CN105709838B - A kind of heteropoly acid ammonium type catalyst and preparation method thereof - Google Patents
A kind of heteropoly acid ammonium type catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of heteropoly acid ammonium type catalyst and preparation method thereof.In the catalyst, active component is ammonium heteropoly acidses, auxiliary agent is nickel oxide, carrier is silica, and its preparation method is that silica support is loaded to organic acid, the alkaline solution containing ammonium or ammonia, heteropoly acid and auxiliary agent successively, obtains catalyst precarsor, again after reduction treatment and polyol reaction processing, organic acid, ammoniumization processing, leaching heteropoly acid solution are loaded successively, through drying and being calcined, obtain catalyst.Catalyst prepared by the inventive method, heteropoly acid exists with ammonium salts, and major part ammonium heteropoly acidses are dispersed in carrier outer surface, and smaller portions are dispersed in carrier duct, catalyst improves the stability of catalyst while with higher low temperature active, selectivity and coking resistivity.Catalyst of the present invention is ethylene reaction produced for the dehydration of raw material especially suitable for the low-concentration ethanol aqueous solution.
Description
Technical field
The present invention relates to a kind of heteropoly acid ammonium type catalyst and preparation method thereof, is used for ethanol dehydration more particularly to one kind
Produce heteropoly acid ammonium salt catalyst of ethene and preparation method thereof.
Background technology
Ethene is as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products
It is 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 by light petroleum fraction crack made from, heavy dependence petroleum resources.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and it has been the task of top priority to develop new renewable alternative energy source.
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, the dependence to petroleum resources can be avoided, 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 value 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 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, 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
The oxygen-containing polyacid that fixed structure is formed by oxygen atom ligand bridging, has the advantages that highly acid.In producing ethylene from dehydration of ethanol
In reaction, heteropolyacid catalyst has the characteristics of reaction temperature is low, selectivity height and high income.
[Chemical Engineering Technology and exploitation, 2010,5 (39) such as Li Benxiang:7-9] report entitled MCM- 41 and 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.For the catalyst using aluminum 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 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 preparation
Method.The catalyst not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and stability is good.
The preparation method of described heteropoly acid ammonium type catalyst, including：
（1）Silica support is added in aqueous solutions of organic acids, stirring to solution is evaporated at 60 DEG C ~ 90 DEG C；
（2）By step（1）Obtained carrier is added in the alkaline solution containing ammonium, filtered, is done at 50 DEG C ~ 90 DEG C
It is dry；Or by step（1）Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C；
（3）The mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added to step（2）In obtained material, 60 DEG C ~
Stirring to solution is evaporated at 90 DEG C；
（4）By step（3）Obtained solid in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, be then calcined at 300 DEG C ~ 550 DEG C 2h ~
6h, catalyst precarsor A is made；
（5）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（6）Polyhydric alcohol solutions are driven into autoclave, Hydrogen Vapor Pressure are then adjusted to 2~4MPa, at 200~300 DEG C
0.5~5.0h of lower reaction；
（7）By step（6）In reacted catalyst precarsor A filter out, at 20 DEG C ~ 50 DEG C, preferably 30 DEG C ~ 50 DEG C
Under, it is dried, until sample surfaces without liquid phase, obtain catalyst precarsor B；
（8）By step（7）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, stirred at 60 DEG C ~ 90 DEG C to
Solution is evaporated, and obtains catalyst precarsor C；
（9）By step（8）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, filtered, 50 DEG C ~ 90
Dried at DEG C；Or by step（8）Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（10）The aqueous solution of heteropoly acid is added to step（9）In obtained catalyst precarsor D, stirred at 60 DEG C ~ 90 DEG C
Mix to solution and be evaporated；
（11）By step（10）Obtained solid is in the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12, then in 300 DEG C ~ 550 DEG C roastings
The h of 2 h ~ 6 is burnt, produces catalyst.
