CN106944152B - Heteropoly acid ammonium salt catalyst and its preparation method - Google Patents
Heteropoly acid ammonium salt catalyst and its preparation method Download PDFInfo
- Publication number
- CN106944152B CN106944152B CN201610003170.4A CN201610003170A CN106944152B CN 106944152 B CN106944152 B CN 106944152B CN 201610003170 A CN201610003170 A CN 201610003170A CN 106944152 B CN106944152 B CN 106944152B
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- preparation
- molecular sieve
- amorphous silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention discloses a kind of heteropoly acid ammonium salt catalyst and its preparation methods.The catalyst includes active component, auxiliary agent and carrier, and active component is ammonium heteropoly acids, and auxiliary agent is nickel, phosphorus and vanadium, and carrier is the molecular sieve of amorphous silica-alumina cladding, and on the basis of the weight of carrier, auxiliary agent is in terms of oxide, P2O5Content be 3.0% ~ 10.0%, V2O5Content be 0.2% ~ 4.0%, NiO content be 8% ~ 20%；On the basis of the weight of catalyst, the content of ammonium heteropoly acids is 8% ~ 30%, and auxiliary agent is 70% ~ 92% with the total content of carrier in terms of oxide.While catalyst of the present invention low temperature active with higher, selectivity and coking resistivity, the stability of catalyst is improved.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 present invention relates to a kind of heteropoly acid ammonium salt catalyst and its preparation methods, produce more particularly to one kind for ethanol dehydration
The carried heteropoly acid ammonium salt in catalysis agent of ethylene and its preparation method.
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.
CN201310509561.X discloses a kind of ZSM-5 molecular sieve catalyst that heteropoly acid is modified, is used for low concentration second
Dehydration of alcohols is ethylene reaction produced.Catalyst shows higher catalytic activity and selectivity, but due to the specific surface of carrier and
Aperture is relatively small, cannot load more heteropoly acids, and excessive heteropoly acid can block the duct of carrier, lead to catalyst activity
Decline, therefore further increasing which limit catalyst activity.
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] reports entitled MCM-41 load Catalyzed by Silicotungstic Acid
The article of producing ethylene from dehydration of ethanol, catalyst are prepared using infusion process.CN200910057539.X discloses a kind of ethanol dehydration
The catalyst of ethylene processed.For the catalyst using aluminium oxide as carrier, active component is heteropoly acid, is prepared using kneading method.It is above-mentioned to urge
Agent shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but working as with low-concentration ethanol is original
When 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 salt catalyst and its systems
Method.The catalyst not only has the characteristics that low temperature active is high, selectivity is good, has strong anti-carbon capacity, and stability is good.
Heteropoly acid ammonium salt catalyst of the present invention, including active component, auxiliary agent and carrier, active component are shown in for ammonium heteropoly acids
Formula (1), auxiliary agent are nickel, phosphorus and vanadium, and carrier is the molecular sieve of amorphous silica-alumina cladding；The weight of amorphous silica-alumina accounts for molecular sieve weight
The 15% ~ 45% of amount, preferably 20% ~ 40%；On the basis of the weight of carrier, auxiliary agent is in terms of oxide, P2O5Content be 3.0% ~
10.0%, V2O5Content be 0.2% ~ 4.0%, NiO content be 8% ~ 20%；On the basis of the weight of catalyst, ammonium heteropoly acids
Content be 8% ~ 30%, preferably 12% ~ 25%, auxiliary agent in terms of oxide with the total content of carrier be 70% ~ 92%, preferably 75% ~
88%；
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 one of ZSM-5,4A, 5A or a variety of, preferably ZSM-5.The molecular sieve is Hydrogen
Molecular sieve, property are as follows: SiO2/Al2O3Molar ratio is 25 ~ 300.
In the heteropoly acid ammonium salt catalyst, ammonium heteropoly acids are distributed in the outer surface of carrier.
