CN106607094A - Olefin skeleton isomerization catalyst and preparation methods and application thereof - Google Patents
Olefin skeleton isomerization catalyst and preparation methods and application thereof Download PDFInfo
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Abstract
The invention relates to an olefin skeleton isomerization catalyst. The olefin skeleton isomerization catalyst contains an amorphous silicon-aluminum carrier and heteropolyacid loaded on the carrier. The olefin skeleton isomerization catalyst provided by the invention has favorable isomerization activity and selectivity, and can isomerize n-alkenes, not subjected to reaction after etherification of catalytic cracking light gasoline, under mild conditions. The invention further relates to a preparation method of the olefin skeleton isomerization catalyst, and the preparation method comprises the following steps: mixing a silicon source solution with an aluminium source solution; adding a heteropolyacid solution to adjust to a certain pH; forming gel at the pH; and then performing aging, drying and roasting treatment. The invention also relates to another preparation method of the olefin skeleton isomerization catalyst, and the preparation method comprises the following steps: mixing a silicon source solution with an aluminium source solution; adjusting pH by use of an acid solution; forming gel at the pH; preparing a carrier through aging, drying and roasting treatment; soaking the carrier in a heteropolyacid solution through an impregnation method; and then performing drying and roasting treatment. The invention further relates to application of the olefin skeleton isomerization catalyst to olefin skeleton isomerization reaction.
Description
Technical field
The present invention relates to a kind of olefin skeletal isomerization catalyst.The invention further relates to the system of the olefin skeletal isomerization catalyst
Preparation Method and application.
Background technology
With economic fast development, requirement more and more higher of the commercial production to environmental conservation, China is to the olefin(e) centent in gasoline
Also more strict standard has been promulgated.However, at present catalytically cracked gasoline accounts for more than 70% in China's motor petrol, wherein alkene
Content is higher.By Etherification of Light FCC Gasoline technology, the activity isomerism alkene in gasoline is set to be converted into corresponding ether with methanol reaction, no
Olefin(e) centent is reduced by only, and octane number can be improved, reduce Lei Shi vapour pressures.But catalytically cracked gasoline contained amount
In alkene, the active olefin that can be etherified only accounts for 20% or so, and remaining is the normal olefine without etherification activity.Need solution badly in this area
It by normal olefin skeleton isomerization is the isomeric olefine that can be etherified that problem certainly is, so as to greatly improve the yield of etherified benzine,
Improve quality, farthest increases the added value of carbon five and the resource of carbon six.
The isomerization catalyst of early stage mainly passes through modified oxide or composite oxides, wherein with halogen modified active oxygen
Change Al catalysts report most.But this kind of catalyst isomerisation conversion is relatively low, easily because coking causes rapid deactivation, uses
Short life.Relative to aluminium oxide, molecular sieve is due to the acid site concentrated with unique duct and intensity distributions, conduct preferably
The catalyst of isomerization reaction.At present the molecular sieve for being applied to C_5 olefins skeletal isomerization of document report mainly have SAPO-11,
ZSM-35, ZSM-22, MCM-22 and FER molecular sieve etc..Hetero atom wherein with SAPO-11 molecular sieves as representative takes
It is that olefin isomerization selectivity is higher for phosphate aluminium molecular sieve and ZSM molecular sieve, is the catalyst with preferable application potential.SAPO
(aluminium silicophosphate) molecular sieve is developed earliest by union carbide corporation of the U.S., is the class point that adjustable port size and adjustable acidity combine
Sub- sieve catalyst, with middle strong acidity.
US5292984 is disclosed using the mixing carbon five of amylene containing 1- 38% as raw material, in reaction pressure 1.8MPa, reaction
Temperature 327-357 DEG C, hydrogen and alkene volume ratio are under conditions of 8,480 hours steady have been carried out to SAPO-11 molecular sieves
Qualitative experiment, n-pentene conversion ratio is more than 70%, and isomeric olefine accounts for more than 93% in product, when reaction pressure is reduced to 1.0MPa
When conversion ratio be declined slightly, but selectivity maintains more than 90%.
US5430221 is disclosed in 260-290 DEG C, 0.2-0.3MPa and Feed space velocities 1.1h-1Under conditions of, by ZSM-35 point
Son sieve is applied to the reaction of n-pentene skeletal isomerization；Due to excellent properties of the ZSM-35 molecular sieve in n-butene isomerization reaction, just
Pentene conversion and iso-amylene selectivity are more than 70%.
CN1511637A discloses one kind and the raw material for containing normal olefine (or pure normal olefine) is carried out the side of skeletal isomerization
Method, the catalyst for using is prepared from for raw material by molecular sieve, modified kaolin and binding agent, and the molecular sieve is SAPO-11
And/or ZSM-35 molecular sieve, modified kaolin is to add chlorination through 500-800 DEG C of high-temperature roasting, acid treatment by Kaolin
Magnesium and/or calcium chloride or ammonium phosphate auxiliary agent are processed, calcination activation is obtained.This catalyst is used for into the bone of C_5 olefins
Frame isomerization reaction, the conversion ratio of n-pentene is more than 70%, and iso-amylene selectivity is more than 85%, single pass life 40-60 hours.
Also document is described 1- amylenes as reaction raw materials, compares tri- kinds of molecules of SAPO-11, BEA and AlMCM-41
Catalytic performance of the sieve to n-pentene skeletal isomerization, the temperature range of investigation is 250 DEG C -400 DEG C (1-Pentene isomerization
Over SAPO-11, BEA and AlMCM-41molecular sieves, Applied Catalysis A:General 340
(2008),1-6).Result of the test shows, for SAPO-11 and AlMCM-41, the selectivity of skeletal isomerization with temperature rising
And improve, and HDBEA is then presented contrary trend, and more C1-C4 products are generated during high temperature, this is due to HDBEA
Measure with more acid and compared with QiangBSuan centers, and the pore structure of catalyst then affects little to catalytic performance.In reaction temperature
400 DEG C, mass space velocity 3.5h-1Under conditions of normal pressure, the n-pentene conversion ratio of SAPO-11 molecular sieves is more than 45%, iso-amylene
Selectivity is up to 95%.
Although molecular sieve catalyst has above-mentioned advantage, production cost height, the not environment friendly used in preparation process are still suffered from
Organic formwork agent the shortcomings of, its service life also has much room for improvement.
The content of the invention
In view of above the deficiencies in the prior art, it is an object of the invention to provide a kind of alkene bone with high activity and high selectivity
Frame isomerization catalyst, the catalyst also has low cost, long service life and environment amenable advantage.The present invention is also provided
The preparation method and application of the catalyst.
The invention provides a kind of olefin skeletal isomerization catalyst, it includes amorphous silicon alumina supporter and is carried on the carrier
Heteropoly acid.
The amorphous silica-alumina is adopted well known to a person skilled in the art altogether prepared by plastic method.
According to the present invention, the weight of the heteropoly acid is preferably the 1-20% of the catalyst weight, more preferably 3.1-14.8%, optimum
Select 5.1-9.9%.
Optionally, the heteropoly acid is preferably in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, silicomolybdic acid, germanotungstic acid and germanium molybdic acid extremely
Few one kind, more preferably phosphotungstic acid and/or phosphomolybdic acid.
In the catalyst, the mol ratio of the silicon, aluminum and heteropoly acid is preferably 1:(0.01-0.5):(0.0001-0.005) it is, more excellent
Select 1:(0.03-0.3):(0.0003-0.004), most preferably 1:(0.1-0.12):(0.001-0.0012).Silicon, aluminum in catalyst
Can be obtained by chemical analysis such as x-ray fluorescence spectrometry with the mol ratio of heteropoly acid.
It is preferred that the specific surface area of the catalyst is 300-800m2/ g, pore volume is 0.1-1.2ml/g, and most probable pore size is
The specific surface area of more preferably described catalyst is 400-700m2/ g, pore volume is 0.2-1.0ml/g, and most probable pore size is
Inventor Jing many experiments find that heteropoly acid is because anion volume is big, symmetry is good and charge density is low, thus performance
Go out the B-acid more higher than traditional inorganic oxacid (sulphuric acid, phosphoric acid etc.), can on amorphous silicon alumina supporter by loaded by heteropoly acid
Change species and the distribution in carrier surface acid site, moreover it is possible to which heteropoly acid is used as into catalytic active component, it is a kind of with height so as to be formed
The olefin skeletal isomerization catalyst of activity and high selectivity.Heteropoly acid is added in the preparation process of amorphous silicon alumina supporter, both
Can also be used for adjusting the pH of reaction system as the active component of catalyst, simplify course of reaction.
Present invention also offers the preparation method of the catalyst, including silicon source solution is mixed with silicon source solution, adds heteropoly acid
Solution is adjusted to certain pH, the plastic under the pH, then carries out aging, dry and calcination process.
According to the present invention, the silicon source is preferably metal silicate, more preferably in sodium silicate, ammonium silicate and potassium silicate at least
It is a kind of；Source of aluminium is preferably inorganic aluminate, the more preferably at least one in aluminum sulfate, aluminum chloride and aluminum nitrate；The acid
Solution is preferably inorganic acid, the more preferably at least one in hydrochloric acid, nitric acid and sulphuric acid.
In embodiments of the present invention, the concentration of source of aluminium solution is preferably 0.02-0.2mol/L, more preferably 0.03-0.1mol/L；
The concentration of the silicon source solution is preferably 0.2-2.0mol/L, more preferably 0.3-1.0mol/L；The concentration of the heteropoly acid is preferably
0.02-0.15mol/L, more preferably 0.05-0.1mol/L；Optionally, the volume ratio of the silicon source solution and silicon source solution is preferably
1:(0.5-2), more preferably 1:(1-1.5).
The present invention does not have particular/special requirement for the order by merging of silicon source solution and silicon source solution, preferably by silicon source solution lentamente Deca
To in silicon source solution；It is preferred that silicon source solution and silicon source solution are mixed at 50-70 DEG C.
According to the present invention, the pH is preferably 2.0-6.0, more preferably 3.0-4.0；The aging temperature is preferably 40-80 DEG C, more
It is preferred that 50-70 DEG C, ageing time is preferably 16-36 hours, more preferably 20-30 hours；The baking temperature is preferably 100-140 DEG C,
More preferably 110-130 DEG C, it is preferably 2-6 hours, more preferably 3-5 hours drying time；The temperature of the calcination process is
450-650 DEG C, preferred 500-600 DEG C, time of calcination process is 2-8 hours, preferred 4-5 hours.In the preferred reality of the present invention
In applying mode, silicon source solution and silicon source solution are mixed, Deca heteropoly acid solution by pH regulator to 3.0-4.0, then at 50-70 DEG C
Stirring 1-3 hours make its plastic, standing carry out burin-in process in aging 24 hours；Ageing products are filtrated to get into filter cake, then will filter
Cake is dried process, and baking temperature is 100-140 DEG C, is dried 2-6 hours；Then desciccate is carried out into calcination process, is roasted
It is 450-650 DEG C to burn temperature, roasting 2-8 hours；Finally product of roasting is pulverized and sieved, you can obtain catalyst.
The present invention has no particular limits to the equipment used in catalyst preparation process, it is possible to use common plastic cans, is dried
And calcining process is then respectively using the drying oven with conveyer belt and roaster.
Present invention also offers another kind of preparation method of the catalyst, including silicon source solution is mixed with silicon source solution, with acid
Solution adjusts pH, the plastic under the pH, through it is aging, be dried and calcination process makes carrier, then by infusion process by institute
Carrier impregnation is stated in heteropoly acid solution, is then dried and calcination process.
According to the present invention, the time of the infusion process is preferably 1-4 hours, more preferably 2-3 hours.
Above two preparation method has the preparation condition of same range, and such as aging, drying can adopt similar temperature with baking process
Degree and time, heteropoly acid can adopt similar species and concentration.
According to this preparation method, in certain embodiments of the present invention, prepare using infusion process carried heteropoly acid after carrier,
Infusion process is adopted well known to a person skilled in the art technological means and reaction condition, preferred equi-volume impregnating；Can by dipping
Increase the content of active component in carrier
According to this preparation method, in a preferred embodiment of the invention, silicon source solution and silicon source solution are mixed, Deca hydrochloric acid
PH regulator to 3.0-4.0 is made its plastic, standing carry out burin-in process in 24 hours by solution then at 50-70 DEG C of stirring 1-3 hour；
Ageing products are filtrated to get into filter cake, then filter cake is dried into process, 100-140 DEG C of baking temperature is dried 2-6 hours；So
Afterwards desciccate is carried out into calcination process, sintering temperature is 450-650 DEG C, roasting 2-8 hours；Finally product of roasting was crushed
Sieve, that is, obtain carrier；The carrier be impregnated in into 1-4 hours in heteropoly acid solution by equi-volume impregnating, then at 100-140 DEG C
Under be dried 2-6 hours；Desciccate is carried out into roasting 2-8 hours in 450-650 DEG C, you can obtain catalyst.
Present invention also offers the catalyst or catalyst the answering in olefin skeletal isomerization reaction obtained according to preparation method
With preferably described olefin skeletal isomerization reaction is etherified benzine skeletal isomerization.
The etherified benzine skeletal isomerization includes the catalyst is loaded on reactor, and etherified benzine is passed through
In the reactor, skeletal isomerization is carried out under uniform temperature, pressure and Feed space velocities, reaction follows product after terminating
Being looped back to methyltertiarvbutyl ether reactor carries out Etherification of Light FCC Gasoline reaction.
The catalytic temperature is preferably 250-400 DEG C, more preferably 300-350 DEG C.The catalyst that the present invention is provided is to isomerization reaction
Temperature it is more sensitive, the olefin conversion for significantly improving can be obtained after slightly heating up, in the industrial production to equipment and energy consumption
Requirement it is relatively low.
The volume of the catalyst is preferably 10-50ml, more preferably 20-40ml；The Feed space velocities are preferably 2.0-5.0h-1, more
It is preferred that 2.5-4.5h-1；The pressure is preferably 0.1-0.3MPa, more preferably normal pressure.
According to the present invention, when reaction temperature is 300-350 DEG C, light gasoline Feed space velocities are 2.5-4.5h after ether-1When, the positive structure alkene of carbon five
Hydrocarbon conversion rate is 65-85%, and iso-amylene selectivity is 80-95%；The normal olefine conversion ratio of carbon six is 55-70%, and dissident's alkene is selected
Property is 90-98%.
Olefin skeletal isomerization reaction of the present invention can be carried out in any ether cracking reactor of disclosed technology, preferably solid
Fixed bed adiabatic reactor, product can loop back methyltertiarvbutyl ether reactor and carry out Etherification of Light FCC Gasoline reaction.
Beneficial effects of the present invention：
1) present invention makes the preparation of carrier with the load of active component while entering in the preparation process of carried heteropoly acid catalyst
OK, the step of simplifying catalyst preparation；Using catalyst of the present invention, cost is significantly reduced compared with molecular sieve, and is made
Standby process does not use the organic template agent of not environment friendly, does not result in environmental pollution.
2) catalyst of the present invention possesses good heterogeneous activity and selectivity for olefin skeletal isomerization reaction, can be by
Unreacted normal olefine isomerization after light FCC gasoline etherificate, generates the isomeric olefine with etherification activity, so as to improve
The yield of etherified benzine.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, it will be appreciated by those skilled in the art that
The following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted actual conditions person in embodiment,
The condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, being to pass through
City available from conventional products.
Embodiment 1
Weigh 19.6g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 60 DEG C of water
Stir in bath to being completely dissolved.Weigh 5.6g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, the Deca in 30 minutes
To in above-mentioned silicon solution, stop 5 minutes.The Salkowski's solution of Deca 0.08mol/L (i.e. 25 weight %) and pH=3.0 is adjusted again,
Stand after continuing to stir 2 hours at 60 DEG C.Filter after aging 24 hours, filter cake is in 120 DEG C of dryings 4 hours, 550 DEG C of roastings
Burn 4 hours, catalyst is obtained after pulverizing and sieving.Jing chemical analysis methods show that the content of phosphotungstic acid in catalyst is 6.1 weight %,
The mol ratio of silicon, aluminum and phosphotungstic acid is 1:0.12:0.0012, the specific surface area of catalyst is 552m2/ g, pore volume is 0.8ml/g,
Most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
300 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1, the main composition of light FCC gasoline is shown in Table 1, etherification reaction
Methanol and ethers are separated afterwards, and the content of normal olefine accounts for more than 40%.The result that reaction is obtained is the normal olefine conversion ratio of carbon five
66.2%, iso-amylene selectivity 86%；The normal olefine conversion ratio 57% of carbon six, dissident's alkene selectivity 95%.
Table 1
Embodiment 2
Weigh 19.6g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 60 DEG C of water
Stir in bath and be completely dissolved.Weigh 5.6g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, the Deca in 30 minutes
To in above-mentioned silicon solution, stop 5 minutes.The phosphorus molybdenum acid solution of Deca 0.08mol/L (i.e. 25 weight %) and pH=3.0 is adjusted again,
Stand after continuing to stir 2 hours at 60 DEG C.Filter after aging 24 hours, filter cake is in 120 DEG C of dryings 4 hours, 550 DEG C of roastings
Burn 4 hours, catalyst is obtained after pulverizing and sieving.Jing chemical analysis methods show that the content of phosphomolybdic acid in catalyst is 5.6 weight %,
The mol ratio of silicon, aluminum and phosphomolybdic acid is 1:0.12:0.0011, the specific surface area of catalyst is 560m2/ g, pore volume is 0.8ml/g,
Most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
300 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 65% of carbon five,
Iso-amylene selectivity 85.5%；The normal olefine conversion ratio 53.6% of carbon six, dissident's alkene selectivity 95%.
Embodiment 3
Weigh 19.6g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 60 DEG C of water
Stir in bath and be completely dissolved.Weigh 5.6g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, the Deca in 30 minutes
To in above-mentioned silicon solution, stop 5 minutes.Again the Salkowski's solution of Deca 0.08mol/L (i.e. 25 weight %) adjusts pH=3.0, in
Continue to stir 2 hours at 60 DEG C, filter after aging 24 hours.Filter cake is dried 4 hours at 120 DEG C, roasting 4 at 550 DEG C
Hour, catalyst is obtained after pulverizing and sieving.Jing chemical analysis methods show that the content of phosphotungstic acid in catalyst is 6.1 weight %,
The mol ratio of silicon, aluminum and phosphotungstic acid is 1:0.12:0.0012, the specific surface area of catalyst is 552m2/ g, pore volume is 0.8ml/g,
Most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
330 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 81.5% of carbon five,
Iso-amylene selectivity 85%；The normal olefine conversion ratio 67.8% of carbon six, dissident's alkene selectivity 95%.
Embodiment 4
Weigh 19.6g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 60 DEG C of water
Stir in bath and be completely dissolved.Weigh 5.6g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, the Deca in 30 minutes
To in above-mentioned silicon solution, stop 5 minutes.Again the hydrochloric acid solution of weight % of Deca 5 adjusts pH=3.0, continues to stir 2 at 60 DEG C
Stand after hour, filter after aging 24 hours.Filter cake is dried 4 hours at 120 DEG C, 550 DEG C of roastings 4 hours, crushes
Silica-alumina supports are obtained after sieve.The Salkowski's solution of 0.08mol/L (i.e. 25 weight %) is prepared, equal-volume is adopted in obtained carrier
Impregnation 2 hours, is then dried 4 hours, 550 DEG C of roastings, 4 hours prepared catalyst at 120 DEG C.Jing chemical analyses
Method show that the content of phosphotungstic acid in catalyst is 6.0 weight %, and the mol ratio of silicon, aluminum and phosphotungstic acid is 1:0.12:0.0012,
The specific surface area of catalyst is 593m2/ g, pore volume is 0.82ml/g, and most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
330 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 80.8% of carbon five,
Iso-amylene selectivity 85%；The normal olefine conversion ratio 66.7% of carbon six, dissident's alkene selectivity 95%.
Embodiment 5
Weigh 9.24g potassium silicate (K2SiO3) 200ml water is dissolved in, in pouring 500ml there-necked flasks into, stir in 60 DEG C of water-baths
Mix to being completely dissolved.Weigh 0.8g aluminum chloride (AlCl3) 200ml water is dissolved in, during above-mentioned silicon solution was added drop-wise in 30 minutes,
Stop 5 minutes.The silico-tungstic acid solution of Deca 0.08mol/L (i.e. 25 weight %) and pH=4.0 is adjusted again, continue to stir at 60 DEG C
Stand after mixing 2 hours, filter after aging 24 hours.Filter cake in 110 DEG C of dryings 2 hours, crush by 500 DEG C of roastings 5 hours
Catalyst is obtained after sieving.Jing chemical analysis methods draw silico-tungstic acid in catalyst content be 13 weight %, silicon, aluminum and silicon tungsten
The mol ratio of acid is 1:0.04:0.003, the specific surface area of catalyst is 537m2/ g, pore volume is 0.80ml/g, and most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
300 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 73.1% of carbon five,
Iso-amylene selectivity 82.0%；The normal olefine conversion ratio 55.4% of carbon six, dissident's alkene selectivity 92.3%.
Embodiment 6
Weigh 56.8g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 70 DEG C of water
Stir in bath and be completely dissolved.Weigh 63g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, the Deca in 30 minutes
To in above-mentioned silicon solution, stop 5 minutes.Again the hydrochloric acid solution of weight % of Deca 5 adjusts pH=5.0, continues to stir 2 at 60 DEG C
Stand after hour, filter after aging 24 hours.Filter cake is dried 6 hours at 140 DEG C, 450 DEG C of roastings 8 hours, crushes
Silica-alumina supports are obtained after sieve.The Salkowski's solution of 0.08mol/L (i.e. 25 weight %) is prepared, equal-volume is adopted in obtained carrier
Impregnation 2 hours, is then dried 6 hours, 450 DEG C of roastings, 8 hours prepared catalyst at 140 DEG C.Jing chemical analyses
Method show that the content of phosphotungstic acid in catalyst is 1.1 weight %, and the mol ratio of silicon, aluminum and phosphotungstic acid is 1:0.45:0.0004,
The specific surface area of catalyst is 633m2/ g, pore volume is 0.87ml/g, and most probable pore size is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
300 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 60.2% of carbon five,
Iso-amylene selectivity 87.4%；The normal olefine conversion ratio 54.5% of carbon six, dissident's alkene selectivity 97.5%.
Comparative example 1
Weigh during 300g boehmites (salic 71 weight %) are added to water heating kettle, while deionized water 900ml is added,
Phosphoric acid 500g (weight % containing orthophosphoric acid 85) and deionized water 900ml is stirring evenly and then adding into, is added after continuing to stir 10 minutes
Enter Ludox 150g (weight % containing silicon dioxide 25), stirring adds different di-n-propylamine 220g after 10 minutes, continue to stir until
Form homogeneous colloids.Water heating kettle is put in baking oven, 120 DEG C of constant temperature is warming up to 4 hours, then to be warming up to 220 DEG C of constant temperature 24 little
When, then cooling, washing, dry and roasting is obtained SAPO-11 sieve samples.
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
330 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 82.4% of carbon five,
Iso-amylene selectivity 84%；The normal olefine conversion ratio 69% of carbon six, dissident's alkene selectivity 92%.
Comparative example 2
Weigh 19.6g sodium silicate (Na2SiO3·9H2O in) being dissolved in 200ml water, in pouring 500ml there-necked flasks into, in 60 DEG C of water-baths
Middle stirring is simultaneously completely dissolved.Weigh 5.6g aluminum sulfate (Al2(SO4)3·16H2O in) being dissolved in 200ml water, it was added drop-wise in 30 minutes
In above-mentioned silicon solution, stop 5 minutes.Again the hydrochloric acid solution of weight % of Deca 5 adjusts pH=3.0, stirring 2 is continued at 60 DEG C little
When after stand, after aging 24 hours filter.Filter cake is dried 4 hours at 120 DEG C, 550 DEG C of roastings 4 hours, pulverizes and sieves
Silica-alumina supports are obtained afterwards.Jing chemical analysis methods show that specific surface area of catalyst is 659m2/ g, pore volume is 0.9ml/g, most probable
Aperture is
Etherified benzine skeletal isomerization reaction is carried out on 100ml fixed bed reactors, loaded catalyst is 30ml, reacted
330 DEG C of temperature, reaction pressure normal pressure, Feed space velocities 2.5h-1.The result that reaction is obtained is the normal olefine conversion ratio 65.4% of carbon five,
Iso-amylene selectivity 87.6%；The normal olefine conversion ratio 55.3% of carbon six, dissident's alkene selectivity 95.1%.
The catalyst that the present invention is provided has good heterogeneous activity and selectivity, and in embodiment 1-6, iso-amylene selectivity is reachable
To more than 87%, dissident's alkene selectivity can reach more than 95%.Compared with embodiment, comparative example 1 prepares SAPO-11 molecular sieves
During used the different di-n-propylamine of organic formwork agent of not environment friendly, and complicated process of preparation, catalyst is relatively costly.Will
The silica-alumina supports of the unsupported heteropoly acid that comparative example 2 is prepared are used for isomerization reaction, the carbon five for obtaining and the normal olefine of carbon six
Conversion ratio is significantly lower than the embodiment of the present application.The catalyst that the present invention is provided is applied to into light FCC gasoline etherificate-isomery work
Skill, unreacted normal olefine isomerization after can light FCC gasoline be etherified in a mild condition generates and there is etherificate to live
The isomeric olefine of property, so as to improve the yield and octane number of etherified benzine.
It should be noted that embodiment described above is only used for explaining the present invention, any limitation of the invention is not constituted.
By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive and explanatory
Vocabulary, rather than limited vocabulary.By regulation the present invention can be modified within the scope of the claims, and
The present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it be related to specific method,
Material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, the present invention can be extended to other
All methods and applications with identical function.
Claims (11)
1. a kind of olefin skeletal isomerization catalyst, comprising amorphous silicon alumina supporter and load heteropoly acid on the carrier.
2. catalyst according to claim 1, it is characterised in that
The weight of the heteropoly acid is the 1-20% of the catalyst weight, preferred 5.1-9.9%；
Preferably, the heteropoly acid is at least in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, silicomolybdic acid, germanotungstic acid and germanium molybdic acid
Kind.
3. catalyst according to claim 1 and 2, it is characterised in that wherein the mol ratio of silicon, aluminum and heteropoly acid is 1:
(0.01-0.5):(0.0001-0.005), preferably 1:(0.03-0.3):(0.0003-0.004), more preferably 1:(0.1-0.12):
(0.001-0.0012)。
4. the catalyst according to any one of claim 1-3, it is characterised in that the specific surface area of the catalyst is 400
-700m2/ g, pore volume is 0.2-1.0ml/g, and most probable pore size is
5. a kind of method for preparing the catalyst as any one of claim 1-4, including silicon source solution is mixed with silicon source solution
Close, add heteropoly acid solution to adjust to certain pH value, then the plastic under the pH value carries out aging, dry and roasting
Process.
6. a kind of method for preparing the catalyst as any one of claim 1-4, including silicon source solution is mixed with silicon source solution
Close, with acid solution pH value is adjusted, the plastic under the pH value is made carrier, then led to through aging, dry and calcination process
Infusion process is crossed by the carrier impregnation in heteropoly acid solution, is then dried and calcination process.
7. the method according to claim 5 or 6, it is characterised in that
The silicon source is metal silicate, the preferably at least one in sodium silicate, ammonium silicate and potassium silicate；
Source of aluminium is inorganic aluminate, preferably at least one in aluminum sulfate, aluminum chloride and aluminum nitrate；And/or
The acid solution is inorganic acid, the preferably at least one in hydrochloric acid, nitric acid and sulphuric acid.
8. the method according to any one of claim 5-7, it is characterised in that
The concentration of source of aluminium solution is 0.02-0.2mol/L, preferred 0.03-0.1mol/L；
The concentration of the silicon source solution is 0.2-2.0mol/L, preferred 0.3-1.0mol/L；
The concentration of the heteropoly acid solution is 0.02-0.15mol/L, preferred 0.05-0.1mol/L；
Preferably, the volume ratio of the silicon source solution and silicon source solution is 1:(0.5-2), preferably 1:(1-1.5).
9. the method according to any one of claim 5-8, it is characterised in that
The pH value is 2.0-6.0, preferred 3.0-4.0；
The aging temperature be 40-80 DEG C, preferred 50-70 DEG C, ageing time be 16-36 hours, preferred 20-30 hours；
The baking temperature be 100-140 DEG C, preferred 110-130 DEG C, drying time be 2-6 hours, preferred 3-5 hours；With/
Or
The temperature of the calcination process is 450-650 DEG C, and preferred 500-600 DEG C, the time of calcination process is 2-8 hours, preferably
4-5 hours.
10. a kind of catalyst as any one of claim 1-4 or according to any one of claim 5-9 method system
Application of the standby catalyst in olefin skeletal isomerization reaction, preferably described olefin skeletal isomerization reaction is etherified benzine bone
Frame isomerization reaction.
11. applications according to claim 10, it is characterised in that the application includes depositing etherified benzine in the catalyst
Under, skeletal isomerization, and the product of the skeletal isomerization are carried out under uniform temperature, pressure and Feed space velocities
Optionally being recycled methyltertiarvbutyl ether reactor carries out Etherification of Light FCC Gasoline reaction；
Preferably, the temperature is 250-400 DEG C, preferred 300-350 DEG C；The Feed space velocities are 2.0-5.0h-1, preferably
2.5-4.5h-1；The pressure be 0.1-0.3MPa, preferred normal pressure.
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