Heteropoly acid ammonium type catalyst of the present invention, including active component, auxiliary agent and carrier, active component are shown in for ammonium heteropoly acidses
Formula（1）, auxiliary agent is nickel oxide, and carrier is silica；On the basis of the weight of catalyst, the contents of ammonium heteropoly acidses for 5% ~
45%, preferably 10% ~ 40%, auxiliary agent using the content that oxide is counted as 3% ~ 18%, preferably 5% ~ 15%, the content of carrier for 37 % ~
92%, preferably 45% ~ 85%；
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
When, m+n=3, n values are 0.1 ~ 1.0.
The property of the silica support is as follows：Specific surface area is 500 ~ 820 m2/ g, pore volume are 0.62 ~ 0.92 mL/g,
Average pore diameter is 4.6 ~ 6.6 nm.
Step（1）Described silica support is prepared with the following method：
A, template is added in the aqueous solution containing organic acid, obtains solution I；
B, silicon source is added in solution I, obtains solution II, then stirred at 60 DEG C ~ 90 DEG C extremely into gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ 24h, then in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, silica is made
Carrier.
In step A, the template is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecane
Base sodium sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be 1000 ~
One or more in 10000 polyethylene glycol, SiO in described template and carrier2Mol ratio be 0.01 ~ 1.2；It is described
Organic acid is citric acid, the one or more in tartaric acid, malic acid, SiO in described organic acid and carrier2Mol ratio be
0.1~1.2。
In step B, described silicon source is the one or more in tetraethyl orthosilicate, Ludox.
In step C, described silica support can be made the silica support of shaping or be not required to the oxygen of shaping
SiClx carrier, those skilled in the art determine according to selected technique.The silica support of shaping, it can use existing
Conventional molding techniques are molded, such as extruded moulding, compression molding etc., and shape can be bar shaped, spherical, sheet etc..It is being molded
During, binding agent and shaping assistant can be added as needed, and binding agent typically uses small porous aluminum oxide.Shaping assistant is such as
Peptizing agent, extrusion aid etc..After step C dryings, silica can be obtained through shaping or without shaping, then through high-temperature roasting
Carrier, wherein the condition being calcined is as follows：2h ~ 6h is calcined at 300 DEG C ~ 800 DEG C.
Step（1）And step（8）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Institute
SiO in the organic acid and carrier stated2Mol ratio be 0.05 ~ 0.5.
Step（1）And step（8）The middle mol ratio for introducing organic acid is 4:1~1:4.
Step（2）And step（10）In, obtained material is added in the alkaline solution containing ammonium and impregnated, during dipping
Between the generally min of 5 min ~ 30.The solid absorption ammonia that will be obtained, adsorption time are generally the min of 5 min ~ 30.Step（2）
And step（10）In, the alkaline solution containing ammonium is ammoniacal liquor, sal volatile, one kind in ammonium bicarbonate soln or more
Kind.
Step（2）And step（10）In, described ammonia can use pure ammonia, can also use the gaseous mixture containing ammonia,
In mixed gas in addition to ammonia, other is the one or more in inert gas such as nitrogen, argon gas.
Step（3）In, the presoma of the auxiliary agent nickel oxide is the one or more in nickel nitrate, nickel acetate.
Step（3）And step（10）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（3）And step（10）The middle mol ratio for introducing heteropoly acid is 4:1~1:4.
Step（5）In, described reduction treatment process is as follows：Under hydrogen atmosphere by catalyst precarsor be warming up to 300 DEG C~
600 DEG C, after handling 4h~8h under 0.1MPa~0.5MPa, it is down to reaction temperature.Wherein reduction treatment can use pure hydrogen,
The hydrogen containing inert gas can also be used, hydrogen volume concentration is 30% ~ 100%.
Step（6）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 polyhydric alcohol solutions is 5%~30%.The addition of polyalcohol
Mass ratio with catalyst precarsor A is 3:1~10:1.
Step（8）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid
With SiO in carrier2Mol ratio be 0.05 ~ 0.50.
It can also be added in described silica support in mesopore molecular sieve, such as SBA-15, SBA-3, MCM-41 etc.
One or more, the weight content of molecular sieve in the carrier is below 10%, and generally 1% ~ 8%.Mesopore molecular sieve can aoxidize
Introduce, can also be introduced during plastic before silicon plastic, can also be introduced after silica plastic, can be with silica support
Kneading introduces in forming process.
Present invention also offers a kind of method of producing ethylene by ethanol dehydration, wherein the catalyst using the present invention.This hair
Bright producing ethylene by ethanol dehydration catalyst is ethylene reaction produced for the dehydration of raw material especially suitable for the low-concentration ethanol aqueous solution.It is described
Preparing ethylene by dehydrating ethanol reaction condition it is as follows：Ethanol water concentration is 5wt% ~ 40wt%, the h of mass space velocity 0.5-1~
15.0 h-1, 180 DEG C ~ 400 DEG C of reaction temperature.
Catalyst of the present invention uses the silica support of bigger serface, using the hydrogenation of auxiliary agent nickel, in autoclave
Interior catalytic polyol liquid-phase hydrogenatin, mainly there are two aspects to act on：One is the liquid alkane absorption of polyalcohol liquid-phase hydrogenatin generation
On a catalyst support, the duct of carrier can be effectively blocked, the heteropoly acid ammonium for making subsequently to load is distributed on carrier surface,
Major part ammonium heteropoly acidses are so made to be dispersed in carrier surface, smaller portions ammonium heteropoly acidses are dispersed in carrier duct；Separately
On the one hand, polyalcohol liquid-phase hydrogenatin can produce carbon distribution on carrier, can weaken the acidity of carrier to a certain extent, reduce and carry
Body acidic site adsorbs the quantity of ammonia, heteropoly acid is mainly reacted with ammonium salt organic acid and generates ammonium heteropoly acidses, contributes to miscellaneous
More acid ammonium salts are dispersed in carrier surface, and can remove above-mentioned carbon deposit through follow-up high-temperature roasting, so effectively retain
This Component Vectors acidic site.The catalyst that the inventive method obtains not only have low temperature active it is high, selectivity good, anti-carbon energy
The characteristics of power is strong, and stability is good.
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：
Weigh 145.8g cetyl trimethylammonium bromides and 205g citric acids are made into mixed solution, by the positive silicic acid of 302mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely into gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, 8 h are then dried at 110 DEG C, compression molding, 3 h is calcined at 580 DEG C, obtains silica support, wherein cetyl
The mol ratio of trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Compare table
Area is 525 m2/ g, pore volume are 0.64 mL/g, and average pore diameter is 4.9 nm.
（2）The preparation of catalyst：
The aqueous solution containing 10.4g citric acids is added in 65g silica supports, stirring to solution steams at 70 DEG C
It is dry；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 31.1g nickel nitrates and 8.6g phosphotungstic acids, stir at 70 DEG C and be evaporated to solution, obtained solid is existed
110 DEG C of 8.0 h of drying, 3.0 h then are calcined at 400 DEG C, catalyst precarsor A is made, is then added in autoclave, hydrogen
450 DEG C are warming up under gas atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds the mountain that 400g mass concentrations are 20%
Pears alcoholic solution, then regulation Hydrogen Vapor Pressure to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out,
Dried at 40 DEG C to carrier surface without liquid phase；It is then added in the aqueous solution containing 20.8g citric acids, is stirred at 70 DEG C
It is evaporated to solution；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Then add
Into the aqueous solution containing 17.3g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained solid is dried 8.0 at 110 DEG C
H, 3.0 h then are calcined at 520 DEG C, (NH is made4)0.2H2.8PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 10wt%,
(NH4)0.2H2.8PW12O40Content is 25wt%.
