silica support obtains catalyst precarsor after loading organic acid, ammoniumization processing, dipping heteropoly acid, then after reduction treatment and furfurol reaction processing, then load organic acid, ammoniumization processing, leaching heteropoly acid solution successively, through drying and being calcined, obtain catalyst.The catalyst that the inventive method is obtained be particularly suitable for use in the low-concentration ethanol aqueous solution be raw material dehydration it is ethylene reaction produced, while with higher low temperature active, selectivity and coking resistivity, improve the stability of catalyst.
Description
Technical field
It is more particularly to a kind of to be used for ethanol dehydration life the invention discloses a kind of preparation method of heteropoly acid ammonium catalyst
Produce the preparation method of the heteropoly acid ammonium salt catalyst of ethene.
Background technology
Ethene is used as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products
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 cracks obtained, heavy dependence petroleum resources by light petroleum fraction.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and the new renewable alternative energy source of exploitation has been the task of top priority.
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, can avoid the dependence to petroleum resources, 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 worth 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 it is cheap as catalyst, preferably, but reaction temperature is high for activity and selectivity, 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
Fixed structure has the advantages that highly acid by the oxygen-containing polyacid of oxygen atom ligand bridging.In producing ethylene from dehydration of ethanol
In reaction, heteropolyacid catalyst has reaction temperature low, and selectivity is high and the characteristics of high income.
[Chemical Engineering Technology and the 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.The catalyst is using aluminum oxide as carrier, and 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 preparation method of heteropoly acid ammonium catalyst.Should
Catalyst obtained by method not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and good stability.
The preparation method of described heteropoly acid ammonium catalyst, including：
（1）Prepare the silica support containing auxiliary agent nickel；
（2）By step（1）Silica support be added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
（3）By step（2）Obtained material is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or
Person is by step（2）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C；
（4）The aqueous solution of heteropoly acid is added to step（3）In obtained material, heating stirring to solution is evaporated；
（5）By step（4）Catalyst precarsor A is made through drying and being calcined in obtained solid；
（6）By step（5）Catalyst precarsor A be added in autoclave, reduction treatment is carried out to it using hydrogen；
（7）Furfuryl aldehyde solution is added in autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, it is anti-at 100 DEG C~300 DEG C
Answer 0.5h~5.0h；
（8）By step（7）In reacted material filtering come out, low temperature drying to sample surfaces is obtained before catalyst without liquid phase
Body B；
（9）By step（8）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
（10）By step（9）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
Dry；Or by step（9）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（11）The aqueous solution of heteropoly acid is added to step（10）In obtained catalyst precarsor D, heating stirring to solution is evaporated；
（12）By step（11）Obtained solid produces catalyst through drying and being calcined.
The heteropoly acid ammonium catalyst that the inventive method is obtained, including active component, auxiliary agent and carrier component, active component is
Ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier component is silica；On the basis of the weight of catalyst, heteropoly acid ammonium
The content of salt is 5% ~ 45%, preferably 15% ~ 40%, more preferably 20% ~ 40%, and auxiliary agent is in terms of oxide, and nickel oxide contains
Measure as 3% ~ 15%, the content of silica is 40% ~ 92%, preferably 45% ~ 82%；
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.
In the inventive method, step（1）The property of silica support containing auxiliary agent nickel is as follows：Specific surface area be 420 ~
780 m2/ g, pore volume is 0.52 ~ 0.82 mL/g, and average pore diameter is 4.2 ~ 6.3 nm.
In the inventive method, step（1）The method for preparing the silica support A containing auxiliary agent nickel is preferably 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 at 60 DEG C ~ 90 DEG C stirring 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, then 300 DEG C ~
550 DEG C of roasting 2.0h ~ 6.0h, are made silica support；
Wherein auxiliary agent nickel can be introduced into carrier using conventional method, can in step A, step B, step C any step or several
Introduced in step, the introducing of auxiliary agent nickel, it would however also be possible to employ such as infusion process, altogether mixing method, glue method.Introduce adoptable during auxiliary agent nickel
One or more of the presoma in nickel nitrate, nickel acetate.
It may be incorporated into other adjuvant components in the inventive method, in silica support, such as boron, in terms of oxide,
Weight content in catalyst is less than 6%.
In the inventive method, other adjuvant components, such as iron, with di-iron trioxide are may be incorporated into silica support A
Meter, weight content in the catalyst is less than 10%.
In the inventive method, other adjuvant components can be introduced into silica support using conventional method, can be in step
In A, step B, step C other adjuvant components, such as infusion process, altogether mixing method, glue method etc. are introduced in any step or a few steps.
Step A, described template is DTAB, DTAC, hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorination
One or more in ammonium, hexamethylenetetramine, described template and step B silicon sources are with SiO2The mol ratio of meter be 0.01 ~
1.2。
Organic acid is the one or more in citric acid, tartaric acid, malic acid in step A, described organic acid and step B
Silicon source is with SiO2The mol ratio of meter is 0.1 ~ 1.2.
In step B, described silicon source is the one or more in tetraethyl orthosilicate, Ludox.
Described silica support can be made the carrier of shaping or be not required to the carrier of shaping, art technology
Personnel determine according to selected technique.The carrier of shaping, can be molded using existing conventional molding techniques, such as is squeezed
Bar is molded, compression molding etc., and shape can be bar shaped, spherical, sheet etc..In forming process, it can add as needed viscous
Agent and shaping assistant are tied, binding agent typically uses small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
Step（4）And step（11）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（4）And step（11）The middle mol ratio for introducing heteropoly acid is 4:1~1:4.
Step（2）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid
With SiO in silica support2Mol ratio be 0.05 ~ 0.50.
Step（3）In, by step（2）Obtained solid, which is added in the alkaline solution containing ammonia, to be impregnated, dip time
Generally 5min ~ 30min；By step（2）Obtained solid absorption ammonia, adsorption time is generally 5min ~ 30min.Step（3）
In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（3）In, described ammonia, which uses pure ammonia or used, removes ammonia in the gaseous mixture containing ammonia, mixed gas
Outside, other one or more in inert nitrogen gas, argon gas.
Step（6）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, it would however also be possible to employ containing lazy
Property gas hydrogen, hydrogen volume concentration be 30% ~ 100%.
Step（7）In, the mass concentration of described furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, the addition of furfural
Amount and step（1）The mass ratio of the silica support of gained is 2:1~10:1, preferably 3:1~10:1.
Step（8）In, low temperature drying can be carried out at room temperature.
Step（9）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid
With SiO in silica support2Mol ratio be 0.05 ~ 0.50.
Step（10）In, by step（9）Obtained solid, which is added in the alkaline solution containing ammonia, to be impregnated, dip time
Generally 5min ~ 30min；By step（9）Obtained solid absorption ammonia, adsorption time is generally 5min ~ 30min.Step
（10）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（10）In, described ammonia, which uses pure ammonia or used, removes ammonia in the gaseous mixture containing ammonia, mixed gas
Outside gas, other is the one or more in inert nitrogen gas, argon gas.
Step（2）, step（4）, step（9）Or step（11）The temperature of middle heating stirring is generally 40~90 DEG C.
Step（5）Or step（12）Described drying and roasting condition is as follows：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then
2h ~ 6h is calcined at 300 DEG C ~ 550 DEG C.Step（5）Or step（12）Identical or different drying and roasting condition can be used.
It is anti-that catalyst prepared by the inventive method is particularly suitable for use in the dehydration ethene that the low-concentration ethanol aqueous solution is raw material
Should.The reaction condition of described preparing ethylene by dehydrating ethanol is as follows：Ethanol water concentration is 5wt% ~ 40wt%, mass space velocity
0.5 h-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, using the hydrogenation of auxiliary agent nickel, in autoclave
Interior catalysis furfural liquid-phase hydrogenatin, mainly there is two aspect effects：One is the liquid alkane absorption of furfural liquid-phase hydrogenatin generation is being urged
On agent carrier, the duct of carrier can be effectively blocked, the heteropoly acid ammonium subsequently loaded is distributed on carrier surface, so
Major part ammonium heteropoly acidses are made to be dispersed in carrier surface, smaller portions ammonium heteropoly acidses are dispersed in carrier duct；The opposing party
Face, furfural liquid-phase hydrogenatin can produce carbon distribution on carrier, can weaken the acidity of carrier to a certain extent, reduce support acidity
The quantity of position absorption ammonia, makes heteropoly acid mainly be reacted with ammonium salt organic acid generation ammonium heteropoly acidses, contributes to heteropoly acid ammonium
Salt is dispersed in carrier surface, and can remove above-mentioned carbon deposit through follow-up high-temperature roasting, so effectively remains this portion
Fractional bearer acidic site.The catalyst that the inventive method is obtained not only has that low temperature active is high, the good, carbon accumulation resisting ability of selectivity is strong
Feature, and good stability.
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 31.1g nickel nitrates, 108.6g cetyl trimethylammonium bromides and 153g citric acids and be made into mixed solution, will
225mL tetraethyl orthosilicates are added in mixed solution, stir 2 h, and then stirring is into gel at 70 DEG C, by gel 40
DEG C h of aging 12, then dries 8 h at 110 DEG C, is calcined 3 h 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 492 m2/ g, pore volume is 0.60 mL/g, and average pore diameter is 4.9 nm.
（2）The preparation of catalyst：
The aqueous solution containing 12.0g citric acids is added in 75g carriers, stirs to solution and is evaporated at 70 DEG C；Obtained thing
Material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added to the water containing 8.6g phosphotungstic acids
In solution, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0 h, be then calcined 3.0 at 400 DEG C
H, is made catalyst precarsor A, is then added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, locates under 0.3MPa
4h is managed, reaction temperature is down to, the furfuryl aldehyde solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa,
3h is reacted at 150 DEG C, after reaction terminates, catalyst filtration is come out, is dried at 40 DEG C to carrier surface without liquid phase；Then
It is added in the aqueous solution containing 24.0g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material is added to ammonium carbonate
10min is impregnated in solution, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 17.3g phosphotungstic acids, at 40 DEG C
Lower stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 520 DEG C, are made
(NH4)0.2H2.8PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 10wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol waters, the h of mass space velocity 8-1, 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 2
（1）The preparation of carrier：
Weigh 38.9g nickel nitrates, 170g cetyl trimethylammonium bromides and 89.6g citric acids and be made into mixed solution, by 212mL
Tetraethyl orthosilicate is added in mixed solution, stirs 2 h, and then stirring is into gel at 70 DEG C, by gel at 40 DEG C
The h of aging 12, then dries 8 h at 110 DEG C, and compression molding is calcined 3 h at 600 DEG C, silica support is obtained, wherein ten
The mol ratio of six alkyl trimethyl ammonium bromides and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support
For：Specific surface area is 520 m2/ g, pore volume is 0.65 mL/g, and average pore diameter is 5.0 nm.
（2）The preparation of catalyst：
The aqueous solution containing 28.8g citric acids is added in 72g carriers, stirs to solution and is evaporated at 70 DEG C；Obtained thing
Material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added to containing 14.5g phosphotungstic acids
In the aqueous solution, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of roastings
3.0 h, are made catalyst precarsor A, are then added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, in 0.3MPa
Lower processing 4h, is down to reaction temperature, adds the furfuryl aldehyde solution that 400g mass concentrations are 20%, then adjusts Hydrogen Vapor Pressure to 3MPa,
2h is reacted at 160 DEG C, after reaction terminates, catalyst filtration is come out, is dried at 40 DEG C to carrier surface without liquid phase；Then
It is added in the aqueous solution containing 28.8g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material is added to ammonium carbonate
10min is impregnated in solution, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 14.5g phosphotungstic acids, at 40 DEG C
Lower stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 500 DEG C, are made
(NH4)0.5H2.5PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 11wt%, (NH4)0.5H2.5PW12O40Content is 28wt%.
The evaluation be the same as Example 1 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 3
（1）The preparation of carrier：
Weigh 46.7g nickel nitrates, 258g cetyl trimethylammonium bromides and 51.0g citric acids and be made into mixed solution, by 201mL
Tetraethyl orthosilicate is added in mixed solution, stirs 2 h, and then stirring is into gel at 70 DEG C, by gel at 40 DEG C
The h of aging 12, then dries 8 h at 110 DEG C, and compression molding is calcined 3 h at 600 DEG C, silica support is obtained, wherein ten
The mol ratio of six alkyl trimethyl ammonium bromides and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Support
For：Specific surface area is 560 m2/ g, pore volume is 0.72 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
The aqueous solution containing 52.3g citric acids is added in 70g silica supports, will stir to solution and be evaporated at 70 DEG C；
Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added to containing 20.7g
In the aqueous solution of phosphotungstic acid, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0 h, Ran Hou
400 DEG C of 3.0 h of roasting, are made catalyst precarsor A, are then added in autoclave, 450 DEG C are warming up under hydrogen atmosphere,
4h is handled under 0.3MPa, reaction temperature is down to, the furfuryl aldehyde solution that 400g mass concentrations are 20% is added, then adjusts hydrogen pressure
Power reacts 3h to 3MPa at 150 DEG C, and after reaction terminates, catalyst filtration is come out, dried at 40 DEG C to carrier surface without
Liquid phase；It is then added in the aqueous solution containing 26.2g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material adds
Enter and 10min is impregnated into sal volatile, dried after filtering at 40 DEG C；It is then added to containing the water-soluble of 10.4g phosphotungstic acids
In liquid, stir to solution and be evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, then 3.0 are calcined at 470 DEG C
H, is made (NH4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%, (NH4)0.7H2.3PW12O40Content is
30wt%。
The evaluation be the same as Example 1 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 628g P123, remaining be the same as Example 3, gained catalyst
For (NH4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%, (NH4)0.7H2.3PW12O40Content is
30wt%, P123 and SiO2Mol ratio be 0.1.Support is：Specific surface area is 540 m2/ g, pore volume is 0.74 mL/g, is put down
Equal bore dia is 5.5 nm.
The evaluation be the same as Example 1 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
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, remaining be the same as Example 3, gained catalyst is (NH4)0.7H3.3SiW12O40-NiO/
SiO2, wherein NiO contents are 12wt%, (NH4)0.7H3.3SiW12O40Content is 30wt%.
The evaluation be the same as Example 1 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 6
Catalyst is made according to embodiment 3, is commented according to the stability that the appreciation condition of embodiment 3 has carried out 100 h to catalyst
Valency is tested, and ethanol conversion and ethylene selectivity the results are shown in Table 2.
Comparative example 1
In embodiment 3, that silica support is added directly into the mixing containing 46.7g nickel nitrates and 31.1g phosphotungstic acids is water-soluble
In liquid, stir to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, then 3.0 are calcined at 350 DEG C
H, is made H3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%, H3PW12O40Content is 30wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 2
In embodiment 3, catalyst precarsor A is added in C6 alkane solvents, impregnates 10min, then filter, done at 40 DEG C
It is dry to carrier surface without liquid phase；It is then added in the aqueous solution containing 26.2g citric acids, stirs to solution and steam at 40 DEG C
It is dry；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；Be then added to containing
In the aqueous solution of 10.4g phosphotungstic acids, stir to solution and be evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, so
3.0 h are calcined at 470 DEG C afterwards, (NH is made4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%,
(NH4)0.7H2.3PW12O40Content is 30wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 3
Catalyst is made according to comparative example 1, is commented according to the stability that the appreciation condition of embodiment 3 has carried out 100 h to catalyst
Valency is tested, and ethanol conversion and ethylene selectivity the results are shown in Table 2.
The conversion ratio and selectivity of 1 each catalyst of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 1 | 98.9 | 98.5 |
| Embodiment 2 | 99.0 | 98.6 |
| Embodiment 3 | 98.8 | 98.5 |
| Embodiment 4 | 99.1 | 98.7 |
| Embodiment 5 | 98.7 | 98.3 |
| Comparative example 1 | 96.5 | 95.3 |
| Comparative example 2 | 97.0 | 96.3 |
The stability test evaluation result of table 2
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 6 | 98.6 | 98.3 |
| Comparative example 3 | 83.1 | 82.1 |
From Tables 1 and 2 result, activity, selectivity and the stability of catalyst of the present invention are significantly better than comparative example catalyst.
Claims (17)
1. a kind of preparation method of heteropoly acid ammonium catalyst, including：
（1）Prepare the silica support containing auxiliary agent nickel；
（2）By step（1）Silica support be added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
（3）By step（2）Obtained material is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or
Person is by step（2）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C；
（4）The aqueous solution of heteropoly acid is added to step（3）In obtained material, heating stirring to solution is evaporated；
（5）By step（4）Catalyst precarsor A is made through drying and being calcined in obtained solid；
（6）By step（5）Catalyst precarsor A be added in autoclave, reduction treatment is carried out to it using hydrogen；
（7）Furfuryl aldehyde solution is added in autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, it is anti-at 100 DEG C~300 DEG C
Answer 0.5h~5.0h；
（8）By step（7）In reacted material filtering come out, low temperature drying to sample surfaces is obtained before catalyst without liquid phase
Body B；
（9）By step（8）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
（10）By step（9）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
Dry；Or by step（9）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（11）The aqueous solution of heteropoly acid is added to step（10）In obtained catalyst precarsor D, heating stirring to solution is evaporated；
（12）By step（11）Obtained solid produces catalyst through drying and being calcined.
2. in accordance with the method for claim 1, it is characterised in that：Described heteropoly acid ammonium catalyst, including active component, help
Agent and carrier component, active component are shown in formula for ammonium heteropoly acidses（1）, auxiliary agent is nickel oxide, and carrier component is silica；To be catalyzed
On the basis of the weight of agent, the content of ammonium heteropoly acidses is 5% ~ 45%, and auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 15%,
The content of silica is 40% ~ 92%；It is preferably as follows：On the basis of the weight of catalyst, the contents of ammonium heteropoly acidses for 15% ~
40%, auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 15%, and the content of silica is 45% ~ 82%；
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.
3. according to the method described in claim 1 or 2, it is characterised in that：Contain boron in silica support, in terms of oxide,
Weight content in catalyst is less than 6%.
4. according to the method described in claim 1 or 2, it is characterised in that：Contain iron in silica support, with di-iron trioxide
Meter, weight content in the catalyst is less than 10%.
5. in accordance with the method for claim 1, it is characterised in that step（1）The property of described silica support is as follows：Than
Surface area is 420 ~ 780 m2/ g, pore volume is 0.52 ~ 0.82 mL/g, and average pore diameter is 4.2 ~ 6.3 nm.
6. according to the method described in claim 1 or 5, it is characterised in that step（1）The preparation method of described silica support
It is 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 at 60 DEG C ~ 90 DEG C stirring 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, then 300 DEG C ~
550 DEG C of roasting 2.0h ~ 6.0h, are made catalyst precarsor A；
Wherein auxiliary agent nickel is introduced in step A, step B, step C in any step or a few steps.
7. in accordance with the method for claim 6, it is characterised in that：In step A, described template is trimethyl
Ammonium bromide, DTAC, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, octadecane
One or more in base trimethylammonium bromide, OTAC, hexamethylenetetramine, described template with
Step B silicon sources are with SiO2The mol ratio of meter is 0.01 ~ 1.2.
8. in accordance with the method for claim 6, it is characterised in that：Organic acid is citric acid, tartaric acid, malic acid in step A
In one or more, described organic acid is with step B silicon sources with SiO2The mol ratio of meter is 0.1 ~ 1.2.
9. in accordance with the method for claim 6, it is characterised in that：In step B, described silicon source is tetraethyl orthosilicate, silicon is molten
One or more in glue.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）And step（11）In, described heteropoly acid is
One or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Step（4）And step（11）The middle mol ratio for introducing heteropoly acid is 4:1
~1:4。
11. in accordance with the method for claim 1, it is characterised in that：Step（2）In, the organic acid is citric acid, winestone
One or more in acid, malic acid；SiO in described organic acid and silica support2Mol ratio be 0.05 ~ 0.50.
12. in accordance with the method for claim 1, it is characterised in that：Step（3）In, by step（2）Obtained solid is added to
Impregnated in alkaline solution containing ammonia, dip time is 5min ~ 30min；By step（2）Obtained solid absorption ammonia, inhales
The attached time is 5min ~ 30min；Step（3）In, the alkaline solution containing ammonium is that ammoniacal liquor, sal volatile, ammonium hydrogen carbonate are molten
One or more in liquid.
13. in accordance with the method for claim 1, it is characterised in that：Step（6）In, described reduction treatment process is as follows：Hydrogen
Catalyst precarsor is warming up to 300 DEG C~600 DEG C under gas atmosphere, 4h~8h is handled under 0.1MPa~0.5MPa.
14. in accordance with the method for claim 1, it is characterised in that：Step（7）In, the mass concentration of described furfuryl aldehyde solution
For 5%~35%, preferably 5%~30%, the addition and step of furfural（1）The mass ratio of the silica support of gained is 2:1~
10:1, preferably 3:1~10:1.
15. in accordance with the method for claim 1, it is characterised in that：Step（9）In, the organic acid is citric acid, winestone
One or more in acid, malic acid；SiO in described organic acid and silica support2Mol ratio be 0.05 ~ 0.50.
16. in accordance with the method for claim 1, it is characterised in that：Step（10）In, by step（9）Obtained solid is added
Impregnated into the alkaline solution containing ammonia, dip time is 5min ~ 30min；By step（9）Obtained solid absorption ammonia,
Adsorption time is 5min ~ 30min；Step（10）In, the alkaline solution containing ammonium is ammoniacal liquor, sal volatile, bicarbonate
One or more in ammonium salt solution.
17. in accordance with the method for claim 1, it is characterised in that：Step（5）Or step（12）Described drying and roasting
Condition is as follows：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 2h ~ 6h is calcined at 300 DEG C ~ 550 DEG C.
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