CN106944143A - heteropoly acid ammonium type catalyst and its preparation method - Google Patents
heteropoly acid ammonium type catalyst and its preparation method Download PDFInfo
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Abstract
The invention discloses a kind of heteropoly acid ammonium type catalyst and its preparation method.The catalyst includes active component, auxiliary agent and carrier component, active component is heteropoly acid and ammonium heteropoly acidses, auxiliary agent is nickel oxide, carrier component is the molecular sieve that amorphous silica-alumina is coated, and its preparation method is that carrier is loaded to organic acid, the alkaline solution containing ammonium or ammonia, heteropoly acid and auxiliary agent successively, obtains catalyst precarsor, after being handled again through reduction treatment, polyalcohol and/or furfurol reaction, heteropoly acid solution is soaked, through drying and being calcined, catalyst is obtained.Catalyst prepared by the inventive method, the active component on surface is based on acid relatively strong heteropoly acid and its ammonium salt, active component in duct is based on acid relatively weak ammonium heteropoly acidses, catalyst improves the stability of catalyst while with higher low temperature active, selectivity and coking resistivity.It is ethylene reaction produced that catalyst of the present invention is particularly suitable for use in the dehydration that the low-concentration ethanol aqueous solution is raw material.
Description
Technical field
It is more particularly to a kind of to be used for ethanol dehydration life the invention discloses a kind of heteropoly acid ammonium type catalyst and its preparation method
Produce the heteropoly acid ammonium type catalyst and its preparation method 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 heteropoly acid ammonium type catalyst and its system
Method.Catalyst obtained by this method not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and stably
Property is good.
The preparation method of described heteropoly acid ammonium type catalyst, including：
（1）Prepare molecular sieve carrier；
（2）Prepare the molecular sieve carrier of amorphous silica-alumina cladding；
（3）By step（2）Obtained carrier is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated；
（4）By step（3）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（1）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C；
（5）By auxiliary agent nickel and loaded by heteropoly acid to step（4）In obtained material, heating stirring to solution is evaporated；
（6）By step（5）Catalyst precarsor A is made through drying and being calcined in obtained solid；
（7）By step（6）Catalyst precarsor A be added in autoclave, reduction treatment is carried out to it using hydrogen；
（8）Polyalcohol and/or furfuryl aldehyde solution are added in autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, at 100 DEG C
0.5h~5.0h is reacted at~300 DEG C；
（9）By step（8）In reacted material filtering come out, low temperature drying to sample surfaces is obtained before catalyst without liquid phase
Body B；
（10）The aqueous solution of heteropoly acid is added to step（9）In obtained catalyst precarsor B, heating stirring to solution is evaporated；
（11）By step（10）Obtained solid produces catalyst through drying and being calcined.
The heteropoly acid ammonium type catalyst that the inventive method is obtained, including active component, auxiliary agent and carrier component, active component
It is that heteropoly acid and ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier component is the molecular sieve that amorphous silica-alumina is coated, its
The weight of middle amorphous silica-alumina accounts for the 15% ~ 45% of molecular sieve, preferably 20% ~ 40%；It is miscellaneous on the basis of the weight of catalyst
The content that polyacid and ammonium heteropoly acidses are counted using heteropoly acid is 5% ~ 30%, and preferably 10% ~ 25%, auxiliary agent is in terms of oxide, nickel oxide
Content be 3% ~ 15%, the content of silica is 55% ~ 92%, preferably 60% ~ 87%；
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.
Described molecular sieve is hydrogen type molecular sieve, the preferably one or more in ZSM-5,4A, 5A, ZSM-5.Institute
The property for stating molecular sieve is as follows：SiO2/Al2O3Mol ratio is 25 ~ 300.
In described amorphous silica-alumina, the weight content of silica is the % of 15 % ~ 50.
Step（1）In, described molecular sieve carrier is to be obtained by dry powder through shaping, dry and roasting.Described molecular sieve
It can be made using conventional method, it is possible to use the commercial product directly bought.Described roasting condition：Sintering temperature is 400 DEG C
~ 700 DEG C, roasting time is the h of 2 h ~ 6.The shape of molecular sieve carrier is typically using spherical, the mm of its particle diameter 0.1 mm ~ 0.5.