The preparation method of the heteropoly acid ammonium salt catalyst, comprising:
(1) molecular sieve carrier of amorphous silica-alumina cladding is prepared；
(2) auxiliary agent nickel, phosphorus and vanadium are loaded on the molecular sieve carrier of amorphous silica-alumina cladding, obtains catalyst precarsor A；
(3) the resulting catalyst precarsor A of step (2) is added in autoclave, it is restored using hydrogen
Processing；
(4) polyalcohol and/or furfuryl aldehyde solution are added in autoclave, then adjusting Hydrogen Vapor Pressure to 2~4MPa,
0.5~5.0h is reacted at 100~300 DEG C；
(5) product that step (4) reaction obtains, through drying to sample surfaces under low temperature without liquid phase, is catalyzed through filtering
Agent precursor B；
(6) the catalyst precarsor B that step (5) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(7) material that step (6) 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 (6) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C；
(8) heteropoly acid aqueous solution is added in the material that step (7) obtains, heating stirring to solution is evaporated；
(9) solid for obtaining step (8) is through dry and roasting to get catalyst.
In step (1), the molecular sieve carrier of the amorphous silica-alumina cladding can be prepared as follows: will first divide
Carrier is made in son sieve, then amorphous silica-alumina is coated on to the surface of molecular sieve carrier using rolling balling method.Molecular sieve carrier is
It is obtained by molecular sieve dry powder through molding, drying and roasting.The molecular sieve can be used conventional method and be made, it is possible to use directly
The commercial product bought.The roasting condition: maturing temperature is 400 DEG C ~ 700 DEG C, and calcining time is the h of 2 h ~ 6.Molecule
The shape of sieve carrier generally uses spherical shape, partial size 0.1 mm ~ 0.5 mm.Amorphous silica-alumina is coated on using rolling balling method
The method on the surface of molecular sieve carrier is as follows: molecular sieve carrier being put into bowling machine, is equably sprinkled into nothing during scrolling
Amorphous silicon-alumina dry powder and penetrating binder, make carrier constantly grow up.Carrier after balling-up is dry 3 at 30 DEG C ~ 50 DEG C
The h of h ~ 24, then in 400 DEG C ~ 700 DEG C roasting 2 h ~ 6 h.In the amorphous silica-alumina silica weight content be 15% ~
50%.The binder is the dilute acid soln that mass concentration is 5% ~ 10%, such as one of acetic acid, nitric acid or a variety of.Binder
Additional amount and amorphous silica-alumina dry powder mass ratio be 0.5 ~ 1.5.
In step (2), method auxiliary agent nickel, phosphorus and vanadium loaded on the molecular sieve carrier of amorphous silica-alumina cladding can be with
It is prepared using conventional infusion process, wherein the presoma of auxiliary agent phosphorus can use phosphoric acid；The presoma of auxiliary agent vanadium can be using inclined
The presoma of ammonium vanadate, auxiliary agent nickel can use one of nickel nitrate, nickel acetate or a variety of.Nickel containing auxiliary agent, phosphorus and vanadium will be used
Maceration extract dipping amorphous silica-alumina cladding molecular sieve carrier after, through dry and roasting, catalyst precarsor A is obtained, wherein doing
Dry and roasting condition is as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, in 300 DEG C ~ 500 DEG C roasting 2h ~ 6h.
In step (3), the reduction treatment process is as follows: under hydrogen atmosphere by catalyst precarsor A 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 (4), 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 catalyst precarsor A obtained by the additional amount of polyalcohol and/or furfural and step (2) is 2:1 ~ 10:1,
Preferably 3:1 ~ 10:1.
In step (6), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
Mass ratio with catalyst precarsor A is 0.1 ~ 0.4.
In step (7), the material that step (6) obtains is added in the alkaline solution containing ammonium and is impregnated, dip time
The generally min of 5 min ~ 30.The solid absorption ammonia that step (6) is obtained, adsorption time are generally the min of 5 min ~ 30.Step
Suddenly in (7), the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (7), pure ammonia is can be used in the ammonia, the gaseous mixture containing ammonia can also be used, in mixed gas
It is other for one of inert gas such as nitrogen, argon gas etc. or a variety of in addition to ammonia.
