CN106944145B - The preparation method of heteropoly acid ammonium catalyst - Google Patents
The 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 silica support for preparing the nickel containing auxiliary agent；Silica support obtains catalyst precarsor after load organic acid, ammoniumization processing, dipping heteropoly acid, then 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 methods of heteropoly acid ammonium catalyst.It should
The resulting catalyst of method not only has the characteristics that low temperature active is high, selectivity is good, has strong anti-carbon capacity, and stability is good.
The preparation method of the heteropoly acid ammonium catalyst, comprising:
(1) silica support containing auxiliary agent nickel is prepared；
(2) silica support of step (1) is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(3) material that step (2) obtains is added in the alkaline solution containing ammonium, through filtering, is done at 40 DEG C ~ 90 DEG C
It is dry；Or the material that step (2) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C；
(4) aqueous solution of heteropoly acid is added in the material that step (3) obtains, heating stirring to solution is evaporated；
(5) catalyst precarsor A is made through dry and roasting in the solid for obtaining step (4)；
(6) the catalyst precarsor A of step (5) is added in autoclave, carries out also original place to it using hydrogen
Reason；
(7) 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；
(8) material filtering after reaction in step (7) is come out, low temperature drying to sample surfaces is catalyzed without liquid phase
Agent precursor B；
(9) the catalyst precarsor B that step (8) obtains being added in aqueous solutions of organic acids, heating stirring to solution is evaporated,
Obtain catalyst precarsor C；
(10) the catalyst precarsor C that step (9) 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 (9) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(11) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (10) obtains, heating stirring to solution
It is evaporated；
(12) solid for obtaining step (11) 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% ~ 45%, preferably 15% ~ 40%, further preferably 20% ~ 40%, and in terms of oxide, nickel oxide contains auxiliary agent
Amount is 3% ~ 15%, and the content of silica is 40% ~ 92%, preferably 45% ~ 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 the silica support of step (1) containing auxiliary agent nickel is as follows: specific surface area be 420 ~
780 m20.52 ~ 0.82 mL/g of/g, Kong Rongwei, average pore diameter are 4.2 ~ 6.3 nm.
In the method for the present invention, the method that step (1) prepares 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 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 support 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 introduced in several steps, the introducing of auxiliary agent nickel, it can also be using such as infusion process, mixing method, altogether glue method.It can be adopted when introducing auxiliary agent nickel
Presoma is selected from one of nickel nitrate, nickel acetate or a variety of.
It may be incorporated into other adjuvant components, such as boron in the method for the present invention, in silica support, 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 silica support 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 silica support 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 carrier can be made in the silica support, be also possible to be not required to molding carrier, art technology
Personnel determine according to selected technique.Molding carrier can be formed using existing conventional molding techniques, for example be squeezed
Item molding, compression molding etc., shape can be bar shaped, spherical shape, sheet etc..In forming process, it is viscous to can according to need addition
Knot agent and shaping assistant, binder generally use small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
In step (4) and step (11), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
The molar ratio that heteropoly acid is introduced in step (4) and step (11) is 4:1 ~ 1:4.
In step (2), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
With SiO in silica support2Molar ratio be 0.05 ~ 0.50.
In step (3), the solid that step (2) obtains is added in the alkaline solution containing ammonia and is impregnated, dip time
Generally 5min ~ 30min；The solid absorption ammonia that step (2) is obtained, adsorption time are generally 5min ~ 30min.Step (3)
In, the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (3), 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.
In step (6), 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 (7), 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 silica support is 2:1 ~ 10:1, preferably 3:1 ~ 10:1.
In step (8), low temperature drying can carry out at room temperature.
In step (9), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
With SiO in silica support2Molar ratio be 0.05 ~ 0.50.
In step (10), the solid that step (9) obtains is added in the alkaline solution containing ammonia and is impregnated, dip time
Generally 5min ~ 30min；The solid absorption ammonia that step (9) is obtained, adsorption time are generally 5min ~ 30min.Step
(10) in, the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (10), the ammonia is using pure ammonia or uses the gaseous mixture containing ammonia, removes ammonia in mixed gas
Outside gas, 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 (2), step (4), step (9) or step (11).