Step（2）In, the molecular sieve carrier of described amorphous silica-alumina cladding is prepared using rolling balling method, and method is such as
Under：By step（1）The molecular sieve of middle preparation is put into bowling machine, be equably sprinkled into rolling process amorphous silica-alumina dry powder and
Binding agent is sprayed into, carrier is constantly grown up.Carrier after balling-up is finished is dried at room temperature for the h of 3 h ~ 24, then 400 DEG C ~
700 DEG C of roasting 2 h ~ 6 h.Step（2）In, described binding agent is the dilute acid soln that mass concentration is the % of 5 % ~ 10, such as second
One or more in acid, nitric acid.The addition of binding agent is 0.5 ~ 1.5 with the mass ratio of amorphous silica-alumina dry powder.
In the inventive method, it may be incorporated into other adjuvant components in catalyst precarsor A, 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 catalyst precarsor A
Meter, weight content in the catalyst is less than 10%.
In the inventive method, other adjuvant components can be introduced into catalyst precarsor A using conventional method, such as are impregnated
Method.
Step（3）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid
With step（2）The mass ratio of resulting vehicle is 0.1 ~ 0.4.
Step（4）In, by step（3）Obtained solid, which is added in the alkaline solution containing ammonia, to be impregnated, dip time
Generally 5min ~ 30min；By step（3）Obtained solid absorption ammonia, adsorption time is generally 5min ~ 30min.Step（4）
In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（4）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（5）In, the method on auxiliary agent nickel and loaded by heteropoly acid to carrier can be used into conventional infusion process, such as
Saturation infusion process.After immersion, using conventional drying and roasting process, drying condition is as follows：In 90 DEG C ~ 120 DEG C dryings
3h ~ 12h, roasting condition is as follows：The h of 2 h ~ 6 is calcined at 300 DEG C ~ 500 DEG C.Step（5）In, nickel source can be using soluble nickel
One or more in salt, generally nickel nitrate, nickel acetate.
Step（5）And step（10）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（5）And step（10）The middle mol ratio for introducing heteropoly acid is 4:1~1:4.
Step（7）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（8）In, described polyalcohol is the one or more in C5~C10 polyalcohols, preferably xylitol, sorb
One or more in alcohol, mannitol, arabite；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably
For 5%~30%, the addition of polyalcohol and/or furfural is 2 with catalyst precarsor A mass ratio:1~10:1, preferably 3:1~
10:1。
Step（9）In, low temperature drying can be carried out at room temperature.
Step（3）, step（5）Or step（10）The temperature of middle heating stirring is generally 40~90 DEG C.
Step（6）Or step（11）The drying and roasting condition are as follows：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, 300
DEG C ~ 550 DEG C of roasting 2h ~ 6h.Step（6）Or step（11）Use and dry and roasting condition can be with identical, can also be different.
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.
In the inventive method, appropriate amorphous silica-alumina is coated in molecular sieve surface, its specific surface area, aperture can be increased
And pore volume, more heteropoly acids can be loaded（Ammonium）, so not but not change molecular sieve carrier overall pore structure, and
And be conducive to improving the total acid content of catalyst.The present invention using auxiliary agent nickel hydrogenation, in autoclave catalytic polyol and/
Or furfural liquid-phase hydrogenatin, mainly there are two aspect effects：One is polyalcohol and/or the liquid alkane of furfural liquid-phase hydrogenatin generation are inhaled
It is attached effectively to block the duct of carrier on a catalyst support, the heteropoly acid subsequently loaded is distributed on carrier surface,
So make the active component on surface based on acid relatively strong heteropoly acid and its ammonium salt, the active component in duct is with acid
Based on the relatively weak ammonium heteropoly acidses of property；On the other hand, polyalcohol and/or furfural liquid-phase hydrogenatin can produce product on carrier
Carbon, makes the declines of the heteropoly acid and carrier subsequently loaded, reduces acid loss, and can remove through follow-up high-temperature roasting
Above-mentioned carbon deposit is removed, this Component Vectors acidic site is so effectively remained.The catalyst that the inventive method is obtained not only has low
The characteristics of warm activity is high, selectivity is good, carbon accumulation resisting ability is strong, 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：
It is the spherical HZSM-5 molecular sieves (SiO of 0.2mm by the particle diameter prepared2/Al2O3Mol ratio is 60) to be added in bowling machine,
Bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica content 20wt%）, spray simultaneously
Enter the acetic acid aqueous solution that mass concentration is 6%, after balling-up is finished, carrier is dried into 12 h at 40 DEG C, then in 500 DEG C of roastings
3 h, obtain the HZSM-5 molecular sieve carriers of amorphous silica-alumina cladding, and wherein amorphous silica-alumina accounts for HZSM-5 molecular sieves
20%。
（2）The preparation of catalyst：
The aqueous solution containing 13.3g citric acids is added in 83g silica supports, stirs to solution and is evaporated at 70 DEG C；
To material be added in sal volatile and impregnate 10min, dried after filtering at 60 DEG C；It is then added to containing 19.5g nitre
