CN106944143B - 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 methods.The catalyst includes active component, auxiliary agent and carrier component, active component is heteropoly acid and ammonium heteropoly acids, auxiliary agent is nickel oxide, carrier component is the molecular sieve of amorphous silica-alumina cladding, and preparation method is that carrier is successively loaded to organic acid, the alkaline solution containing ammonium or ammonia, heteropoly acid and auxiliary agent, obtains catalyst precarsor, again after the processing of reduction treatment, polyalcohol and/or furfurol reaction, heteropoly acid solution is soaked, through dry and roasting, obtains catalyst.The catalyst of the method for the present invention preparation, the active component on surface is based on acid relatively stronger heteropoly acid and its ammonium salt, active component in duct is based on acid relatively weak ammonium heteropoly acids, catalyst improves the stability of catalyst while low temperature active with higher, selectivity and coking resistivity.Catalyst of the present invention is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material.
Description
Technical field
The invention discloses a kind of heteropoly acid ammonium type catalyst and its preparation methods, raw for ethanol dehydration more particularly to one kind
Produce the heteropoly acid ammonium type catalyst and its preparation method 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 heteropoly acid ammonium type catalyst and its systems
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 type catalyst, comprising:
(1) molecular sieve carrier is prepared；
(2) molecular sieve carrier of amorphous silica-alumina cladding is prepared；
(3) carrier that step (2) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(4) material that step (3) 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 (1) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C；
(5) in the material for obtaining auxiliary agent nickel and loaded by heteropoly acid to step (4), heating stirring to solution is evaporated；
(6) catalyst precarsor A is made through dry and roasting in the solid for obtaining step (5)；
(7) the catalyst precarsor A of step (6) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(8) polyalcohol and/or furfuryl aldehyde solution are added in autoclave, then adjusting Hydrogen Vapor Pressure to 2~4MPa,
0.5h~5.0h is reacted at 100 DEG C~300 DEG C；
(9) material filtering after reaction in step (8) is come out, low temperature drying to sample surfaces is catalyzed without liquid phase
Agent precursor B；
(10) aqueous solution of heteropoly acid is added in the catalyst precarsor B that step (9) obtains, heating stirring to solution is steamed
It is dry；
(11) solid for obtaining step (10) is through dry and roasting to get catalyst.
The heteropoly acid ammonium type catalyst that the method for the present invention obtains, including active component, auxiliary agent and carrier component, active component
To see formula (1) for heteropoly acid and ammonium heteropoly acids, auxiliary agent is nickel oxide, and carrier component is the molecular sieve of amorphous silica-alumina cladding,
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 of polyacid and ammonium heteropoly acids in terms of heteropoly acid is 5% ~ 30%, preferably 10% ~ 25%, and 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, 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.
The molecular sieve is hydrogen type molecular sieve, selected from one of ZSM-5,4A, 5A or a variety of, preferably ZSM-5.Institute
The property for stating molecular sieve is as follows: SiO2/Al2O3Molar ratio is 25 ~ 300.
In the amorphous silica-alumina, the weight content of silica is the % of 15 % ~ 50.
In step (1), the molecular sieve carrier is to be obtained by dry powder through molding, drying and roasting.The molecular sieve
Conventional method can be used to be made, it is possible to use the commercial product directly bought.The roasting condition: maturing temperature is 400 DEG C
~ 700 DEG C, calcining time is the h of 2 h ~ 6.The shape of molecular sieve carrier generally uses spherical shape, partial size 0.1 mm ~ 0.5 mm.
In step (2), the molecular sieve carrier of the amorphous silica-alumina cladding is prepared using rolling balling method, and method is such as
Under: the molecular sieve prepared in step (1) is put into bowling machine, be equably sprinkled into during scrolling amorphous silica-alumina dry powder and
Binder is sprayed into, carrier is made constantly to grow up.Carrier after balling-up 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.In step (2), the binder is the dilute acid soln that mass concentration is the % of 5 % ~ 10, such as second
One of acid, nitric acid are a variety of.The additional amount of binder and the mass ratio of amorphous silica-alumina dry powder are 0.5 ~ 1.5.