In step (8), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
In step (6) or step (8), the heating stirring is generally carried out at 40 DEG C ~ 90 DEG C.
Drying described in step (9) and roasting condition are as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300 DEG C ~
550 DEG C of roasting 2 h ~ 6 h.
The present invention also provides a kind of methods of producing ethylene by ethanol dehydration, wherein using catalyst of the invention.This hair
Bright catalyst is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material.The ethanol dehydration prepares second
The reaction condition of alkene is as follows: ethanol water concentration is 5wt% ~ 40wt%, 0.5 h of mass space velocity-1~15.0 h-1, reaction temperature
160 ℃~400℃。
Compared with prior art, catalyst of the present invention has the following advantages that and feature:
(1) in catalyst of the present invention, the modification of auxiliary agent phosphorus and vanadium to carrier is conducive to the acidity for improving carrier, molecular sieve
Surface coats suitable amorphous silica-alumina, can increase its specific surface area, aperture and Kong Rong, can load more miscellaneous more
Acid ammonium salt, so not but not change molecular sieve carrier whole pore structure, and be conducive to improve catalyst total acid content；
(2) hydrogenation of auxiliary agent nickel is utilized, catalytic polyol and/or furfural liquid-phase hydrogenatin, mainly have in autoclave
Two aspect effects: one is the liquid alkane absorption that polyalcohol and/or furfural liquid-phase hydrogenatin generate is on a catalyst support, it can
The duct for effectively blocking carrier, is distributed in the heteropoly acid ammonium of subsequent load on carrier outer surface；On the other hand, polyalcohol
And/or furfural liquid-phase hydrogenatin can generate carbon distribution on carrier, can weaken the acidity of carrier to a certain extent, reduce carrier acid
Property position absorption ammonia quantity, so that heteropoly acid is mainly reacted with ammonium salt organic acid and generate 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 in this way
Component Vectors acidic site.The catalyst that the method for the present invention obtains not only have low temperature active it is high, selectivity it is good, have strong anti-carbon capacity
The characteristics of, 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 mass concentration be 6% acetic acid aqueous solution, after balling-up, carrier is dried at room temperature for 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:
It weighs the carrier 75.7g prepared and is added to mixing containing 27.4g nickel nitrate, 6.1g phosphoric acid and 1.1g ammonium metavanadate
It in Heshui solution, stirs at 70 DEG C and is evaporated to solution, obtained material is made in 110 DEG C of dry 8h in 400 DEG C of roasting 3h
Catalyst precarsor A.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, at 0.3MPa
4h is handled, reaction temperature is down to, the sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 260 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then plus
Enter into the aqueous solution containing 12.6g citric acid, stirring to solution is evaporated at 40 DEG C；It is molten that obtained material is added to ammonium carbonate
10min is impregnated in liquid, it is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 12.4g 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 500 DEG C of 3.0 h of roasting, catalyst is made,
Wherein (NH4)0.5H2.5PW12O40Content is 12wt%, and NiO content is 8wt%, P in carrier2O5Content be 5 wt%, V2O5Contain
Amount is 1 wt%.
(3) catalyst characterization:
It is taken a little in the surrounding in catalyst granules section and centre, elemental analysis is carried out to each point by SEM, the results showed that
Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and ammonium heteropoly acids are not detected in intermediate each point, illustrates using this side
The catalyst of method preparation, the dispersion that ammonium heteropoly acids have had on catalyst surface, and be not impregnated with into duct.
