CN106944148B - A kind of preparation method of heteropoly acid ammonium catalyst - Google Patents
A kind of preparation method of heteropoly acid ammonium catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of heteropoly acid ammonium catalyst.The catalyst includes active component, auxiliary agent and carrier component, and active component is ammonium heteropoly acids, and auxiliary agent is nickel oxide, and carrier component is silica, and preparation method is the catalyst precarsor A for preparing the nickel containing auxiliary agent；Catalyst precarsor A is after reduction treatment and furfurol reaction processing, then successively loads organic acid, ammoniumization processing, leaching heteropoly acid solution and obtain catalyst through dry and roasting.The catalyst that the method for the present invention obtains is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material, while low temperature active with higher, selectivity and coking resistivity, improves the stability of catalyst.
Description
Technical field
The invention discloses a kind of preparation methods of heteropoly acid ammonium catalyst, raw for ethanol dehydration more particularly to one kind
Produce the preparation method of the heteropoly acid ammonium salt catalyst of ethylene.
Background technique
Flagship product of the ethylene as basic Organic Chemicals and petro chemical industry, about 75% chemical products
It is to be prepared by raw material of ethylene, therefore the size of ethylene yield has become one national oil development of chemical industry water of measurement
Flat important symbol.Traditional ethylene is mainly the heavy dependence petroleum resources as made from light petroleum fraction cracking.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and developing new renewable alternative energy source has been the task of top priority.
Recently, ethyl alcohol especially recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, and is had
Green, sustainable, various advantages such as reaction condition is mild and product ethylene is with high purity.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 always this method production ethylene, and this point more has realistic meaning to the country of oil-poor and few oil.Ethanol dehydration prepares second
Alkene has the great potential for partly or entirely replacing obtaining ethylene from petroleum.Therefore, research producing ethylene from dehydration of ethanol has great
Economic value and strategic importance.
There are many catalyst for ethanol delydration to ethylene report, mainly activated alumina, molecular sieve and heteropoly acid etc..It is living
Property aluminium 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, stablize；Reaction temperature is low, and reaction velocity is big, but
Catalyst life is short, and amplification factor is small, limits its industrialized production.Heteropoly acid is by central atom and coordination atom with one
Fixed structure passes through oxygen-containing polyacid made of oxygen atom ligand bridging, has many advantages, such as highly acid.In producing ethylene from dehydration of ethanol
The characteristics of in reaction, heteropolyacid catalyst has reaction temperature low, selectivity height and high income.
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] reports the entitled load of MCM- 41 silico-tungstic acid and urges
Change the article of producing ethylene from dehydration of ethanol, catalyst is prepared using infusion process.It is de- that CN200910057539.X discloses a kind of ethyl alcohol
The catalyst of water ethylene.For the catalyst using aluminium 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 works as with low-concentration ethanol and be
When raw material, catalyst activity is decreased obviously, and stability is bad.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of preparation sides of heteropoly acid ammonium catalyst
Method.The resulting catalyst of this method not only has the characteristics that low temperature active is high, selectivity is good, has strong anti-carbon capacity, and stablizes
Property is good.
The preparation method of the heteropoly acid ammonium catalyst, comprising:
(1) the silica catalyst support A containing auxiliary agent nickel is prepared；
(2) the silica catalyst support A of step (1) is added in autoclave, it is gone back using hydrogen
Original place reason；
(3) furfuryl aldehyde solution is added in autoclave, then adjusts Hydrogen Vapor Pressure to 2~4MPa, at 100 DEG C~300 DEG C
Lower reaction 0.5h~5.0h；
(4) material filtering after reaction in step (3) is come out, low temperature drying to sample surfaces is catalyzed without liquid phase
Agent precursor B；
(5) the catalyst precarsor B that step (4) obtains being added in aqueous solutions of organic acids, heating stirring to solution is evaporated,
Obtain catalyst precarsor C；
(6) the catalyst precarsor C that step (5) obtains is added in the alkaline solution containing ammonium, through filtering, 40 DEG C ~ 90
It is dry at DEG C；Or the material that step (5) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(7) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (6) obtains, heating stirring to solution is steamed
It is dry；
(8) solid for obtaining step (7) is through dry and roasting to get catalyst.
The heteropoly acid ammonium catalyst that the method for the present invention obtains, including active component, auxiliary agent and carrier component, active component be
Ammonium heteropoly acids are shown in formula (1) that 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% ~ 40%, preferably 15% ~ 35%, and auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 15%, and silica contains
Amount is 45% ~ 92%, preferably 50% ~ 82%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P
When, m+n=3, n value is 0.1 ~ 1.0.