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, for example be impregnated
Method.
In step (3), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
Mass ratio with step (2) resulting vehicle is 0.1 ~ 0.4.
In step (4), the solid that step (3) obtains is added in the alkaline solution containing ammonia and is impregnated, dip time
Generally 5min ~ 30min；The solid absorption ammonia that step (3) is obtained, adsorption time are generally 5min ~ 30min.Step (4)
In, the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (4), 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 (5), the method on auxiliary agent nickel and loaded by heteropoly acid to carrier can be used into conventional infusion process, such as
It is saturated infusion process.After immersion, as follows using conventional drying and roasting process, drying condition: in 90 DEG C ~ 120 DEG C dryings
3h ~ 12h, roasting condition are as follows: in 300 DEG C ~ 500 DEG C roasting 2 h ~ 6 h.In step (5), nickel source can be using soluble nickel
One of salt, generally nickel nitrate, nickel acetate are a variety of.
In step (5) and step (10), 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 (5) and step (10) is 4:1 ~ 1:4.
In step (7), 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 (8), the polyalcohol is one of C5~C10 polyalcohol or a variety of, preferably xylitol, sorb
One of alcohol, mannitol, arabite are a variety of；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably
It is 5%~30%, the mass ratio of the additional amount of polyalcohol and/or furfural and catalyst precarsor A are 2:1 ~ 10:1, preferably 3:1 ~
10:1。
In step (9), low temperature drying can carry out at room temperature.
The temperature of heating stirring is generally 40~90 DEG C in step (3), step (5) or step (10).
Step (6) or step (11) 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 dry and roasting condition may be the same or different.
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.
In the method for the present invention, suitable amorphous silica-alumina is coated in molecular sieve surface, its specific surface area, aperture can be increased
And Kong Rong, can load more heteropoly acids (ammonium), so not but not change molecular sieve carrier whole pore structure, and
And be conducive to improve the total acid content of catalyst.The present invention utilize auxiliary agent nickel hydrogenation, in autoclave catalytic polyol and/
Or furfural liquid-phase hydrogenatin, mainly there are two aspect effects: one is the liquid alkane that polyalcohol and/or furfural liquid-phase hydrogenatin generate is inhaled
It is attached effectively to block the duct of carrier on a catalyst support, it is distributed the heteropoly acid of subsequent load on the surface of the carrier,
Make the active component on surface based on acid relatively stronger heteropoly acid and its ammonium salt in this way, the active component in duct is with acid
Based on the relatively weak ammonium heteropoly acids of property；On the other hand, polyalcohol and/or furfural liquid-phase hydrogenatin can generate product on carrier
Carbon makes the heteropoly acid of subsequent load and the declines of carrier, reduces acid loss, and can remove through subsequent high-temperature roasting
Above-mentioned carbon deposit is removed, effectively remains this Component Vectors acidic site in this way.The catalyst that the method for the present invention obtains not only has low
Warm activity is high, selectivity is good, the characteristics of having strong anti-carbon capacity, 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 is 0.2mm spherical shape HZSM-5 molecular sieve (SiO by the partial size prepared2/Al2O3Molar ratio is 60) to be added to spin
In machine, bowling machine is started, amorphous silica-alumina dry powder (in terms of butt, silica content 20wt%) is equably sprinkled into machine, together
When spray into the acetic acid aqueous solution that mass concentration is 6%, after balling-up, by carrier at 40 DEG C dry 12 h, then at 500 DEG C
3 h are roasted, obtain the HZSM-5 molecular sieve carrier of amorphous silica-alumina cladding, wherein amorphous silica-alumina accounts for HZSM-5 molecular sieve
20%.
