CN105646128B - A kind of method that catalytic dehydration of ethanol prepares ethene - Google Patents
A kind of method that catalytic dehydration of ethanol prepares ethene Download PDFInfo
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- CN105646128B CN105646128B CN201410713651.5A CN201410713651A CN105646128B CN 105646128 B CN105646128 B CN 105646128B CN 201410713651 A CN201410713651 A CN 201410713651A CN 105646128 B CN105646128 B CN 105646128B
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Abstract
The invention discloses a kind of method that catalytic dehydration of ethanol prepares ethene.This method is catalyst A and catalyst B including at least two beds, and catalyst A compositions are as follows：Active component is ammonium heteropoly acidses, and auxiliary agent is boron oxide, and carrier is silica, and catalyst B compositions are as follows：Active component is ammonium heteropoly acidses, and auxiliary agent is nickel oxide, and carrier is silica.The present invention is cooperated using above two catalyst, is given full play to respective advantage, is improved the combined reaction performance of reaction system, has higher activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of method that catalytic dehydration of ethanol prepares ethene, and combination catalyst is used more particularly to one kind
Method for producing ethylene from dehydration of ethanol.
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 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.
Producing ethylene from dehydration of ethanol is the endothermic reaction, and main reaction is that a molecules of ethanol catalytic reaction obtains a molecule ethene and one
Molecular water, with the progress of reaction, along reactor axis to dehydration content, which occurs, for the ethanol in raw material gradually reduces, water
Content gradually rises, and the larger temperature difference also occurs in catalyst bed interlayer, and the catalyst contact of bottom bed is containing big all the time
The low-concentration ethanol raw material of water is measured, and catalyst bottom bed temperature substantially reduces, and this can directly influence lower catalytic agent
Performance, cause the catalyst activity of reactor lower part substantially to reduce, so as to influence the activity of integer catalyzer, selectivity and steady
It is qualitative.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of method of producing ethylene from dehydration of ethanol.Should
When method is used for producing ethylene from dehydration of ethanol, have the advantages that high ethanol conversion, selectivity and stability are good.
The method of producing ethylene from dehydration of ethanol of the present invention, including two beds are catalyst A and catalyst B, wherein
Ethanol raw material first contacts with catalyst A, is then contacted again with catalyst B；
Catalyst A composition is as follows：Active component is that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is boron oxide, and carrier is oxidation
Silicon；On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 3% ~ 35%, preferably 10% ~ 30%, more preferably
15% ~ 28%, for auxiliary agent using the content that oxide is counted as 3% ~ 8%, the content of carrier is 57% ~ 94 %, preferably 62% ~ 87%；
Hm(NH4)nBA12O40（1）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, m+n=4, n values are 0.1 ~ 1.0；When B 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.
Catalyst B composition is as follows：
Active component is that ammonium heteropoly acidses are shown in formula（2）, auxiliary agent is nickel oxide, and carrier is silica；With the weight of catalyst
On the basis of, the contents of ammonium heteropoly acidses is 3% ~ 35%, preferably 12% ~ 30%, more preferably 18% ~ 30%, and auxiliary agent is to aoxidize
The content of thing meter is 3% ~ 18%, preferably 5% ~ 15%, and the content of carrier is 47% ~ 94%, preferably 55% ~ 83%, further preferably
For 55% ~ 77%；
Hu(NH4)vBA12O40（2）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, u+v=4, v values are 0.1 ~ 1.0；When B represents P
When, u+v=3, v 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.
In the present invention, catalyst A preparation method, including：
（1）Silica support is added in alkane solvent, then filtered, at 20 DEG C ~ 50 DEG C, preferably 30 DEG C ~ 50 DEG C
Lower drying is to carrier surface without liquid phase；
（2）By step（1）Obtained material is added in aqueous solutions of organic acids, and stirring to solution steams at 60 DEG C ~ 90 DEG C
It is dry；
（3）By step（2）Obtained material is added in the alkaline solution containing ammonium, filtered, is done at 50 DEG C ~ 90 DEG C
It is dry, or by step（2）Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C；
（4）The mixed aqueous solution of auxiliary agent presoma and heteropoly acid is added to step（3）In obtained material, 60 DEG C ~
Stirring to solution is evaporated at 90 DEG C；
（5）By step（4）Then obtained solid is calcined 2 in the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12 at 300 DEG C ~ 550 DEG C
The h of h ~ 6, produces catalyst.
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 the h of the h of aging 8 ~ 24, then in the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12, through into
Type, the h of 2 h ~ 6 is calcined at 300 DEG C ~ 800 DEG C, obtains silica support.