In the mixed aqueous solution of sour nickel and 4.1g phosphotungstic acid, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dryings
8.0 h, are then calcined 3.0 h at 500 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave, hydrogen
400 DEG C are warming up under gas atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the mountain that 400g mass concentrations are 20% is added
Pears alcoholic solution, then adjusts Hydrogen Vapor Pressure to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out,
Dry at room temperature to carrier surface without liquid phase；Be then added in the aqueous solution containing 8.3g phosphotungstic acids, stirred at 70 DEG C to
Solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 400 DEG C, catalyst, wherein NiO is made
Content is 5wt%, and phosphotungstic acid and its amounts of ammonium salt are 12wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol waters, mass space velocity 5h-1, 250 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：
It is the spherical HZSM-5 molecular sieves (SiO of 0.3mm by the particle diameter prepared2/Al2O3Mol ratio is 100) to be added to bowling machine
In, bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica weight content 30%）, together
When spray into mass concentration be 6% acetic acid aqueous solution, after balling-up is finished, by carrier at 40 DEG C dry 12h, then 500 DEG C roasting
3h is burnt, the HZSM-5 molecular sieve carriers of amorphous silica-alumina cladding are obtained, wherein amorphous silica-alumina accounts for HZSM-5 molecular sieves
30%。
（2）The preparation of catalyst：
The aqueous solution containing 28.8g citric acids is added in 72g silica supports, stirs to solution and is evaporated at 70 DEG C；
To material be added in sal volatile and impregnate 10min, dried after filtering at 60 DEG C；It is then added to containing 39.0g nitre
In the mixed aqueous solution of sour nickel and 9.3g phosphotungstic acid, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dryings
8.0 h, are then calcined 3.0 h at 470 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave, hydrogen
400 DEG C are warming up under gas atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, add the chaff that 400g mass concentrations are 20%
Aldehyde solution, then adjusts Hydrogen Vapor Pressure to 3MPa, 3h is reacted at 150 DEG C, after reaction terminates, catalyst filtration is come out, room
Temperature is lower to be dried to carrier surface without liquid phase；It is then added in the aqueous solution containing 9.3g phosphotungstic acids, is stirred at 70 DEG C to molten
Liquid is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 400 DEG C, catalyst is made, wherein NiO contains
Measure as 10wt%, phosphotungstic acid and its amounts of ammonium salt are 18wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol waters, mass space velocity 6h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts
After reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 3
（1）The preparation of carrier：
It is the spherical HZSM-5 molecular sieves (SiO of 0.4mm by the particle diameter prepared2/Al2O3Mol ratio is 150) to be added to bowling machine
In, bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica content 40wt%）, simultaneously
The acetic acid aqueous solution that mass concentration is 6% is sprayed into, after balling-up is finished, carrier is dried into 12 h at 40 DEG C, then in 500 DEG C of roastings
3 h are burnt, the HZSM-5 molecular sieve carriers of amorphous silica-alumina cladding are obtained, wherein amorphous silica-alumina accounts for HZSM-5 molecular sieves
40%。
（2）The preparation of catalyst：
The aqueous solution containing 46.3g citric acids is added in 62g silica supports, stirs to solution and is evaporated at 70 DEG C；
To material be added in sal volatile and impregnate 10min, dried after filtering at 60 DEG C；It is then added to containing 54.6g nitre
In the mixed aqueous solution of sour nickel and 16.6g phosphotungstic acid, stir to solution and be evaporated at 70 DEG C, obtained solid is dry at 110 DEG C
Dry 8.0 h, is then calcined 3.0 h at 520 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave,
400 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, it is 20% to add 400g mass concentrations
Sorbitol solution, then adjusts Hydrogen Vapor Pressure to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is gone out
Come, dry at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 8.3g phosphotungstic acids, is stirred at 70 DEG C
It is evaporated to solution；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 400 DEG C, catalyst is made, wherein
NiO contents are 14wt%, and phosphotungstic acid and its amounts of ammonium salt are 24wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol waters, mass space velocity 8h-1, 230 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts
After reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 4
In embodiment 3, HZSM-5 is changed to 4A molecular sieves, phosphotungstic acid is changed to silico-tungstic acid, and citric acid is changed to tartaric acid, tartaric acid
Mass ratio with carrier is 0.35, remaining be the same as Example 3, catalyst is made, wherein NiO contents are 14wt%, silico-tungstic acid and its ammonium
Salt content is 24wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 5
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, carrier is added directly into the mixed aqueous solution containing 54.6g nickel nitrates and 24.8g phosphotungstic acids,
Stir to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 350 DEG C, is made and urges
Agent, wherein NiO contents are 14wt%, H3PW12O40Content is 24wt%.
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, the consumption of adjustment HZSM-5 dry powder and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecular sieve weights
Catalyst is made, and wherein NiO contents are 14wt%, and phosphotungstic acid and its amounts of ammonium salt are 24wt% in the 5% of amount, remaining be the same as Example 3.
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
In embodiment 3, the consumption of adjustment HZSM-5 dry powder and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecular sieve weights
Catalyst is made, and wherein NiO contents are 14wt%, and phosphotungstic acid and its amounts of ammonium salt are 24wt% in the 70% of amount, remaining be the same as Example 3
。
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 4
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 8.3g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；
By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 520 DEG C, catalyst is made, wherein NiO contents are
14wt%, phosphotungstic acid and its amounts of ammonium salt are 24wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 5
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 | 99.2 | 99.1 |
| Embodiment 2 | 99.1 | 99.0 |
| Embodiment 3 | 99.4 | 99.5 |
| Embodiment 4 | 99.3 | 99.3 |
| Comparative example 1 | 95.4 | 95.6 |
| Comparative example 2 | 92.7 | 92.9 |
| Comparative example 3 | 93.5 | 93.6 |
| Comparative example 4 | 97.0 | 97.1 |
The stability test evaluation result of table 2
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 5 | 99.2 | 99.3 |
| Comparative example 5 | 83.0 | 82.5 |
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 (18)
1. a kind of preparation method of heteropoly acid ammonium type catalyst, including：
（1）Prepare molecular sieve carrier；
（2）Prepare the molecular sieve carrier of amorphous silica-alumina cladding；
（3）By step（2）Obtained carrier is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated；
（4）By step（3）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（1）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C；
（5）By auxiliary agent nickel and loaded by heteropoly acid to step（4）In obtained material, heating stirring to solution is evaporated；
（6）By step（5）Catalyst precarsor A is made through drying and being calcined in obtained solid；
（7）By step（6）Catalyst precarsor A be added in autoclave, reduction treatment is carried out to it using hydrogen；
（8）Polyalcohol and/or furfuryl aldehyde solution are added in autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, at 100 DEG C
0.5h~5.0h is reacted at~300 DEG C；
（9）By step（8）In reacted material filtering come out, low temperature drying to sample surfaces is obtained before catalyst without liquid phase
Body B；
（10）The aqueous solution of heteropoly acid is added to step（9）In obtained catalyst precarsor B, heating stirring to solution is evaporated；
（11）By step（10）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 type catalyst, including active component,
Auxiliary agent and carrier component, heteropoly acid and ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier component is amorphous silica-alumina bag
The weight of the molecular sieve covered, wherein amorphous silica-alumina accounts for the 15% ~ 45% of molecular sieve, preferably 20% ~ 40%；With catalyst
On the basis of weight, the content that heteropoly acid and ammonium heteropoly acidses are counted using heteropoly acid as 5% ~ 30%, auxiliary agent in terms of oxide, nickel oxide
Content is 3% ~ 15%, and the content of silica is 55% ~ 92%；Preferably：On the basis of the weight of catalyst, heteropoly acid and heteropoly acid
The content that ammonium salt is counted using heteropoly acid is 10% ~ 25%, auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 15%, and silica contains
Measure as 60% ~ 87%；
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 catalyst precarsor A, 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 catalyst precarsor A, with di-iron trioxide
Meter, weight content in the catalyst is less than 10%.