In the method for the present invention, the property of catalyst precarsor A of the step (1) containing auxiliary agent nickel is as follows: specific surface area be 500 ~
820 m20.62 ~ 0.92 mL/g of/g, Kong Rongwei, average pore diameter are 4.6 ~ 6.6 nm.
In the method for the present invention, the method that step (1) prepares the silica catalyst 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 stirred at 60 DEG C ~ 90 DEG C at gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ for 24 hours, then in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300
DEG C ~ 550 DEG C of roasting 2.0h ~ 6.0h, silica catalyst support A is made；
Wherein auxiliary agent nickel can be introduced into carrier using conventional method, can in step A, step B, step C any step
Or it is introduced in several steps, such as infusion process, mixing method, altogether glue method etc..When introducing auxiliary agent nickel adoptable presoma be selected from nickel nitrate,
One of nickel acetate is a variety of.
In the method for the present invention, it may be incorporated into other adjuvant components, such as boron in catalyst precarsor A, in terms of oxide,
Weight content in catalyst is 6% or less.
In the method for the present invention, it may be incorporated into other adjuvant components, such as iron in catalyst precarsor A, with di-iron trioxide
Meter, weight content in the catalyst are 10% or less.
In the method for the present invention, other adjuvant components can be introduced into catalyst precarsor A using conventional method, can be in step
A, other adjuvant components, such as infusion process, mixing method, altogether glue method etc. are introduced in any step or a few steps in step B, step C.
Step A, the template are dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorination
One of ammonium, hexamethylenetetramine are a variety of, and the template and step B silicon source are with SiO2The molar ratio of meter be 0.01 ~
1.2。
Organic acid is one of citric acid, tartaric acid, malic acid or a variety of, the organic acid and step B in step A
Silicon source is with SiO2The molar ratio of meter is 0.1 ~ 1.2.
In step B, the silicon source is one of ethyl orthosilicate, silica solution or a variety of.
Molding catalyst carrier can be made in the catalyst carrier A, be also possible to be not required to molding catalyst load
Body, those skilled in the art determine according to selected technique.Molding catalyst carrier, can using existing routine at
Type technology forms, such as extruded moulding, compression molding etc., and shape can be bar shaped, spherical shape, sheet etc..In forming process,
It can according to need addition binder and shaping assistant, binder generally use small porous aluminum oxide.Shaping assistant such as peptizing agent,
Extrusion aid etc..
In step (7), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
In step (2), the 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 at 0.1MPa~0.5MPa.Wherein reduction treatment can use pure hydrogen, can also be using containing lazy
Property gas hydrogen, hydrogen volume concentration be 30% ~ 100%.
In step (3), the mass concentration of the furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, the addition of furfural
The mass ratio of amount and step (1) resulting catalyst carrier A are 2:1 ~ 10:1, preferably 3:1 ~ 10:1.
In step (4), low temperature drying can carry out at room temperature.
In step (5), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
With SiO in catalyst carrier A2Molar ratio be 0.05 ~ 0.50.
In step (6), the solid that step (5) obtains is added in the alkaline solution containing ammonia and is impregnated, dip time
Generally 5min ~ 30min；The solid absorption ammonia that step (5) is obtained, adsorption time are generally 5min ~ 30min.Step (6)
In, the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (7), the ammonia is using pure ammonia or uses the gaseous mixture containing ammonia, removes ammonia in mixed gas
Outside, other is one of inert nitrogen gas, argon gas or a variety of.
The temperature of heating stirring is generally 40~90 DEG C in step (5) or step (7).
Drying described in step (8) and roasting condition are as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300 DEG C ~
550 DEG C of roasting 2h ~ 6h.
The catalyst of the method for the present invention preparation is anti-especially suitable for the dehydration ethylene that low-concentration ethanol aqueous solution is raw material
It answers.The reaction condition of the 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 has two aspect effects: one is the liquid alkane that furfural liquid-phase hydrogenatin generates is adsorbed on and urges
On agent carrier, the duct of carrier can be effectively blocked, is distributed in the heteropoly acid ammonium of subsequent load on carrier outer surface；Separately
On the one hand, furfural liquid-phase hydrogenatin can generate carbon distribution on carrier, can weaken the acidity of carrier to a certain extent, reduce carrier
Acidic site adsorbs the quantity of ammonia, so that heteropoly acid is mainly reacted with ammonium salt organic acid and generates ammonium heteropoly acids, facilitates miscellaneous more
Acid ammonium salt is evenly dispersed in carrier surface, and can remove above-mentioned carbon deposit through subsequent high-temperature roasting, effectively remains in this way
This Component Vectors acidic site.The catalyst that the method for the present invention obtains not only have low temperature active it is high, selectivity good, carbon accumulation resisting ability
Strong feature, and stability is good.