(4) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
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 that 0.3mm spherical shape HZSM-5 molecular sieve (silica alumina ratio 100) is added in bowling machine by the partial size prepared,
Bowling machine is started, amorphous silica-alumina dry powder (in terms of butt, silica weight content 30%) is equably sprinkled into machine, simultaneously
The acetic acid aqueous solution that mass concentration is 6% is sprayed into, after balling-up, carrier is dried into 12h at 40 DEG C, is then roasted at 500 DEG C
3h obtains the HZSM-5 molecular sieve carrier of amorphous silica-alumina cladding, and wherein amorphous silica-alumina accounts for HZSM-5 molecular sieve
30%。
(2) preparation of catalyst:
It weighs the carrier 65.6g prepared and is added to mixing containing 38.3g nickel nitrate, 6.8g phosphoric acid and 2.1g ammonium metavanadate
It in Heshui solution, stirs at 70 DEG C and is evaporated to solution, obtained material is made in 110 DEG C of dry 8h in 400 DEG C of roasting 3h
Catalyst precarsor A.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, at 0.3MPa
4h is handled, reaction temperature is down to, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 150 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then it is added
Into the aqueous solution containing 16.4g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material is added to sal volatile
Middle dipping 10min is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 18.6g phosphotungstic acid, is stirred at 70 DEG C
It mixes to solution and is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, catalyst is made,
In (NH4)0.7H2.3PW12O40Content is 18wt%, and NiO content is 12wt%, P in carrier2O5Content be 6 wt%, V2O5Contain
Amount is 2 wt%.
(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 50g partial size prepared2/Al2O3Molar ratio is 150) to be added to
In bowling machine, start bowling machine, be equably sprinkled into machine 20g amorphous silica-alumina dry powder (in terms of butt, silica content
40wt%), while the acetic acid aqueous solution that mass concentration is 6% is sprayed into, after balling-up, carrier is dried into 12 h at 40 DEG C, so
Afterwards in 500 DEG C of 3 h of roasting, the HZSM-5 molecular sieve carrier of amorphous silica-alumina cladding is obtained, wherein amorphous silica-alumina accounts for HZSM-5
The 40% of molecular sieve.
(2) preparation of catalyst:
Weigh the mixing water that the carrier 56.2g prepared is added to 47.3g nickel nitrate, 7.4g phosphoric acid and 2.9g ammonium metavanadate
It in solution, stirs at 70 DEG C and is evaporated to solution, catalysis is made in 400 DEG C of roasting 3h in 110 DEG C of dry 8h in obtained material
Agent precursor A.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, is handled at 0.3MPa
4h is down to reaction temperature, the sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 260 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then it is added
Into the aqueous solution containing 19.7g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material is added to sal volatile
Middle dipping 10min is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 24.8g phosphotungstic acid, is stirred at 70 DEG C
It mixes to solution and is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 520 DEG C of 3.0 h of roasting, catalyst is made,
In (NH4)0.2H2.8PW12O40Content is 24wt%.NiO content is 16wt%, P in carrier2O5Content be 7 wt%, V2O5Content
For 3 wt%.
(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 with embodiment 3 catalyst is made, wherein (NH in remaining4)0.2H3.8SiW12O40Content is
24wt%, NiO content is 16wt%, P in carrier2O5Content be 7 wt %, V2O5Content be 3 wt%.
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, catalyst precarsor A is added in the aqueous solution containing 24.8g phosphotungstic acid, is stirred at 70 DEG C
It is evaporated to solution；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
H3PW12O40Content is 24wt%, and NiO content is 16wt%, P in carrier2O5Content be 7 wt%, V2O5Content be 3 wt%.
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 19.7g 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 24.8g 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 520 DEG C of 3.0 h of roasting, catalyst is made, wherein (NH4)0.2H2.8PW12O40Content is 24wt%.NiO content is in carrier
16wt%, P2O5Content be 7 wt%, V2O5Content be 3 wt%.
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 and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecular sieve weight
The 5% of amount, with embodiment 3 catalyst is made, wherein (NH in remaining4)0.2H2.8PW12O40Content is 24wt%, NiO content in carrier
For 16wt%, P2O5Content be 7wt%, V2O5Content be 3wt%.
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, the dosage for adjusting HZSM-5 and amorphous silica-alumina, makes amorphous silica-alumina account for HZSM-5 molecular sieve weight
The 70% of amount, with embodiment 3 catalyst is made, wherein (NH in remaining4)0.2H2.8PW12O40Content is 24wt%, and NiO contains in carrier
Amount is 16wt%, P2O5Content be 7%, V2O5Content be 3%.