5. according to the method described in claim 1 or 2, it is characterised in that：Described molecular sieve is hydrogen type molecular sieve, selected from ZSM-
5th, the one or more in 4A, 5A；The property of the molecular sieve is as follows：SiO2/Al2O3Mol ratio is 25 ~ 300.
6. according to the method described in claim 1 or 2, it is characterised in that：The shape of molecular sieve carrier uses spherical, its particle diameter
0.1 mm~0.5 mm。
7. according to the method described in claim 1 or 6, it is characterised in that：Step（2）In, what described amorphous silica-alumina was coated
Molecular sieve carrier is prepared using rolling balling method, and method is as follows：By step（1）The molecular sieve of middle preparation is put into bowling machine,
Equably be sprinkled into rolling process amorphous silica-alumina dry powder and spray into binding agent, carrier is constantly grown up, balling-up finish after load
Body is dried at room temperature for the h of 3 h ~ 24, and the h of 2 h ~ 6 is then calcined at 400 DEG C ~ 700 DEG C；Described binding agent is mass concentration
For 5% ~ 10% dilute acid soln, the addition of binding agent is 0.5 ~ 1.5 with the mass ratio of amorphous silica-alumina dry powder.
8. in accordance with the method for claim 7, it is characterised in that：Siliconoxide mass content is 15 in described amorphous silica-alumina
%~50 %。
9. in accordance with the method for claim 1, it is characterised in that：Step（3）In, the organic acid be citric acid, tartaric acid,
One or more in malic acid；Described organic acid and step（2）The mass ratio of resulting vehicle is 0.1 ~ 0.4.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）In, by step（3）Obtained solid is added to
Impregnated in alkaline solution containing ammonia, dip time is 5min ~ 30min；By step（3）Obtained solid absorption ammonia, inhales
The attached time is 5min ~ 30min；Step（4）In, the alkaline solution containing ammonium is that ammoniacal liquor, sal volatile, ammonium hydrogen carbonate are molten
One or more in liquid.
11. in accordance with the method for claim 1, it is characterised in that：Step（3）In, by auxiliary agent nickel and loaded by heteropoly acid to carrying
Method on body uses infusion process, after immersion, as follows with roasting condition using drying：90 DEG C ~ 120 DEG C dry 3h ~
12h, the h of 2 h ~ 6 is calcined at 300 DEG C ~ 500 DEG C.
12. in accordance with the method for claim 1, it is characterised in that：Step（5）And step（10）In, described heteropoly acid is
One or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；Step（5）And step（10）The middle mol ratio for introducing heteropoly acid is 4:1
~1:4。
13. in accordance with the method for claim 1, it is characterised in that：Step（7）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（8）In, described polyalcohol is many members of C5~C10
One or more in alcohol；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, polyalcohol
And/or the addition of furfural and catalyst precarsor A mass ratio are 2:1~10:1, preferably 3:1~10:1.
15. in accordance with the method for claim 1, it is characterised in that：Step（6）Or step（11）The drying and roasting condition
It is as follows：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, 2h ~ 6h is calcined at 300 DEG C ~ 550 DEG C.
16. a kind of heteropoly acid ammonium type catalyst, it is characterised in that：It is prepared by any described method of claim 1~15.
17. a kind of method of producing ethylene from dehydration of ethanol, it is characterised in that：Using the catalyst described in claim 16.
18. in accordance with the method for claim 17, it is characterised in that：This method is adopted using the low-concentration ethanol aqueous solution as raw material
With fixed-bed process, the reaction condition of described preparing ethylene by dehydrating ethanol is as follows：Ethanol water concentration is 5wt% ~ 40wt%,
The h of mass space velocity 0.5-1~15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
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| CN108187744A (en) * | 2018-01-27 | 2018-06-22 | 邵阳学院 | A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal |
| CN115155650A (en) * | 2022-08-01 | 2022-10-11 | 浙江医药股份有限公司新昌制药厂 | Catalyst and preparation method and application thereof |
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