（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
8 h-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 opens
Begin after reacting 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：
Weigh 200g cetyl trimethylammonium bromides and 105.7g citric acids are made into mixed solution, by the positive silicic acid of 250mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely into gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, 8 h are then dried at 110 DEG C, compression molding, 3 h is calcined at 600 DEG C, obtains silica support, wherein cetyl
The mol ratio of trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Compare table
Area is 570 m2/ g, pore volume are 0.72 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
The aqueous solution containing 24.4g citric acids is added in 61g silica supports, stirring to solution steams at 70 DEG C
It is dry；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 38.9g nickel nitrates and 14.5g phosphotungstic acids, stir at 70 DEG C and be evaporated to solution, obtained solid is existed
110 DEG C of 8.0 h of drying, 3.0 h then are calcined at 400 DEG C, catalyst precarsor A is made, is then added in autoclave, hydrogen
450 DEG C are warming up under gas atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds the mountain that 400g mass concentrations are 20%
Pears alcoholic solution, then regulation Hydrogen Vapor Pressure to 3MPa, 2h is reacted at 300 DEG C, after reaction terminates, catalyst filtration is come out,
Dried at 40 DEG C to carrier surface without liquid phase；It is then added in the aqueous solution containing 24.4g citric acids, is stirred at 70 DEG C
It is evaporated to solution；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Then add
Into the aqueous solution containing 14.5g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained solid is dried 8.0 at 110 DEG C
H, 3.0 h then are calcined at 500 DEG C, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 11wt%,
(NH4)0.5H2.5PW12O40Content is 28wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 3
（1）The preparation of carrier：
Weigh 316g cetyl trimethylammonium bromides and 62.4g citric acids are made into mixed solution, by the positive silicic acid four of 246mL
Ethyl ester is added in mixed solution, stirs 2 h, then at 70 DEG C stirring into gel, by gel at 40 DEG C the h of aging 12,
Then 8 h are dried at 110 DEG C, compression molding, 3 h is calcined at 600 DEG C, obtains silica support, wherein cetyl three
The mol ratio of methyl bromide ammonium and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Support is：Compare surface
Product is 630 m2/ g, pore volume are 0.81 mL/g, and average pore diameter is 5.1 nm.
（2）The preparation of catalyst：
The aqueous solution containing 43.3g citric acids is added in 58g silica supports, will stir to solution and steam at 70 DEG C
It is dry；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Be then added to containing
In the mixed aqueous solution of 46.7g nickel nitrates and 20.7g phosphotungstic acids, stir at 70 DEG C and be evaporated to solution, obtained solid is existed
110 DEG C of 8.0 h of drying, 3.0 h then are calcined at 400 DEG C, catalyst precarsor A is made, is then added in autoclave, hydrogen
450 DEG C are warming up under gas atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds the mountain that 400g mass concentrations are 20%
Pears alcoholic solution, then regulation Hydrogen Vapor Pressure to 3MPa, 2h is reacted at 300 DEG C, after reaction terminates, catalyst filtration is come out,
Dried at 40 DEG C to carrier surface without liquid phase；It is then added in the aqueous solution containing 21.7g citric acids, is stirred at 70 DEG C
It is evaporated to solution；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；Then add
Into the aqueous solution containing 10.4g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；Obtained solid is dried 8.0 at 110 DEG C
H, 3.0 h then are calcined at 470 DEG C, (NH is made4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%,
(NH4)0.7H2.3PW12O40Content is 30wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 628g P123, with embodiment 3, gained is urged for remaining
Agent is (NH4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%, (NH4)0.7H2.3PW12O40Content is
30wt%, P123 and SiO2Mol ratio be 0.1.Support is：Specific surface area is 610 m2/ g, pore volume are 0.84 mL/g, are put down
Equal bore dia is 5.5 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 5
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, 10min is impregnated in sal volatile and is changed to inhale
Attached 10v% NH3/ Ar gaseous mixture 10min, with embodiment 3, gained catalyst is (NH for remaining4)0.7H3.3SiW12O40-
NiO/SiO2, wherein NiO contents are 12wt%, (NH4)0.7H3.3SiW12O40Content is 30wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 6
Catalyst is made according to embodiment 3, has carried out 100 h stabilization to catalyst according to the appreciation 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 46.7g nickel nitrates and 31.1g phosphotungstic acids
In, stirring to solution is 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,
H is made3PW12O40-NiO/SiO2Catalyst, wherein NiO contents are 12wt%, H3PW12O40Content is 30wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
Catalyst is made according to comparative example 1, has carried out 100 h stabilization to catalyst according to the appreciation 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
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 98.8 | 98.3 |
| Embodiment 2 | 98.9 | 98.5 |
| Embodiment 3 | 98.7 | 98.4 |
| Embodiment 4 | 98.9 | 98.5 |
| Embodiment 5 | 98.5 | 98.1 |
| Comparative example 1 | 96.5 | 95.3 |
The stability test evaluation result of table 2
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 6 | 98.5 | 98.2 |
| Comparative example 2 | 83.1 | 82.1 |
From Tables 1 and 2 result, activity, selectivity and the stability of catalyst of the present invention are urged significantly better than comparative example
Agent.
Claims (20)
1. a kind of preparation method of heteropoly acid ammonium type catalyst, including：
（1）Silica support is added in aqueous solutions of organic acids, stirring to solution is evaporated at 60 DEG C~90 DEG C；
（2）By step（1）Obtained carrier is added in the alkaline solution containing ammonium, filtered, is dried at 50 DEG C~90 DEG C；Or
Person is by step（1）Obtained material adsorbs ammonia at 50 DEG C~90 DEG C；
（3）The mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added to step（2）In obtained material, at 60 DEG C~90 DEG C
Lower stirring is evaporated to solution, and auxiliary agent is nickel oxide；
（4）By step（3）Obtained solid in 90 DEG C~120 DEG C dry 3h~12h, be then calcined at 300 DEG C~550 DEG C 2h~
6h, catalyst precarsor A is made；
（5）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（6）Polyhydric alcohol solutions are driven into autoclave, then adjust Hydrogen Vapor Pressure to 2~4MPa, it is anti-at 200~300 DEG C
Answer 0.5~5.0h；
（7）By step（6）In reacted catalyst precarsor A filter out, be dried at 20 DEG C~50 DEG C, until sample
Surface obtains catalyst precarsor B without liquid phase；
（8）By step（7）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, is stirred at 60 DEG C~90 DEG C to molten
Liquid is evaporated, and obtains catalyst precarsor C；
（9）By step（8）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, filtered, at 50 DEG C~90 DEG C
Dry；Or by step（8）Obtained material adsorbs ammonia at 50 DEG C~90 DEG C, obtains catalyst precarsor D；
（10）The aqueous solution of heteropoly acid is added to step（9）In obtained catalyst precarsor D, stirred at 60 DEG C~90 DEG C to
Solution is evaporated；
（11）By step（10）Then obtained solid is calcined 2h in 90 DEG C~120 DEG C dry 3h~12h at 300 DEG C~550 DEG C
~6h, produces catalyst.
2. according to the preparation method described in claim 1, it is characterised in that described catalyst, including active component, auxiliary agent and
Carrier, active component are that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is nickel oxide, and carrier is silica；Using the weight of catalyst as base
Standard, the contents of ammonium heteropoly acidses are 5%~45%, auxiliary agent using the content that oxide is counted as 3%~18%, the content of carrier is 37%~
92%；
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 preparation method described in claim 2, it is characterised in that：On the basis of the weight of catalyst, ammonium heteropoly acidses
Content be 10%~40%, for auxiliary agent using the content that oxide is counted as 5%~15%, the content of carrier is 45%~85%.
4. according to the preparation method described in claim 1, it is characterised in that：The property of the silica support is as follows：Compare surface
Product is 500~820m2/ g, pore volume are 0.62~0.92mL/g, and average pore diameter is 4.6~6.6nm.
5. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described silica support is using as follows
It is prepared by method：
A, template is added in the aqueous solution containing organic acid, obtains solution I；
B, silicon source is added in solution I, obtains solution II, then stirred at 60 DEG C~90 DEG C extremely into gel；
C, by gel at 20 DEG C~50 DEG C aging 8h~24h, then in 90 DEG C~120 DEG C dry 3h~12h, silica is made
Carrier.
6. according to the preparation method described in claim 5, it is characterised in that：In step A, the template is cetyl front three
Base ammonium bromide, hexadecyltrimethylammonium chloride, lauryl sodium sulfate, triblock polymer P123, triblock polymer
One or more in F127, triblock polymer F108, the polyethylene glycol that molecular weight is 1000~10000, described template
Agent and SiO in carrier2Mol ratio be 0.01~1.2；The organic acid be citric acid, tartaric acid, one kind in malic acid or
It is a variety of, SiO in described organic acid and carrier2Mol ratio be 0.1~1.2.
7. according to the preparation method described in claim 5, it is characterised in that：In step B, described silicon source be tetraethyl orthosilicate,
One or more in Ludox.
8. according to the preparation method described in claim 1, it is characterised in that：Step（1）Or step（8）In, the organic acid is
One or more in citric acid, tartaric acid, malic acid；SiO in described organic acid and carrier2Mol ratio for 0.05~
0.50。
9. according to the preparation method described in claim 1, it is characterised in that：Step（1）Or step（8）It is middle to introduce rubbing for organic acid
You are than being 4:1~1:4.
10. according to the preparation method described in claim 1, it is characterised in that：Step（2）Or step（10）In, the thing that will obtain
Material, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is 5min~30min；The solid absorption ammonia that will be obtained,
Adsorption time is 5min~30min；The described alkaline solution containing ammonium is in ammoniacal liquor, sal volatile, ammonium bicarbonate soln
It is one or more；Described ammonia uses pure ammonia, or uses the gaseous mixture containing ammonia, in mixed gas in addition to ammonia, its
It is that inert gas is one or more in nitrogen, argon gas.
11. according to the preparation method described in claim 1, it is characterised in that：Step（3）In, the auxiliary agent presoma is nitric acid
One or more in nickel, nickel acetate.
12. according to the preparation method described in claim 1, it is characterised in that：Step（3）Or step（10）In, described is miscellaneous more
Acid is phosphotungstic acid, the one or more in silico-tungstic acid, phosphomolybdic acid.
13. according to the preparation method described in claim 1, it is characterised in that：Step（3）And step（10）Middle introducing heteropoly acid
Mol ratio is 4:1~1:4.
14. according to the preparation method described in claim 1, it is characterised in that：Step（5）In, described reduction treatment process is such as
Under：Catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, 4h~8h is handled under 0.1MPa~0.5MPa；Wherein
Reduction treatment uses pure hydrogen, or uses the hydrogen containing inert gas, and hydrogen volume concentration is 30%~100%.
15. according to the preparation method described in claim 1, it is characterised in that：Step（6）In, described polyalcohol is C5~C10
One or more in polyalcohol；The mass concentration of polyhydric alcohol solutions is 5%~30%；The addition and catalyst precarsor of polyalcohol
A mass ratio is 3:1~10:1.
16. according to the preparation method described in claim 1, it is characterised in that：Step（6）In, described polyalcohol be xylitol,
One or more in sorbierite, mannitol, arabite.
17. according to the preparation method described in claim 1, it is characterised in that：Contain mesoporous molecular in described silica support
The one or more in SBA-15, SBA-3, MCM-41 are sieved, the weight content of molecular sieve in the carrier is below 10%.
A kind of 18. heteropoly acid ammonium salt catalyst, it is characterised in that：Prepared using any described method of claim 1~17.
A kind of 19. method of producing ethylene by ethanol dehydration, it is characterised in that：Using the catalyst described in claim 18.
20. in accordance with the method for claim 19, it is characterised in that：This method using the low-concentration ethanol aqueous solution as raw material, its
Reaction condition is as follows：Ethanol water concentration is 5wt%~40wt%, mass space velocity 0.5h-1~15.0h-1, 180 DEG C of reaction temperature
~400 DEG C.
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|---|---|---|---|---|
| JPS5414908A (en) * | 1977-07-04 | 1979-02-03 | Tokuyama Soda Co Ltd | Preparation of ethers |
| RU2130338C1 (en) * | 1997-04-22 | 1999-05-20 | Каменский Анатолий Александрович | Catalyst for direct ethylene to ethanol hydration |
| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
| CN101157019A (en) * | 2007-10-26 | 2008-04-09 | 太原理工大学 | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414908A (en) * | 1977-07-04 | 1979-02-03 | Tokuyama Soda Co Ltd | Preparation of ethers |
| RU2130338C1 (en) * | 1997-04-22 | 1999-05-20 | Каменский Анатолий Александрович | Catalyst for direct ethylene to ethanol hydration |
| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
| CN101157019A (en) * | 2007-10-26 | 2008-04-09 | 太原理工大学 | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method |
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