(2) preparation of catalyst:
Aqueous solution containing 13.3g citric acid is added in 83g silica support, stirring to solution steams 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 mixed aqueous solution of 19.5g nickel nitrate and 4.1g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, obtained solid is existed
Catalyst precarsor A is made then in 500 DEG C of 3.0 h of roasting in 110 DEG C of 8.0 h of drying.It is anti-that catalyst precarsor A is added to high pressure
It answers in kettle, 400 DEG C is warming up under hydrogen atmosphere, handle 4h at 0.3MPa, be down to reaction temperature, 400g mass concentration is added
For 20% sorbitol solution, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction, by catalyst
It filters out, dries at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 8.3g 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 400 DEG C of 3.0 h of roasting, catalysis is made
Agent, wherein NiO content is 5wt%, and phosphotungstic acid and its amounts of ammonium salt are 12wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
5h-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 is 0.3mm spherical shape HZSM-5 molecular sieve (SiO by the partial size prepared2/Al2O3Molar ratio is 100) to be added to spin
In machine, bowling machine is started, amorphous silica-alumina dry powder (in terms of butt, silica weight content 30%) is equably sprinkled into machine,
The acetic acid aqueous solution that mass concentration is 6% is sprayed into simultaneously, after balling-up, carrier is dried into 12h at 40 DEG C, then at 500 DEG C
3h is roasted, obtains the HZSM-5 molecular sieve carrier of amorphous silica-alumina cladding, wherein amorphous silica-alumina accounts for HZSM-5 molecular sieve
30%.
(2) preparation of catalyst:
Aqueous solution containing 28.8g citric acid is added in 72g silica support, stirring to solution steams 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 mixed aqueous solution of 39.0g nickel nitrate and 9.3g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, obtained solid is existed
Catalyst precarsor A is made then in 470 DEG C of 3.0 h of roasting in 110 DEG C of 8.0 h of drying.It is anti-that catalyst precarsor A is added to high pressure
It answers in kettle, 400 DEG C is warming up under hydrogen atmosphere, handle 4h at 0.3MPa, be down to reaction temperature, 400g mass concentration is added
For 20% furfuryl aldehyde solution, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 150 DEG C, after reaction, by catalyst mistake
It filters out and, dry at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 9.3g phosphotungstic acid, at 70 DEG C
Stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of 3.0 h of roasting, catalyst is made,
Wherein NiO content is 10wt%, and phosphotungstic acid and its amounts of ammonium salt are 18wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
6h-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 is 0.4mm spherical shape HZSM-5 molecular sieve (SiO by the partial size prepared2/Al2O3Molar ratio is 150) to be added to spin
In machine, bowling machine is started, amorphous silica-alumina dry powder (in terms of butt, silica content 40wt%) is equably sprinkled into machine, together
When spray into the acetic acid aqueous solution that mass concentration is 6%, after balling-up, by carrier at 40 DEG C dry 12 h, then at 500 DEG C
3 h are roasted, obtain the HZSM-5 molecular sieve carrier of amorphous silica-alumina cladding, wherein amorphous silica-alumina accounts for HZSM-5 molecular sieve
40%.
(2) preparation of catalyst:
Aqueous solution containing 46.3g citric acid is added in 62g silica support, stirring to solution steams 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 mixed aqueous solution of 54.6g nickel nitrate and 16.6g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, obtained solid is existed
Catalyst precarsor A is made then in 520 DEG C of 3.0 h of roasting in 110 DEG C of 8.0 h of drying.It is anti-that catalyst precarsor A is added to high pressure
It answers in kettle, 400 DEG C is warming up under hydrogen atmosphere, handle 4h at 0.3MPa, be down to reaction temperature, 400g mass concentration is added
For 20% sorbitol solution, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction, by catalyst
It filters out, dries at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 8.3g 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 400 DEG C of 3.0 h of roasting, catalysis is made
Agent, wherein NiO content is 14wt%, and phosphotungstic acid and its amounts of ammonium salt are 24wt%.
(3) 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, 230 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, HZSM-5 is changed to 4A molecular sieve, phosphotungstic acid is changed to silico-tungstic acid, and citric acid is changed to tartaric acid, wine
The mass ratio of stone acid and carrier is 0.35, and catalyst is made with embodiment 3 in remaining, and wherein NiO content is 14wt%, silico-tungstic acid and
Its amounts of ammonium salt is 24wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Embodiment 5
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, carrier is added directly into the mixed aqueous solution containing 54.6g nickel nitrate and 24.8g phosphotungstic acid
In, stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, then in 350 DEG C of 3.0 h of roasting,
Catalyst is made, wherein NiO content is 14wt%, H3PW12O40Content is 24wt%.
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, the dosage for adjusting HZSM-5 dry powder and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecule
The 5% of weight is sieved, catalyst is made with embodiment 3 in remaining, and wherein NiO content is 14wt%, and phosphotungstic acid and its amounts of ammonium salt are
24wt%。
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 3
In embodiment 3, the dosage for adjusting HZSM-5 dry powder and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecule
The 70% of weight is sieved, catalyst is made with embodiment 3 in remaining, and wherein NiO content is 14wt%, and phosphotungstic acid and its amounts of ammonium salt are
24wt% 。
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 4
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 8.3g phosphotungstic acid, stirs at 70 DEG C to solution
It 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, catalyst is made, wherein NiO content
For 14wt%, phosphotungstic acid and its amounts of ammonium salt are 24wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 5
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 | 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 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 5 | 99.2 | 99.3 |
| Comparative example 5 | 83.0 | 82.5 |
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 (19)
1. a kind of preparation method of heteropoly acid ammonium type catalyst, comprising:
(1) molecular sieve carrier is prepared；
(2) molecular sieve carrier of amorphous silica-alumina cladding is prepared；
(3) carrier that step (2) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(4) material that step (3) 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 (3) obtains is adsorbed ammonia at 40 DEG C ~ 90 DEG C by person；
(5) in the material for obtaining auxiliary agent nickel and loaded by heteropoly acid to step (4), heating stirring to solution is evaporated；
(6) catalyst precarsor A is made through dry and roasting in the solid for obtaining step (5)；
(7) the catalyst precarsor A of step (6) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(8) polyalcohol and/or furfuryl aldehyde solution are added in autoclave, then adjust Hydrogen Vapor Pressure to 2~4MPa, at 100 DEG C
0.5h~5.0h is reacted at~300 DEG C；
(9) material filtering after reaction in step (8) is come out, low temperature drying to sample surfaces is without liquid phase, before obtaining catalyst
Body B；
(10) aqueous solution of heteropoly acid is added in the catalyst precarsor B that step (9) obtains, heating stirring to solution is evaporated；
(11) solid for obtaining step (10) is through dry and roasting to get catalyst；
Wherein, the molar ratio of heteropoly acid is introduced as 4:1 ~ 1:4 in step (5) and step (10)；In step (3), the organic acid
For one of citric acid, tartaric acid, malic acid or a variety of；The organic acid and the mass ratio of step (2) resulting vehicle are
0.1~0.4；In step (8), the polyalcohol is one of C5~C10 polyalcohol or a variety of；Polyalcohol and/or furfural are molten
The mass concentration of liquid is 5%~35%, and the mass ratio of the additional amount and catalyst precarsor A of polyalcohol and/or furfural is 2:1 ~ 10:1.
2. preparation method described in accordance with the claim 1, it is characterised in that: the heteropoly acid ammonium type catalyst, including activity
Component, auxiliary agent and carrier component, heteropoly acid and ammonium heteropoly acids are shown in formula (1) that auxiliary agent is nickel oxide, and carrier component is amorphous silicon
The molecular sieve of aluminium cladding, wherein the weight of amorphous silica-alumina accounts for the 15% ~ 45% of molecular sieve；Using the weight of catalyst as base
The content of standard, heteropoly acid and ammonium heteropoly acids in terms of heteropoly acid is 5% ~ 30%, and the content of nickel oxide is 3% ~ 15%, and silica contains
Amount is 55% ~ 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: in the carrier, the weight of amorphous silica-alumina is accounted for
The 20% ~ 40% of molecular sieve.
4. preparation method described in accordance with the claim 1, it is characterised in that: on the basis of the weight of catalyst, heteropoly acid and miscellaneous
Content of the polyacid ammonium salt in terms of heteropoly acid is 10% ~ 25%, and auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 15%, silica
Content be 60% ~ 87%.
5. preparation method according to claim 1 or 2, it is characterised in that: contain boron in catalyst precarsor A, with oxide
Meter, weight content in the catalyst are 6% or less.
6. preparation method according to claim 1 or 2, it is characterised in that: contain iron in catalyst precarsor A, with three oxidations
Two iron meters, weight content in the catalyst are 10% or less.
7. preparation method according to claim 1 or 2, it is characterised in that: the molecular sieve is hydrogen type molecular sieve, is selected from
One of ZSM-5,4A, 5A or a variety of；The property of the molecular sieve is as follows: SiO2/Al2O3Molar ratio is 25 ~ 300.
8. preparation method according to claim 1 or 2, it is characterised in that: the shape of molecular sieve carrier is using spherical, grain
Diameter 0.1 mm ~ 0.5 mm.
9. preparation method described in accordance with the claim 1, it is characterised in that: in step (2), the amorphous silica-alumina cladding
Molecular sieve carrier is prepared using rolling balling method, the method is as follows: the molecular sieve prepared in step (1) is put into bowling machine,
It is equably sprinkled into amorphous silica-alumina dry powder in rolling process and sprays into binder, so that carrier is constantly grown up, the load after balling-up
Body is dried at room temperature for the h of 3 h ~ 24, then in 400 DEG C ~ 700 DEG C roasting 2 h ~ 6 h；The binder is mass concentration
For 5% ~ 10% dilute acid soln, the additional amount of binder and the mass ratio of amorphous silica-alumina dry powder are 0.5 ~ 1.5.
10. preparation method according to claim 9, it is characterised in that: siliconoxide mass contains in the amorphous silica-alumina
Amount is the % of 15 % ~ 50.
11. preparation method described in accordance with the claim 1, it is characterised in that: in step (4), the material that step (3) obtains is added
Enter and impregnated into the alkaline solution containing ammonium, dip time is 5min ~ 30min；The material that step (3) is obtained adsorbs ammonia
Gas, adsorption time are 5min ~ 30min；In step (4), 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 (5), by auxiliary agent nickel and loaded by heteropoly acid
Method on to carrier uses infusion process, after immersion, as follows using dry and roasting condition: in 90 DEG C ~ 120 DEG C dry 3h
~ 12h, in 300 DEG C ~ 500 DEG C roasting 2 h ~ 6 h.
13. preparation method described in accordance with the claim 1, it is characterised in that: in step (5) and step (10), described is miscellaneous more
Acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
14. preparation method described in accordance with the claim 1, it is characterised in that: in step (7), 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.
15. preparation method described in accordance with the claim 1, it is characterised in that: in step (8), polyalcohol and/or furfuryl aldehyde solution
Mass concentration is 5%~30%, and the mass ratio of the additional amount and catalyst precarsor A of polyalcohol and/or furfural is 3:1 ~ 10:1.
16. preparation method described in accordance with the claim 1, it is characterised in that: step (6) or step (11) drying and roasting
Condition is as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, in 300 DEG C ~ 550 DEG C roasting 2h ~ 6h.
17. a kind of heteropoly acid ammonium type catalyst, it is characterised in that: any method preparation of claim 1~16.
18. a kind of method of producing ethylene from dehydration of ethanol, it is characterised in that: using the catalyst described in claim 17.
19. according to the method for claim 18, it is characterised in that: this method is adopted using low-concentration ethanol aqueous solution as raw material
Reaction condition with fixed-bed process, the preparing ethylene by dehydrating ethanol is as follows: ethanol water concentration is 5wt% ~ 40wt%,
0.5 h of mass space velocity-1~15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
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| CN102295511A (en) * | 2011-07-01 | 2011-12-28 | 华东理工大学 | Novel catalysis technology for preparing long chain alkane from biomass derivative furfural or HMF |
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| CN102295511A (en) * | 2011-07-01 | 2011-12-28 | 华东理工大学 | Novel catalysis technology for preparing long chain alkane from biomass derivative furfural or HMF |
| CN104588105A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method of catalyst used for producing dimethyl ether through methanol dehydration |
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