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, the shaping of described silica support can use existing conventional molding techniques to carry out, such as extrusion
Shaping, compression molding etc., shape can be bar shaped, spherical, sheet etc..In forming process, bonding can be added as needed
Agent and shaping assistant, binding agent typically use small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
Step（1）In, described solvent is C5~C10One or more in liquid n-alkane, gasoline, diesel oil, solvent
Volume ratio with silica support is 1 ~ 3.Silica support add time for being impregnated in alkane solvent be generally 5 min ~
20 min。
Step（2）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.
Step（3）In, by step（2）Obtained material, which is added in the alkaline solution containing ammonium, to be impregnated, dip time
The min of generally 5 min ~ 30.By step（2）Obtained solid absorption ammonia, adsorption time are generally the min of 5 min ~ 30.Step
Suddenly（3）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（3）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（4）In, auxiliary agent presoma is boric acid；Described heteropoly acid is one kind in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid
It is or a variety of.
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.
Catalyst B preparation method, including：
（1）Auxiliary agent precursor water solution is added in silica support, stirring to solution is evaporated at 60 DEG C ~ 90 DEG C；
（2）By step（1）Then obtained solid is calcined 2 h in 90 DEG C ~ 120 DEG C dry 3h ~ 12h at 300 DEG C ~ 500 DEG C
~ 6 h, catalyst precarsor A is made；
（3）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（4）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；
（5）By step（4）In reacted catalyst precarsor A filter out, at 20 DEG C ~ 50 DEG C, preferably 30 DEG C ~ 50 DEG C
Under be dried, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（6）By step（5）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；
（7）By step（6）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, filtered, 50 DEG C ~ 90
Dried at DEG C；Or by step（6）Obtained material adsorbs ammonia at 50 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（8）The aqueous solution of heteropoly acid is added to step（7）In obtained catalyst precarsor D, stirred at 60 DEG C ~ 90 DEG C
It is evaporated to solution；
（9）By step（8）Then obtained solid is calcined 2 in the h of 90 DEG C ~ 120 DEG C dry 3h ~ 12 at 300 DEG C ~ 550 DEG C
The h of h ~ 6, produces catalyst.
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, through drying, silica support is made.
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.
In step C, described drying and roasting are carried out using usual manner, and it is as follows to dry the condition typically used: 90℃
~ 120 DEG C of dry 3h ~ 12h, roasting are typically calcined the h of 2 h ~ 6 at 300 DEG C ~ 800 DEG C.
Step（1）In, described auxiliary agent presoma is soluble nickel salt, generally one kind in nickel nitrate, nickel acetate
It is or a variety of.
Step（3）In, described reduction treatment process is as follows：Under hydrogen atmosphere by catalyst precarsor be warming up to 300 DEG C~
600 DEG C, 4h~8h is handled under 0.1MPa~0.5MPa.Wherein reduction treatment can use pure hydrogen, can also use containing lazy
Property gas hydrogen, hydrogen volume concentration be 30% ~ 100%.
Step（4）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（6）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.
Step（7）In, by step（6）Obtained catalyst precarsor C, which is added in the alkaline solution containing ammonium, to be impregnated, leaching
The stain time is generally the min of 5 min ~ 30.By step（6）Obtained catalyst precarsor C absorption ammonias, adsorption time are generally 5
min~30 min.Step（7）In, the alkaline solution containing ammonium is one in ammoniacal liquor, sal volatile, ammonium bicarbonate soln
Kind is a variety of.
Step（7）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（8）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
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.
In described catalyst A and B, ammonium heteropoly acidses are distributed on silica support for eggshell type, i.e. ammonium heteropoly acidses
It is evenly distributed on the surfaces externally and internally of carrier.
In the inventive method, the weight content of ammonium heteropoly acidses is not less than ammonium heteropoly acidses in catalyst A in catalyst B
Weight content.
Described catalyst A and catalyst B admission space ratio are 4:1 ~1:4.
The method of preparing ethylene by dehydrating ethanol of the present invention is as follows using fixed-bed process, reaction condition：Mass space velocity 0.5
h-1~12.0 h-1, 180 DEG C ~ 400 DEG C of reaction temperature.
Compared with prior art, the present invention has advantages below：
In the inventive method, the catalyst B of use, in low-concentration ethanol raw material dehydration is ethylene reaction produced there is low temperature to live
Property it is high the advantages of, be seated in catalyst A downstream, can be obviously improved bed temperature reduces what catalyst system was brought
Negative effect, catalyst A and catalyst B is cooperated and give full play to respective advantage, enable catalyst system for a long time
The higher activity and selectivity of holding, feed throughput substantially increases, and has higher product yield.
Embodiment
With reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
1st, catalyst preparation：
It is prepared by catalyst A
（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, through compression molding, be calcined 3 h at 580 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Than
Surface 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 silica support of preparation is added in C6 alkane solvents, 10min is impregnated, then filters, is dried at 40 DEG C
To carrier surface without liquid phase；It is then added in the aqueous solution containing 26.9g citric acids, stirring to solution is evaporated at 70 DEG C；
Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added to containing 7.1g boron
In the mixed aqueous solution of acid and 12.4g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dryings
8.0 h, 3.0 h then are calcined at 500 DEG C, (NH is made4)0.5H2.5PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is
4wt%, (NH4)0.5H2.5PW12O40Content is 12wt%.
It is prepared by catalyst B
（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, through compression molding, be calcined 3 h at 580 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Than
Surface 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：
27.2 g nickel nitrates are dissolved in deionized water, are added in 81g silica supports, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of drys 8.0 h, 3.0 h are then calcined at 400 DEG C, obtained catalyst precarsor A, are then added
Into autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds 400g
Mass concentration is 20% sorbitol solution, then regulation Hydrogen Vapor Pressure to 3MPa, and 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 to containing the water-soluble of 38.9g citric acids
In liquid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, 60 after filtering
Dried at DEG C；It is then added in the aqueous solution containing 12.4g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By what is obtained
Then solid is calcined 3.0 h in 110 DEG C of dry 8.0 h at 500 DEG C, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst,
Wherein NiO contents are 7wt%, (NH4)0.5H2.5PW12O40Content is 12wt%.
2nd, the evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol waters, first with being catalyzed
Agent A is contacted, and is then contacted again with catalyst B, and wherein catalyst A and catalyst B admission space ratio is 3:1, totally 20 mL, matter
Measure air speed 5h-1, 260 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, are then down to reaction
After temperature starts reaction 200 hours, product is analyzed by gas-chromatography, calculates ethanol conversion and ethylene selectivity, as a result
It is shown in Table 1.
Embodiment 2
Catalyst A and B admission space ratio are 1 in selection example 1:1, mass space velocity 5h-1, 260 DEG C of reaction temperature, its
Its appreciation condition is constant, and ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 3
Catalyst A preparation：
（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, through compression molding, be calcined 3 h at 600 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Than
Surface 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 silica support of preparation is added in C6 alkane solvents, 10min is impregnated, then filters, is dried at 40 DEG C
To carrier surface without liquid phase；It is then added in the aqueous solution containing 42.3g citric acids, stirring to solution is evaporated at 70 DEG C；
Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added to containing 8.9 boron
In the mixed aqueous solution of acid and 18.7g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dryings
8.0 h, 3.0 h then are calcined at 500 DEG C, (NH is made4)0.5H2.5PW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is
5wt%, (NH4)0.5H2.5PW12O40Content is 18wt%.
Catalyst B preparation：
（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, through compression molding, be calcined 3 h at 600 DEG C, obtain silica support, wherein hexadecane
The mol ratio of base trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Than
Surface 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：
35.0 g nickel nitrates are dissolved in deionized water, are added in 73g silica supports, stirring to solution steams at 70 DEG C
It is dry, by obtained solid in 110 DEG C of drys 8.0 h, 3.0 h are then calcined at 400 DEG C, obtained catalyst precarsor A, are then added
Into autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, is down to reaction temperature, adds 400g
Mass concentration is 20% sorbitol solution, then regulation Hydrogen Vapor Pressure to 3MPa, and 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 to containing the water-soluble of 58.4g citric acids
In liquid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, 60 after filtering
Dried at DEG C；It is then added in the aqueous solution containing 18.7g phosphotungstic acids, stirring to solution is evaporated at 70 DEG C；By what is obtained
Then solid is calcined 3.0 h in 110 DEG C of dry 8.0 h at 500 DEG C, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst,
Wherein NiO contents are 9wt%, (NH4)0.5H2.5PW12O40Content is 18wt%.
Catalyst A and B admission space ratio are 1:2, mass space velocity 5h-1, 250 DEG C of reaction temperature, other appreciation conditions are not
Become, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Embodiment 4
In embodiment 1, phosphotungstic acid is changed to silico-tungstic acid, with embodiment 1, gained catalyst A is (NH for remaining4)0.5H3.5SiW12O40-B2O3/SiO2Catalyst, wherein B2O3Content is 4wt%, (NH4)0.5H3.5SiW12O40Content is 10wt%.Urge
Agent B is (NH4)0.5H3.5SiW12O40-NiO/SiO2Catalyst, wherein NiO contents are 7wt%, (NH4)0.5H3.5SiW12O40Content
For 12wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Comparative example 1
Catalyst A in embodiment 1 is used alone, the evaluation of catalyst is the same as embodiment 1, ethanol conversion and ethylene selectivity
It the results are shown in Table 1.
The evaluation result of 1 each example of table
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 98.0 | 97.8 |
| Embodiment 2 | 99.3 | 99.1 |
| Embodiment 3 | 98.8 | 98.5 |
| Embodiment 4 | 97.8 | 97.7 |
| Comparative example 1 | 95.8 | 95.4 |
Claims (7)
1. a kind of method that catalytic dehydration of ethanol prepares ethene, including two beds are catalyst A and catalyst B, its
Middle ethanol raw material first contacts with catalyst A, is then contacted again with catalyst B；
Catalyst A composition is as follows：Active component is that ammonium heteropoly acidses are shown in formula（1）, auxiliary agent is boron oxide, and carrier is silica；
On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 3% ~ 35%, and auxiliary agent carries using the content that oxide is counted as 3% ~ 8%
The content of body is 57% ~ 94%；
Hm(NH4)nBA12O40（1）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, m+n=4, n values are 0.1 ~ 1.0；When B represents P, m+
N=3, n value are 0.1 ~ 1.0；
Catalyst B composition is as follows：Active component is that ammonium heteropoly acidses are shown in formula（2）, auxiliary agent is nickel oxide, and carrier is silica；
On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 3% ~ 35%, and auxiliary agent carries using the content that oxide is counted as 3% ~ 18%
The content of body is 47% ~ 94%；
Hu(NH4)vBA12O40（2）
Wherein A represents W or Mo, B represent Si or P；When B represents Si, u+v=4, v values are 0.1 ~ 1.0；When B represents P, u+
V=3, v value are 0.1 ~ 1.0；
In described catalyst A and B, the property of silica support is as follows：Specific surface area is 500 ~ 820 m2/ g, pore volume be 0.62 ~
0.92 mL/g, average pore diameter are 4.6 ~ 6.6 nm；
In described catalyst A and catalyst B, ammonium heteropoly acidses are distributed on silica support in eggshell type.
2. in accordance with the method for claim 1, it is characterised in that：Described catalyst A, on the basis of the weight of catalyst,
The content of ammonium heteropoly acidses is 10% ~ 30%, and for auxiliary agent using the content that oxide is counted as 3% ~ 8%, the content of carrier is 62% ~ 87%.
3. in accordance with the method for claim 1, it is characterised in that：Described catalyst B, on the basis of the weight of catalyst,
The content of ammonium heteropoly acidses is 12% ~ 30%, and for auxiliary agent using the content that oxide is counted as 5% ~ 15%, the content of carrier is 55% ~ 83%.
4. in accordance with the method for claim 1, it is characterised in that：Described catalyst B, on the basis of the weight of catalyst,
The content of ammonium heteropoly acidses is 18% ~ 30%, and for auxiliary agent using the content that oxide is counted as 5% ~ 15%, the content of carrier is 55% ~ 77%.
5. according to any described method of claim 1 ~ 4, it is characterised in that：The weight of ammonium heteropoly acidses in described catalyst B
Measure the weight content that content is not less than ammonium heteropoly acidses in catalyst A.
6. in accordance with the method for claim 1, it is characterised in that：Described catalyst A and catalyst B admission space ratio are
4:1 ~1:4。
7. in accordance with the method for claim 1, it is characterised in that：Using fixed-bed process, preparing ethylene by dehydrating ethanol it is anti-
Answer condition as follows：The h of mass space velocity 0.5-1~12.0 h-1, 180 DEG C ~ 400 DEG C of reaction temperature.
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| EP1982761A1 (en) * | 2006-11-22 | 2008-10-22 | BP Chemicals Limited | Supported heteropolyacid catalysts |
| CN101940938A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Heteropolyacid modified alumina ethanol dehydration catalyst and preparation method thereof |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1982761A1 (en) * | 2006-11-22 | 2008-10-22 | BP Chemicals Limited | Supported heteropolyacid catalysts |
| CN101940938A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Heteropolyacid modified alumina ethanol dehydration catalyst and preparation method thereof |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
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| 杂多酸催化剂催化乙醇脱水制乙烯;赵本良等;《东北师大学报自然科学版》;19971231(第3期);第41-43页 * |
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