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 | 99.0 | 99.1 |
| Embodiment 2 | 98.8 | 98.8 |
| Embodiment 3 | 99.1 | 99.2 |
| Embodiment 4 | 99.0 | 99.0 |
| Comparative example 1 | 96.9 | 96.3 |
| Comparative example 2 | 97.2 | 97.5 |
| Comparative example 3 | 95.1 | 95.0 |
| Comparative example 4 | 95.8 | 95.9 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 5 | 98.9 | 99.0 |
| Comparative example 5 | 85.2 | 85.1 |
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 (22)
1. a kind of preparation method of heteropoly acid ammonium salt catalyst, the heteropoly acid ammonium salt catalyst include active component, auxiliary agent
And carrier, active component are that ammonium heteropoly acids are shown in formula (1), auxiliary agent is nickel, phosphorus and vanadium, and carrier is the molecule of amorphous silica-alumina cladding
Sieve；The weight of amorphous silica-alumina accounts for the 15% ~ 45% of molecular sieve；On the basis of the weight of carrier, auxiliary agent in terms of oxide,
P2O5Content be 3.0% ~ 10.0%, V2O5Content be 0.2% ~ 4.0%, NiO content be 8% ~ 20%；With the weight of catalyst
On the basis of, the content of ammonium heteropoly acids is 8% ~ 30%, and auxiliary agent is 70% ~ 92% with the total content of carrier in terms of oxide；
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；
The preparation method of the catalyst, comprising:
(1) molecular sieve carrier of amorphous silica-alumina cladding is prepared；
(2) auxiliary agent nickel, phosphorus and vanadium are loaded on the molecular sieve carrier of amorphous silica-alumina cladding, obtains catalyst precarsor A；
(3) the resulting catalyst precarsor A of step (2) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(4) polyalcohol and/or furfuryl aldehyde solution are added in autoclave, then adjusting Hydrogen Vapor Pressure to 2~4MPa,
0.5~5.0h is reacted at 100~300 DEG C；
(5) product that step (4) reaction obtains is through filtering, through drying to sample surfaces without liquid phase, before obtaining catalyst under low temperature
Body B；
(6) the catalyst precarsor B that step (5) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated；
(7) material that step (6) 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 (6) obtains is adsorbed ammonia at 40 DEG C ~ 90 DEG C by person；
(8) heteropoly acid aqueous solution is added in the material that step (7) obtains, heating stirring to solution is evaporated；
(9) solid for obtaining step (8) is through dry and roasting to get catalyst.
2. 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 point
The 20% ~ 40% of son sieve weight.
3. preparation method described in accordance with the claim 1, it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acids
Content be 12% ~ 25%, auxiliary agent in terms of oxide with the total content of carrier be 75% ~ 88%.
4. preparation method described in accordance with the claim 1, it is characterised in that: the molecular sieve is one in ZSM-5,4A, 5A
Kind is a variety of.
5. preparation method described in accordance with the claim 1, it is characterised in that: the molecular sieve is ZSM-5.
6. according to preparation method described in claim 1 or 4, it is characterised in that: the molecular sieve is hydrogen type molecular sieve, property
It is as follows: SiO2/Al2O3Molar ratio is 25 ~ 300.
7. preparation method described in accordance with the claim 1, it is characterised in that silica weight content in the amorphous silica-alumina
It is 15% ~ 50%.
8. preparation method described in accordance with the claim 1, it is characterised in that in the heteropoly acid ammonium salt catalyst, heteropoly acid ammonium
Salt distribution is in the outer surface of carrier.
9. preparation method described in accordance with the claim 1, it is characterised in that: in step (1), the amorphous silica-alumina cladding
Molecular sieve carrier, the preparation method is as follows: first by system with molecular sieve for preparing at carrier, then rolling balling method is used to be coated on amorphous silica-alumina
The surface of molecular sieve carrier.