Drying described in step (5) or step (12) and roasting condition are as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then
In 300 DEG C ~ 550 DEG C roasting 2h ~ 6h.Step (5) or step (12) can use identical or different drying and roasting condition.
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 the heteropoly acid ammonium of subsequent load on the surface of the carrier, in this way
Major part ammonium heteropoly acids are made to be dispersed in carrier surface, smaller portions ammonium heteropoly acids are dispersed in carrier duct；Another party
Face, furfural liquid-phase hydrogenatin can generate 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 react with ammonium salt organic acid and generates ammonium heteropoly acids, facilitate heteropoly acid ammonium
Salt is evenly dispersed in carrier surface, and can remove above-mentioned carbon deposit through subsequent high-temperature roasting, effectively remains this portion in this way
Fractional bearer acidic site.The catalyst that the method for the present invention obtains not only has that low temperature active is high, selectivity is good, has strong anti-carbon capacity
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 31.1g nickel nitrate, 108.6g cetyl trimethylammonium bromide and 153g citric acid and is made into mixed solution, it will
225mL tetraethyl orthosilicate is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, by gel 40
DEG C 12 h of aging, then dry 8 h in 580 DEG C of 3 h of roasting obtain silica support, wherein cetyl at 110 DEG C
The molar ratio of trimethylammonium bromide and silica is 0.3, and the molar ratio of citric acid and silica is 0.8.Support are as follows: compare table
Area is 492 m20.60 mL/g of/g, Kong Rongwei, average pore diameter are 4.9 nm.
(2) preparation of catalyst:
Aqueous solution containing 12.0g citric acid is added in 75g carrier, stirring to solution is evaporated at 70 DEG C；It obtains
Material be added in sal volatile and impregnate 10min, it is dry at 60 DEG C after filtering；It is then added to containing 8.6g phosphotungstic acid
Aqueous solution in, stirring is evaporated to solution 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 burnt, catalyst precarsor A is made, is then added in autoclave, 400 DEG C is warming up under hydrogen atmosphere,
4h is handled under 0.3MPa, is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusts Hydrogen Vapor Pressure
To 3MPa, 3h is reacted at 150 DEG C, after reaction, catalyst filtration is come out, at 40 DEG C dry to carrier surface without
Liquid phase；It is then added in the aqueous solution containing 24.0g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material adds
Enter and impregnates 10min into sal volatile, it is dry at 40 DEG C after filtering；It is then added to containing the water-soluble of 17.3g phosphotungstic acid
In liquid, stirring to solution is evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 then are roasted at 520 DEG C
(NH is made in h4)0.2H2.8PW12O40-NiO/SiO2Catalyst, wherein NiO content is 10wt%, (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
8 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 2
(1) preparation of carrier:
It weighs 38.9g nickel nitrate, 170g cetyl trimethylammonium bromide and 89.6g citric acid and is made into mixed solution, it will
212mL tetraethyl orthosilicate is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, by gel 40
12 h of aging at DEG C, then dry 8 h, compression molding obtain silica support in 600 DEG C of 3 h of roasting at 110 DEG C,
The molar ratio of middle cetyl trimethylammonium bromide and silica is 0.5, and the molar ratio of citric acid and silica is 0.5.Carrier
Property are as follows: specific surface area is 520 m20.65 mL/g of/g, Kong Rongwei, average pore diameter are 5.0 nm.
(2) preparation of catalyst:
Aqueous solution containing 28.8g citric acid is added in 72g carrier, stirring to solution is evaporated at 70 DEG C；It obtains
Material be added in sal volatile and impregnate 10min, it is dry at 60 DEG C after filtering；It is then added to containing 14.5g phosphorus tungsten
In the aqueous solution of acid, stirring to solution is evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0 h, then at 400 DEG C
3.0 h are roasted, catalyst precarsor A is made, is then added in autoclave, 450 DEG C is warming up under hydrogen atmosphere,
4h is handled under 0.3MPa, is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusts Hydrogen Vapor Pressure
To 3MPa, 2h is reacted at 160 DEG C, after reaction, catalyst filtration is come out, and is dried at 40 DEG C to carrier surface aneroid
Phase；It is then added in the aqueous solution containing 28.8g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material is added
10min is impregnated into sal volatile, it is dry at 40 DEG C after filtering；It is then added to the aqueous solution containing 14.5g phosphotungstic acid
In, stirring to solution is evaporated at 40 DEG C；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 11wt%, (NH4)0.5H2.5PW12O40Content is
28wt%。
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 3
(1) preparation of carrier:
It weighs 46.7g nickel nitrate, 258g cetyl trimethylammonium bromide and 51.0g citric acid and is made into mixed solution, it will
201mL tetraethyl orthosilicate is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, by gel 40
12 h of aging at DEG C, then dry 8 h, compression molding obtain silica support in 600 DEG C of 3 h of roasting at 110 DEG C,
The molar ratio of middle cetyl trimethylammonium bromide and silica is 0.8, and the molar ratio of citric acid and silica is 0.3.Carrier
Property are as follows: specific surface area is 560 m20.72 mL/g of/g, Kong Rongwei, average pore diameter are 5.1 nm.
(2) preparation of catalyst:
Aqueous solution containing 52.3g citric acid is added in 70g silica support, will stir to solution and steam at 70 DEG C
It is dry；Obtained material, which is added in sal volatile, impregnates 10min, dry at 60 DEG C after filtering；Be then added to containing
In the aqueous solution of 20.7g phosphotungstic acid, stirring to solution is evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0 h, so
Afterwards in 400 DEG C of 3.0 h of roasting, catalyst precarsor A is made, is then added in autoclave, is warming up to 450 under hydrogen atmosphere
DEG C, 4h is handled at 0.3MPa, is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusts hydrogen
Pressure reacts 3h at 150 DEG C, after reaction, catalyst filtration is come out, dry at 40 DEG C to carrier surface to 3MPa
Without liquid phase；It is then added in the aqueous solution containing 26.2g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material
It is added in sal volatile and impregnates 10min, it is dry at 40 DEG C after filtering；It is then added to the water containing 10.4g phosphotungstic acid
In solution, stirring to solution is evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 then are roasted at 470 DEG C
(NH is made in h4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.7H2.3PW12O40Content is
30wt%。
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 628g P123, with embodiment 3, gained is urged for remaining
Agent is (NH4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.7H2.3PW12O40Content is
30wt%, P123 and SiO2Molar ratio be 0.1.Support are as follows: specific surface area is 540 m20.74 mL/g of/g, Kong Rongwei is put down
Equal bore dia is 5.5 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, 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)0.7H3.3SiW12O40-
NiO/SiO2, wherein NiO content is 12wt%, (NH4)0.7H3.3SiW12O40Content is 30wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 6
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 31.1g 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 30wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
In embodiment 3, catalyst precarsor A is added in C6 alkane solvent, impregnates 10min, then filters, at 40 DEG C
Lower drying is to carrier surface without liquid phase；It is then added in the aqueous solution containing 26.2g citric acid, stirs at 40 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, dry at 40 DEG C after filtering；Be then added to containing
In the aqueous solution of 10.4g phosphotungstic acid, stirring to solution is evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, so
Afterwards in 470 DEG C of 3.0 h of roasting, (NH is made4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%,
(NH4)0.7H2.3PW12O40Content is 30wt%.
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 | 98.9 | 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 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 6 | 98.6 | 98.3 |
| Comparative example 3 | 83.1 | 82.1 |
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 (16)
1. a kind of preparation method of heteropoly acid ammonium catalyst, comprising:
(1) silica support containing auxiliary agent nickel is prepared；
(2) silica support of step (1) is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(3) material that step (2) obtains is added in the alkaline solution containing ammonium, it is dry at 40 DEG C ~ 90 DEG C through filtering；Or
The material that step (2) obtains is adsorbed ammonia at 40 DEG C ~ 90 DEG C by person；
(4) aqueous solution of heteropoly acid is added in the material that step (3) obtains, heating stirring to solution is evaporated；
(5) catalyst precarsor A is made through dry and roasting in the solid for obtaining step (4)；
(6) the catalyst precarsor A of step (5) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(7) 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；
(8) material filtering after reaction in step (7) is come out, low temperature drying to sample surfaces is without liquid phase, before obtaining catalyst
Body B；
(9) the catalyst precarsor B that step (8) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
(10) the catalyst precarsor C that step (9) obtains is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
It is dry；Or the catalyst precarsor C that step (9) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(11) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (10) obtains, heating stirring to solution is evaporated；
(12) solid for obtaining step (11) is through dry and roasting to get catalyst；
Wherein, the molar ratio of heteropoly acid is introduced as 4:1 ~ 1:4 in step (4) and step (11)；In step (2), the organic acid
For one of citric acid, tartaric acid, malic acid or a variety of；SiO in the organic acid and silica support2Molar ratio be
0.05~0.50；In step (9), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of；Described is organic
Acid and SiO in silica support2Molar ratio be 0.05 ~ 0.50.
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% ~ 45%, and for auxiliary agent in terms of oxide, the content of nickel oxide is 3%
~ 15%, the content of silica is 40% ~ 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 according to claim 2, it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acids
Content be 15% ~ 40%, for auxiliary agent in terms of oxide, the content of nickel oxide is 3% ~ 15%, and the content of silica is 45% ~ 82%.
4. preparation method according to claim 1 or 2, it is characterised in that: contain boron in silica support, with oxide
Meter, weight content in the catalyst are 6% or less.
5. preparation method according to claim 1 or 2, it is characterised in that: contain iron in silica support, with three oxidations two
Iron meter, weight content in the catalyst are 10% or less.
6. preparation method described in accordance with the claim 1, it is characterised in that the property of silica support described in step (1) is such as
Under: specific surface area is 420 ~ 780 m20.52 ~ 0.82 mL/g of/g, Kong Rongwei, average pore diameter are 4.2 ~ 6.3 nm.
7. according to preparation method described in claim 1 or 6, it is characterised in that the preparation of silica support described in step (1)
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 support；
Wherein auxiliary agent nickel introduces in any step or a few steps in step A, step B, step C；In step A organic acid be citric acid,
One of tartaric acid, malic acid are a variety of, and the organic acid and step B silicon source are with SiO2The molar ratio of meter is 0.1 ~ 1.2.
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: in step B, the silicon source be ethyl orthosilicate,
One of silica solution is a variety of.
10. preparation method described in accordance with the claim 1, it is characterised in that: in step (4) and step (11), described is miscellaneous more
Acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
11. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), the material that step (2) obtains is added
Enter and impregnated into the alkaline solution containing ammonium, dip time is 5min ~ 30min；The material that step (2) is obtained adsorbs ammonia
Gas, adsorption time are 5min ~ 30min；In step (3), the alkaline solution containing ammonium is ammonium hydroxide, sal volatile, carbonic acid
One of hydrogen ammonium salt solution is a variety of.
12. preparation method described in accordance with the claim 1, it is characterised in that: in step (6), the reduction treatment process is such as
Under: catalyst precarsor A 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 (7), 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 silica support are 2:1 ~ 10:1.
14. preparation method according to claim 13, it is characterised in that: in step (7), the quality of the furfuryl aldehyde solution
Concentration is 5%~30%, and the additional amount of furfural and the mass ratio of step (1) resulting silica support are 3:1 ~ 10:1.
15. preparation method described in accordance with the claim 1, it is characterised in that: in step (10), catalysis that step (9) is obtained
Agent precursor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is 5min ~ 30min；It is urged what step (9) obtained
Agent precursor C adsorbs ammonia, and adsorption time is 5min ~ 30min；In step (10), the alkaline solution containing ammonium be ammonium hydroxide,
One of sal volatile, ammonium bicarbonate soln are a variety of.
16. preparation method described in accordance with the claim 1, it is characterised in that: drying and roasting described in step (5) or step (12)
The condition of burning is as follows: 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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