Specific embodiment
Below with reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) preparation of carrier:
It weighs 145.8g cetyl trimethylammonium bromide and 205g citric acid is 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 at gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, then dry 8 h at 110 DEG C after compression molding, in 580 DEG C of 3 h of roasting, obtain silica support, wherein hexadecane
The molar ratio of base trimethylammonium bromide and silica is 0.3, and the molar ratio of citric acid and silica is 0.8.
31.1 g nickel nitrates are dissolved in deionized water, are added in 77g silica support, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of 3.0 h of roasting, nickeliferous catalyst carrier A is made,
Property are as follows: specific surface area is 500 m20.61 mL/g of/g, Kong Rongwei, average pore diameter are 4.9 nm.
(2) preparation of catalyst:
Catalyst carrier A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, is handled at 0.3MPa
4h is down to reaction temperature, and the furfuryl aldehyde solution that 400g mass concentration is 20% is added, and then adjusts Hydrogen Vapor Pressure to 3MPa, 140
3h is reacted at DEG C, after reaction, catalyst filtration is come out, and is dried to carrier surface at 40 DEG C without liquid phase；Then it is added
Into the aqueous solution containing 37.0g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material is added to sal volatile
Middle dipping 10min is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 15.6g phosphotungstic acid, is stirred at 70 DEG C
It mixes to solution and is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 500 DEG C of 3.0 h of roasting, (NH is made4)0.5H2.5PW12O40/NiO-SiO2Catalyst, wherein NiO content is 8wt%, (NH4)0.5H2.5PW12O40Content is 15wt%.
(3) catalyst characterization:
It is taken a little in the surrounding in catalyst granules section and centre, elemental analysis is carried out to each point by SEM, the results showed that
Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and ammonium heteropoly acids are not detected in intermediate each point, illustrates using this side
The catalyst of method preparation, the dispersion that ammonium heteropoly acids have had on catalyst surface, and be not impregnated with into duct.
(4) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
4 h-1, 250 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning 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) preparation of carrier:
It weighs 200g cetyl trimethylammonium bromide and 105.7g citric acid is 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 at gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, then dry 8 h at 110 DEG C obtain silica support, wherein cetyl in 600 DEG C of 3 h of roasting after compression molding
The molar ratio of trimethylammonium bromide and silica is 0.5, and the molar ratio of citric acid and silica is 0.5.
38.9 g nickel nitrates are dissolved in deionized water, are added in 70g silica support, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of 3.0 h of roasting, nickeliferous catalyst carrier A is made,
Property are as follows: specific surface area is 530 m2/ g, Kong Rongwei 0.67mL/g, average pore diameter are 5.1 nm.
(2) preparation of catalyst:
Catalyst carrier A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, is handled at 0.3MPa
4h is down to reaction temperature, and the furfuryl aldehyde solution that 400g mass concentration is 20% is added, and then adjusts Hydrogen Vapor Pressure to 3MPa, 160
2h is reacted at DEG C, after reaction, catalyst filtration is come out, and is dried to carrier surface at 40 DEG C without liquid phase；Then it is added
Into the aqueous solution containing 56.0g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material is added to sal volatile
Middle dipping 10min is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 20.7g phosphotungstic acid, is stirred at 70 DEG C
It mixes to solution and is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, (NH is made4)0.7H2.3PW12O40/NiO-SiO2Catalyst, wherein NiO content is 10wt%, (NH4)0.7H2.3PW12O40Content is 20wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
4 h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning 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) preparation of carrier:
It weighs 316g cetyl trimethylammonium bromide and 62.4g citric acid is made into mixed solution, by the positive silicic acid four of 246mL
Ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, by gel aging at 30 DEG C ~ 50 DEG C
12 h, then dry 8 h at 110 DEG C obtain silica support, wherein 16 in 650 DEG C of 3 h of roasting after compression molding
The molar ratio of alkyl trimethyl ammonium bromide and silica is 0.8, and the molar ratio of citric acid and silica is 0.3.
46.7 g nickel nitrates are dissolved in deionized water, are added in 63g silica support, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of 3.0 h of roasting, nickeliferous catalyst carrier A is made,
Carrier are as follows: specific surface area is 560 m20.73 mL/g of/g, Kong Rongwei, average pore diameter are 5.2 nm.
(2) preparation of catalyst:
Catalyst carrier A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, is handled at 0.3MPa
4h is down to reaction temperature, and the furfuryl aldehyde solution that 400g mass concentration is 20% is added, and then adjusts Hydrogen Vapor Pressure to 3MPa, 150
3h is reacted at DEG C, after reaction, catalyst filtration is come out, and is dried to carrier surface at 40 DEG C without liquid phase；Then it is added
Into the aqueous solution containing 70.6g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material is added to sal volatile
Middle dipping 10min is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 25.9g phosphotungstic acid, is stirred at 70 DEG C
It mixes to solution and is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 520 DEG C of 3.0 h of roasting, (NH is made4)0.2H2.8PW12O40/NiO-SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
7 h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning 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/NiO-SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.2H2.8PW12O40Content is
25wt%, P123 and SiO2Molar ratio be 0.1.Support are as follows: specific surface area is 540 m20.76 mL/g of/g, Kong Rongwei is put down
Equal bore dia is 5.6 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/
NiO-SiO2, wherein NiO content is 12wt%, (NH4)0.2H3.8SiW12O40Content is 25wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Embodiment 6
(1) silica support prepared by selection example 3；
54.5 g nickel nitrates are dissolved in deionized water, are added in 56g silica support, stirring to solution steams at 70 DEG C
It is dry, obtain nickeliferous catalyst carrier A；
(2) preparation of catalyst:
Nickeliferous catalyst carrier A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, in 0.3MPa
Lower processing 4h is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 150 DEG C, after reaction, catalyst filtration is come out, and is dried to carrier surface at 40 DEG C without liquid phase；Then
It is added in the aqueous solution containing 62.7g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material is added to ammonium carbonate
10min is impregnated in solution, it is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 31.1g phosphotungstic acid, at 70 DEG C
Lower stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 520 DEG C of 3.0 h of roasting, it is made
(NH4)0.2H2.8PW12O40-NiO/SiO2Catalyst, wherein NiO content is 14wt%, (NH4)0.2H2.8PW12O40Content is 30wt%.
(4) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
8h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning 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 7
Catalyst is made according to embodiment 3, has carried out the stabilization of 100 h to catalyst according to the evaluation 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, silica support is added directly into the mixing containing 46.7g nickel nitrate and 25.9g phosphotungstic acid
In aqueous solution, stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, then roasted at 350 DEG C
H is made in 3.0 h3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%, H3PW12O40Content is 25wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
The silica support 63g prepared in embodiment 3 is added in C6 alkane solvent, 10min is impregnated, then filters,
It dries to carrier surface at 40 DEG C without liquid phase；It is then added in the aqueous solution containing 70.6g citric acid, is stirred at 70 DEG C
It is evaporated to solution；Obtained material, which is added in sal volatile, impregnates 10min, dry at 60 DEG C after filtering；Then it is added
Into the mixed aqueous solution containing 46.7g nickel nitrate and 25.9g phosphotungstic acid, stirring to solution is evaporated at 70 DEG C；By what is obtained
In 110 DEG C of dry 8.0 h, then in 520 DEG C of 3.0 h of roasting, (NH is made in solid4)0.2H2.8PW12O40-NiO/SiO2Catalyst,
Wherein NiO content is 12wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 3
Catalyst is made according to comparative example 1, has carried out the stabilization of 100 h to catalyst according to the evaluation 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
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 1 | 98.5 | 98.2 |
| Embodiment 2 | 98.3 | 98.1 |
| Embodiment 3 | 99.1 | 98.8 |
| Embodiment 4 | 99.4 | 99.2 |
| Embodiment 5 | 98.9 | 98.8 |
| Embodiment 6 | 99.5 | 99.3 |
| Comparative example 1 | 96.0 | 95.1 |
| Comparative example 2 | 96.4 | 96.2 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 7 | 98.9 | 98.6 |
| Comparative example 3 | 83.1 | 82.0 |
By Tables 1 and 2 result as it can be seen that activity, selectivity and the stability of catalyst of the present invention are urged significantly better than comparative example
Agent.
Claims (17)
1. a kind of preparation method of heteropoly acid ammonium catalyst, comprising:
(1) the silica catalyst support A containing auxiliary agent nickel is prepared；
(2) the silica catalyst support A of step (1) is added in autoclave, carries out also original place to it using hydrogen
Reason；
(3) furfuryl aldehyde solution is added in autoclave, then adjusting Hydrogen Vapor Pressure to 2~4MPa, it is anti-at 100 DEG C~300 DEG C
Answer 0.5h~5.0h；
(4) material filtering after reaction in step (3) is come out, low temperature drying to sample surfaces is without liquid phase, before obtaining catalyst
Body B；
(5) the catalyst precarsor B that step (4) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
(6) the catalyst precarsor C that step (5) obtains is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
It is dry；Or the material that step (5) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(7) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (6) obtains, heating stirring to solution is evaporated；
(8) solid for obtaining step (7) is through dry and roasting to get catalyst.
2. preparation method described in accordance with the claim 1, it is characterised in that: the heteropoly acid ammonium catalyst, including active group
Point, auxiliary agent and carrier component, active component is that ammonium heteropoly acids are shown in formula (1) that auxiliary agent is nickel oxide, and carrier component is silica；
On the basis of the weight of catalyst, the content of ammonium heteropoly acids is 5% ~ 40%, and for auxiliary agent in terms of oxide, the content of nickel oxide is 3%
~ 15%, the content of silica is 45% ~ 92%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P, m
+ n=3, n value are 0.1 ~ 1.0.
3. preparation method described in accordance with the claim 1, it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acids
Content be 15% ~ 35%, for auxiliary agent in terms of oxide, the content of nickel oxide is 3% ~ 15%, and the content of silica is 50% ~ 82%.
4. preparation method according to claim 1 or 2, it is characterised in that: the silica catalyst support A containing auxiliary agent nickel
In contain boron, in terms of oxide, weight content in the catalyst is 6% or less.
5. preparation method according to claim 1 or 2, it is characterised in that: the silica catalyst support A containing auxiliary agent nickel
In contain iron, in terms of di-iron trioxide, weight content in the catalyst is 10% or less.
6. preparation method described in accordance with the claim 1, it is characterised in that the silica containing auxiliary agent nickel described in step (1) is urged
The property of agent carrier A is as follows: specific surface area is 500 ~ 820m20.62 ~ 0.92 mL/g of/g, Kong Rongwei, average pore diameter are
4.6~6.6 nm。
7. according to preparation method described in claim 1 or 6, it is characterised in that the oxidation containing auxiliary agent nickel described in step (1)
Silicon catalyst carrier A's the preparation method 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 stirred at 60 DEG C ~ 90 DEG C at gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ for 24 hours, 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 catalyst support A；
Wherein auxiliary agent nickel introduces in any step or a few steps in step A, step B, step C.
8. preparation method according to claim 7, it is characterised in that: in step A, the template is dodecyl three
Methyl bromide ammonium, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, ten
One of eight alkyl trimethyl ammonium bromides, octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of, the template
Agent and step B silicon source are with SiO2The molar ratio of meter is 0.01 ~ 1.2.
9. preparation method according to claim 7, it is characterised in that: organic acid is citric acid, tartaric acid, apple in step A
One of tartaric acid is a variety of, and the organic acid and step B silicon source are with SiO2The molar ratio of meter is 0.1 ~ 1.2.
10. preparation method according to claim 7, it is characterised in that: in step B, the silicon source be ethyl orthosilicate,
One of silica solution is a variety of.
11. preparation method described in accordance with the claim 1, it is characterised in that: in step (7), the heteropoly acid be phosphotungstic acid,
One of silico-tungstic acid, phosphomolybdic acid are a variety of.
12. preparation method described in accordance with the claim 1, it is characterised in that: in step (2), the reduction treatment process is such as
Under: catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, 4h~8h is handled at 0.1MPa~0.5MPa.
13. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), the quality of the furfuryl aldehyde solution
Concentration is 5%~35%, and the additional amount of furfural and the mass ratio of step (1) resulting catalyst carrier A are 2:1 ~ 10:1.
14. preparation method described in claim 1, it is characterised in that: in step (3), the mass concentration of the furfuryl aldehyde solution
It is 5%~30%, the additional amount of furfural and the mass ratio of step (1) resulting catalyst carrier A are 3:1 ~ 10:1.
15. preparation method described in accordance with the claim 1, it is characterised in that: in step (5), the organic acid is citric acid, wine
One of stone acid, malic acid are a variety of；SiO in the organic acid and catalyst carrier A2Molar ratio be 0.05 ~ 0.50.
16. preparation method described in accordance with the claim 1, it is characterised in that: in step (6), catalyst that step (5) is obtained
Precursor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is 5min ~ 30min；The catalysis that step (5) is obtained
Agent precursor C adsorbs ammonia, and adsorption time is 5min ~ 30min；In step (6), the alkaline solution containing ammonium is ammonium hydroxide, carbon
One of acid ammonium solution, ammonium bicarbonate soln are a variety of.
17. preparation method described in accordance with the claim 1, it is characterised in that: drying described in step (8) and roasting condition are such as
Under: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then in 300 DEG C ~ 550 DEG C roasting 2h ~ 6h.
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