10. preparation method according to claim 9, it is characterised in that: molecular sieve carrier be by molecular sieve dry powder through molding,
Dry and roast and obtain, the roasting condition: maturing temperature is 400 DEG C ~ 700 DEG C, and calcining time is the h of 2 h ~ 6, molecular sieve
The shape of carrier is using spherical, partial size 0.1 mm ~ 0.5 mm.
11. preparation method according to claim 9, it is characterised in that: coated amorphous silica-alumina using rolling balling method
Method on the surface of molecular sieve carrier is as follows: molecular sieve carrier being put into bowling machine, is equably sprinkled into during scrolling
Amorphous silica-alumina dry powder and penetrating binder, make carrier constantly grow up, the carrier after balling-up is dry at 30 DEG C ~ 50 DEG C
The h of 3 h ~ 24, then in 400 DEG C ~ 700 DEG C roasting 2 h ~ 6 h；The binder is the diluted acid that mass concentration is 5% ~ 10%
Solution, the additional amount of binder and the mass ratio of amorphous silica-alumina dry powder are 0.5 ~ 1.5.
12. preparation method described in accordance with the claim 1, it is characterised in that: in step (2), auxiliary agent nickel, phosphorus and vanadium are loaded to
Method on the molecular sieve carrier of amorphous silica-alumina cladding is prepared using infusion process, is soaked with the maceration extract of nickel containing auxiliary agent, phosphorus and vanadium
After the molecular sieve carrier of stain amorphous silica-alumina cladding, through dry and roasting, catalyst precarsor A is obtained, wherein dry and roasting
Condition is as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, in 300 DEG C ~ 500 DEG C roasting 2h ~ 6h.
13. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), 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.
14. preparation method described in accordance with the claim 1, it is characterised in that: in step (4), the polyalcohol is C5~C10
One of polyalcohol is a variety of；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, polyalcohol and/or furfural
The mass ratio of catalyst precarsor A obtained by additional amount and step (2) is 2:1 ~ 10:1.
15. preparation method according to claim 14, it is characterised in that: in step (4), polyalcohol and/or furfuryl aldehyde solution
Mass concentration be 5%~30%, the mass ratio of additional amount and step (2) gained the catalyst precarsor A of polyalcohol and/or furfural are
3:1~10:1。
16. preparation method described in accordance with the claim 1, it is characterised in that: in step (6), the organic acid is citric acid, wine
One of stone acid, malic acid are a variety of；The mass ratio of the organic acid and catalyst precarsor A is 0.1 ~ 0.4.
17. preparation method described in accordance with the claim 1, it is characterised in that: in step (7), the material that step (6) obtains is added
Enter and impregnated into the alkaline solution containing ammonium, dip time is the min of 5 min ~ 30；The material that step (6) is obtained adsorbs ammonia
Gas, adsorption time are the min of 5 min ~ 30；In step (7), the alkaline solution containing ammonium is ammonium hydroxide, sal volatile, carbon
One of sour hydrogen ammonium salt solution is a variety of.
18. preparation method described in accordance with the claim 1, it is characterised in that: in step (8), the heteropoly acid be phosphotungstic acid,
One of silico-tungstic acid, phosphomolybdic acid are a variety of.
19. preparation method described in accordance with the claim 1, it is characterised in that: drying described in step (9) and roasting condition are such as
Under: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then in 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h.
20. a kind of heteropoly acid ammonium salt catalyst, it is characterised in that: obtained using any preparation method of claim 1~19
It arrives.
21. a kind of method of producing ethylene by ethanol dehydration, it is characterised in that: using the catalyst described in claim 20.
22. according to the method for claim 21, it is characterised in that: the reaction condition of the producing ethylene by ethanol dehydration is such as
Under: 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610003170.4A CN106944152B (en) | 2016-01-07 | 2016-01-07 | Heteropoly acid ammonium salt catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610003170.4A CN106944152B (en) | 2016-01-07 | 2016-01-07 | Heteropoly acid ammonium salt catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944152A CN106944152A (en) | 2017-07-14 |
| CN106944152B true CN106944152B (en) | 2019-06-11 |
Family
ID=59465280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610003170.4A Active CN106944152B (en) | 2016-01-07 | 2016-01-07 | Heteropoly acid ammonium salt catalyst and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944152B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926091B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Heteropolyacid ammonium salt catalyst and preparation method thereof |
| CN112279764B (en) * | 2019-07-24 | 2022-11-08 | 万华化学集团股份有限公司 | Preparation method of 3-ethoxy ethyl propionate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007283A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | ZSM-5 molecular sieve modified catalyst and its preparation method and application |
| CN101214451A (en) * | 2007-12-29 | 2008-07-09 | 大连理工大学 | Novel composite solid acid catalyst and application |
| CN101327443A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院上海有机化学研究所 | Molecular sieve catalyst, preparation method and use in preparing ethylene by dehydrating ethanol |
| 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 |
| CN104588104A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol |
-
2016
- 2016-01-07 CN CN201610003170.4A patent/CN106944152B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007283A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | ZSM-5 molecular sieve modified catalyst and its preparation method and application |
| CN101214451A (en) * | 2007-12-29 | 2008-07-09 | 大连理工大学 | Novel composite solid acid catalyst and application |
| CN101327443A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院上海有机化学研究所 | Molecular sieve catalyst, preparation method and use in preparing ethylene by dehydrating ethanol |
| 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 |
| CN104588104A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944152A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106944147B (en) | Heteropoly acid ammonium type catalyst and preparation method thereof | |
| CN106944139B (en) | A kind of heteropoly acid ammonium salt catalyst and preparation method thereof | |
| KR20140050531A (en) | Ordered mesoporous-silica based catalysts for the production of 1,3-butadiene and production method of 1,3-butadiene using thereof | |
| CN106944143B (en) | Heteropoly acid ammonium type catalyst and its preparation method | |
| CN106944152B (en) | Heteropoly acid ammonium salt catalyst and its preparation method | |
| CN105727978B (en) | A kind of method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation | |
| CN106944136B (en) | A kind of heteropoly acid ammonium salt form catalyst and its preparation method | |
| CN106944144B (en) | The preparation method of heteropoly acid ammonium type catalyst | |
| CN105642351B (en) | Heteropoly acid ammonium salt catalyst and preparation method thereof | |
| CN106944149B (en) | A kind of heteropoly acid ammonium salt catalyst and its preparation method | |
| CN105709824B (en) | A kind of heteropoly acid ammonium salt catalyst and its preparation method | |
| CN106944148B (en) | A kind of preparation method of heteropoly acid ammonium catalyst | |
| CN106944145B (en) | The preparation method of heteropoly acid ammonium catalyst | |
| CN105727979B (en) | A kind of method for preparing catalyst for preparing propene by oxidative dehydrogenation of propane | |
| CN105709837B (en) | Heteropoly acid ammonium salt catalyst and its preparation method | |
| CN109926091A (en) | A kind of heteropoly acid ammonium salt catalyst and preparation method thereof | |
| CN105709838B (en) | A kind of heteropoly acid ammonium type catalyst and preparation method thereof | |
| CN106944115B (en) | A kind of heteropoly acid ammonium salt form catalyst and preparation method thereof | |
| CN105646130B (en) | The method of producing ethylene from dehydration of ethanol | |
| CN106944146B (en) | A kind of preparation method of heteropoly acid ammonium catalyst | |
| CN105712823B (en) | A kind of method by producing ethylene by ethanol dehydration | |
| CN105712822B (en) | A kind of method by preparing ethylene by dehydrating ethanol | |
| CN105709839B (en) | A kind of preparation method of heteropoly acid ammonium catalyst | |
| CN105709823B (en) | A kind of heteropoly acid ammonium salt catalyst and preparation method thereof | |
| CN105709825B (en) | Heteropoly acid ammonium catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |