CN109718854A - A kind of solid acid catalysts and the preparation method and application thereof - Google Patents
A kind of solid acid catalysts and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of solid acid catalysts and the preparation method and application thereof；The catalyst is using heteropoly acid or peroxide heteropoly acid as main active component, using the anion exchange resin of such as flowering structure as carrier:Wherein: X indicates that halogen, y indicate the integer between 1~10, and m, n are positive integer, m:n=1:10~1:100, R5、R6、R7Any one in the straight chained alkyl, phenyl or benzyl for being 1~18 independently selected from carbon atom number.The present invention is by mixing heteropoly acid or peroxide heteropoly acid solution with the vector resin being swollen, and at a temperature of 20~60 DEG C, stirs 5~20h, then filter, wash, dry, obtains solid acid catalyst.The catalyst heat resistance is good, long service life, and is easily recycled, environmental-friendly, is suitable for cyclopentadiene oxidation and generates bicyclopentadiene dioxide, reaction yield is greater than 90%.
Description
Technical field
The invention belongs to chemical industry catalysis technical field, it is related to a kind of solid acid catalysts and preparation method thereof and answers
With.
Background technique
Heteropoly acid is the more uniform pure Bronsted acid of acid strength, can efficient catalyzed alkene epoxidation reaction and to ring
Border is friendly.Heteropoly acid (HPA) is to pass through oxygen by central atom P, Si, As, Ge etc., coordination atom Mo, V, W etc. with certain structure
The oxygen-containing multi-acid salt general name of Atomic coordinate bridging composition, the most strikingly heteropoly acid of structure with Keggin in catalysis reaction
Salt.Smaller (1~the 10m of solid acid catalysts specific surface area2G-1), and recycling is difficult, it is effectively carried on carrier
, it can be achieved that heterogeneousization of homogeneous catalytic reaction, is conducive to the separation of product and catalyst, the carrier of use mainly has two after upper
Silica, active carbon, molecular sieve, metal oxide, ion exchange resin, polymer porous material etc..Heteropoly acid after load
Active constituent specific surface area increases, and catalytic activity also significantly improves, and catalyst easily recycles, and is suitable for continuous production, is conducive to
Production cost is reduced, product quality is improved, this plays huge impetus for the realization of industrialization of heteropoly acid catalysis.
Nineteen eighty-three, Venturello report Na2WO4/H3PO4/H2O2Biphasic catalysis epoxidation systems are in phase transfer catalysis (PTC)
In the presence of agent, react to the conversion ratio of most of alkene such as 1- octene, cyclohexene, styrene all 95% or more, epoxides
Selectivity is 80% or so.Ishii is reported by heteropoly acid H3PWl2O40Or H3PMo12O40With hexadecylpyridinium chloride group
At catalyst in the presence of, epoxidation reaction is carried out to a variety of organic substrates with 35% hydrogen peroxide, homogeneously even
It can effectively carry out in a two-phase system.Xi Zuwei etc. is reported with H2O2For oxygen source, under cryogenic, quaternary phosphorus
Tungsten heteropoly compound Q3[PW4O16(Q=quaternary ammonium salt) can a variety of alkene such as efficient catalytic cyclohexene, propylene, 1- octene, styrene
Epoxidation reaction, the selection rate of conversion ratio and epoxides is mostly 90% or so.From the point of view of existing document report, quaternary ammonium
The generally existing catalyst recycling of salt form phosphorus tungsten heteropoly compound (Venturello-Ishii) catalyst system is difficult, reuses secondary
The disadvantages of number is few.In reaction with catalyst preparation DCPDDO, since DCPD boiling point is high, reaction product aoxidizes dicyclopentadiene
For solid, product is undesirable with separation and recovery of catalyst, affects the quality of product, and catalyst reusability is bad (at most
It is 2 times), so that process costs be made to improve, it is unfavorable for industrializing.Li Li is loaded to 12- phosphotungstic acid without airborne using infusion process
Body SiO2On, though solving the problems, such as the recycling of catalyst, use degradation active after 1 time.Wang Yong grid etc. report chloromethane
Base macroporous polystyrene-divinyl benzene crosslinked resin (PS) graft N-benzyl-N, N- dimethyl dodecyl base quaternary ammonium peroxide
Phospho heteropoly tungstate is three-phase flash, using 50% industrial hydrogen peroxide as oxidant, optimizes and prepares DCPDDO's
Reaction condition, at optimum conditions, for the yield of DCPDDO up to 89% or more, catalyst recycling is convenient, and reuses 7 times not
See that activity is substantially reduced.From the point of view of existing technology, heteropolyacid salt or peroxide heteropolyacid salt are carried on quaternary ion and handed over
Resin is changed, using hydrogen peroxide as oxygen source, DCPD is oxidized to DCPDDO with reaction yield height, environmental friendly, catalyst recycling side
Just the advantages that.But existing quaternary ammonium anion exchange resin heat resistance is poor, and at 60~70 DEG C of reaction temperature, reaction
Raw material is under conditions of catalyst average contact time general 15 hours, and quaternary ammonium salt group gradually decomposes obviously in reaction process,
Cause catalyst activity component heteropoly acid or peroxide heteropoly acid to be lost, influences catalyst service life.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of solid acid catalysts and preparation method thereof with
Using.Process for synthetic catalyst of the invention is simple, and catalyst has heat-resist, service life stabilization, environmental-friendly, is suitable for alkene
The epoxidation reaction of hydrocarbon.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of solid acid catalysts, which is loaded catalyst, with heteropoly acid or mistake
Oxa- polyacid is active component, using poly- halogenated styrenes-divinylbenzene quaternary phosphine salt type anion exchange resin body as carrier, is carried
Shown in the structure of body such as general formula (1):
Wherein: 1 on phenyl ring, 2,3,4,5,6 be the carbon atoms numbered in phenyl ring, and X indicates that halogen, y indicate between 1~10
Integer, m, n are positive integer, m:n=1:10~1:100, R5、R6、R7The straight chain alkane for being 1~18 independently selected from carbon atom number
Any one in base, phenyl or benzyl.
In the present invention, the mass percentage of active component is 26.6%~52.4% in catalyst.
In the present invention, X is selected from any one of F, Cl or Br, and y indicates the integer between 1~6, R5、R6、R7Independently select
From methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, dodecyl, myristyl, cetyl or octadecane
It is any in base.
In the present invention, the connected , quaternary alkylphosphonium salt ionic group of any carbon atoms on a benzene ring of X and general formula (1) middle number 2,3,4
R5R6R7P+(CH2) y and No. 1 carbon atom of phenyl ring represented by general formula (1) and any in the four carbon atom except the connected carbon atom of X
It is a to be connected, form or mixtures thereof poly- halogenated styrenes-divinylbenzene quaternary phosphine salt type anion exchange resin of different structure.
In the present invention, poly- halogenated styrenes-divinylbenzene quaternary phosphine salt type anion exchange resin carrier exchange capacity
3.5~4.2mmol/g.
In the present invention, heteropoly acid is by the hetero atom including including P, Si, Fe, Co, Ni, Nb, Ta, As, Se, Zr, Ga etc.
The oxygen-containing polyacid constituted is coordinated by oxygen atom bridging with the polyatom including including Mo, W, V, Ni, Nb etc., is preferably
Structure with Keggin, can be any in 12 phosphotungstic acids, 12 silico-tungstic acids, 12 silicomolybdic acid or 12 phosphomolybdate.
The present invention also provides a kind of preparation methods of above-mentioned solid acid catalysts, the specific steps are as follows:
A. the carrier of 3 parts by weight general formula (1) structures is taken, the solvent that 3~10 parts by weight are added is swollen；
B. it takes the heteropoly acid of 10~15 parts by weight to be dissolved in polar solvent and is configured to heteropoly acid solution；Or take 10~15 parts
Weight heteropoly acid dissolution mass concentration be 5%~70% aqueous hydrogen peroxide solution in, 20~30 DEG C at a temperature of, reaction
2~5h generates peroxide heteropoly acid solution；
C. the step B heteropoly acid generated or peroxide heteropoly acid solution are mixed with the carrier being swollen that step A is obtained,
At a temperature of 20~60 DEG C, 5~20h is stirred；It filters, washs again, it is dry to constant weight, obtain solid acid catalysts.
In the present invention, in step A, the solvent for carrier swelling is selected from methanol, ethyl alcohol, acetone, chloromethanes, two chloroethenes
Any one or a few in alkane, tetrahydrofuran or 1,4- dioxane；In step B, the polarity for preparing heteropoly acid solution is molten
Agent in water, methanol, ethyl alcohol, acetone, chloromethanes, dichloroethanes, tetrahydrofuran or 1,4- dioxane any one or
It is several.
In the present invention, in step B, heteropoly acid heteropoly acid solution preparation method: is dissolved in the poles such as water, alcohol, ketone, ether, ester
Heteropoly acid solution formed in property solvent, is preferably dissolved in the small easy volatile solvent of the surface tension such as ethyl alcohol, acetone, ether and is formed
Solution, concentration 0.005g/ml~0.5g/ml of heteropoly acid, preferred concentration be 0.02~0.3g/ml.
In the present invention, in step B, peroxide heteropoly acid solution is prepared, a certain amount of heteropoly acid solid is taken to be slowly added into matter
Measuring concentration is in 5%~70% hydrogenperoxide steam generator m (heteropoly acid): m (H2O2)=1:1~1:3 (mass ratio), at 20~30 DEG C
Under, 2~5h is stirred, oxa- polyacid solution is obtained.
The present invention also provides a kind of application of above-mentioned heteropolyacid catalyst in epoxidation reaction of olefines.Catalyst can be with
It, can also be by general formula (2) by cycloolefins epoxidations such as cyclopentene, cyclohexene, cyclo-octene, cyclododecene, norbornene, a- firpenes
Class olefin oxidation generates general formula (3) class compound, the R in general formula (2), general formula (3)1、R2、R3、R4It is independent selected from hydrogen, C1~
It is the straight chained alkyl of C14, branched alkyl, naphthenic base, any in aryl.Preferably, alkene is dicyclopentadiene DCPD.
In the present invention, catalyst activity and stability are checked and rated using fixed bed continuous reaction technique.Stable anti-
It answers under process conditions, catalyst activity and stability are to be influenced on bicyclopentadiene dioxide reaction yield with the reaction time to comment
Valence.
Bicyclopentadiene dioxide reaction yield: in the unit time, bicyclopentadiene dioxide is generated in reactor
(DCPDDO) molal quantity divided by the unit time enter reactor dicyclopentadiene (DCPD) molal quantity.
Compared to the prior art, the beneficial effects of the present invention are method for preparing catalyst of the present invention is simple；Using poly- halogen
It is carrier for styrene-divinylbenzene quaternary phosphine salt type anion exchange resin, catalyst heat resistance is preferable, mentions in the present invention
Under the reaction condition of confession, catalyst stabilization is run 500 hours, and reactivity is basically unchanged.
Detailed description of the invention
Fig. 1 is the activity rating curve of the catalyst in Application Example 1 of the invention.
Specific embodiment
The present invention is further illustrated with embodiment below, but the invention is not limited to following embodiments.
Anion exchange resin structure used in Examples 1 to 6 is shown in Formulas I~III respectively.
Embodiment 1
In tri- mouthfuls of glass flasks of 1000ml, addition exchange capacity is 3.5mmol/g, structure quaternary alkylphosphonium salt yin shown in formula I
5h is stirred at room temperature in ion exchange resin 3g (butt), dehydrated alcohol 40g, and the 12 phosphorus tungsten that concentration is 0.025g/ml are then added
Heteropoly acid solution acid (H3PW12O40.nH2O) ethanol solution 350g, room temperature, mechanical stirring 20h turn the material in three-necked flask
It moves on in funnel, filters, separate solvent, be further washed with distilled water solid catalyst particle, with 0.2% silver nitrate solution
After distilled water halogen-free ionic after monitoring washing, the catalyst solid in funnel is put into baking oven, 50 DEG C, perseverance is arrived in normal pressure, drying
Weight, obtains 6.1g catalyst, loaded by heteropoly acid amount 50.8%.
Embodiment 2
In tri- mouthfuls of glass flasks of 500ml, investment exchange capacity is 4.2mmol/g, the structure yin of the quaternary alkylphosphonium salt as shown in Formula II
5h is stirred at room temperature in ion exchange resin 3g (butt), acetone 100g, and the 12 silicon tungsten heteroacid that concentration is 0.20g/ml are then added
Solution acid (H4SiW12O40.nH2Material in three-necked flask is transferred to funnel by O) acetone soln 70g, room temperature, mechanical stirring 5h
In, it filters, separates solvent, be further washed with distilled water solid catalyst particle, monitor washing with 0.2% silver nitrate solution
After distilled water halogen-free ionic afterwards, the catalyst solid in funnel is put into baking oven, 40 DEG C, constant weight is arrived in normal pressure, drying, obtains
4.1g catalyst, loaded by heteropoly acid amount 26.6%.
Embodiment 3
In tri- mouthfuls of glass flasks of 1000ml, addition exchange capacity is 3.5mmol/g, structure quaternary alkylphosphonium salt as shown in formula III
5h is stirred at room temperature in anion exchange resin 3g (butt), dichloroethanes 90g, and 12 phosphorus that concentration is 0.025g/ml are then added
Molybdenum heteropolyacid solution acid (H3PMo12O40.nH2O) ethanol solution 700g, room temperature, mechanical stirring 15h, by the material in three-necked flask
It is transferred in funnel, filters, separate solvent, be further washed with distilled water solid catalyst particle, it is molten with 0.2% silver nitrate
After distilled water halogen-free ionic after liquid monitoring washing, the catalyst solid in funnel is put into baking oven, 60 DEG C, normal pressure, drying is arrived
Constant weight obtains 6.3g catalyst, loaded by heteropoly acid amount 52.4%.
Embodiment 4
In tri- mouthfuls of glass flasks of 500ml, addition exchange capacity be 3.5mmol/g, structure quaternary alkylphosphonium salt yin shown in formula I from
5h is stirred at room temperature in sub-exchange resin 3g (butt), dehydrated alcohol 30g；12g phosphotungstic acid is weighed, 50g matter is then added
It measures in the hydrogenperoxide steam generator that concentration is 30%, 20 DEG C, stirs 2h, oxa- polyacid solution is obtained；By peroxide phosphorus heteropoly tungstic acid
Solution is added in the ion exchange resin being swollen, room temperature, mechanical stirring 10h, and the material in three-necked flask is transferred to leakage
It in bucket, filters, separates solvent, be further washed with distilled water solid catalyst particle, washed with 0.2% silver nitrate solution monitoring
After distilled water halogen-free ionic after washing, the catalyst solid in funnel is put into baking oven, 50 DEG C, constant weight is arrived in normal pressure, drying, obtains
5.2g catalyst, peroxide phosphorus heteropoly tungstic acid load capacity 42.3%.
Embodiment 5
In tri- mouthfuls of glass flasks of 500ml, addition exchange capacity be 3.5mmol/g, structure quaternary alkylphosphonium salt yin shown in formula I from
5h is stirred at room temperature in sub-exchange resin 3g (butt), dehydrated alcohol 30g；12g phosphotungstic acid is weighed, 300g is then added
In the hydrogenperoxide steam generator that mass concentration is 5%, 20 DEG C, 2h is stirred, oxa- polyacid solution is obtained；By peroxide phosphorus heteropoly tungstic acid
Solution is added in the ion exchange resin being swollen, room temperature, mechanical stirring 10h, and the material in three-necked flask is transferred to leakage
It in bucket, filters, separates solvent, be further washed with distilled water solid catalyst particle, washed with 0.2% silver nitrate solution monitoring
After distilled water halogen-free ionic after washing, the catalyst solid in funnel is put into baking oven, 50 DEG C, constant weight is arrived in normal pressure, drying, obtains
5.0g catalyst, peroxide phosphorus heteropoly tungstic acid load capacity 40.0%.
Embodiment 6
In tri- mouthfuls of glass flasks of 1000ml, addition exchange capacity is 3.5mmol/g, structure quaternary alkylphosphonium salt yin shown in formula I
5h is stirred at room temperature in ion exchange resin 3g (butt), dehydrated alcohol 30g；12g phosphotungstic acid is weighed, 52g is then added
In the hydrogenperoxide steam generator that mass concentration is 70%, 20 DEG C, 5h is stirred, oxa- polyacid solution is obtained；Peroxide phosphorus tungsten is miscellaneous more
Acid solution is added in the ion exchange resin being swollen, and separately plus 300g dehydrated alcohol, room temperature, mechanical stirring 20h burn three mouthfuls
Material in bottle is transferred in funnel, is filtered, is separated solvent, be further washed with distilled water solid catalyst particle, with 0.2%
Silver nitrate solution monitoring washing after distilled water halogen-free ionic after, the catalyst solid in funnel is put into baking oven, 80 DEG C, often
Pressure, drying arrive constant weight, obtain 5.80g catalyst, peroxide phosphorus heteropoly tungstic acid load capacity 48.3%.
Application Example 1
Prepared catalyst reactivity of the present invention is investigated, fixed bed reaction technique is 20mm in internal diameter, and length is
In the jacket type stainless steel tubular reactor of 1000mm, catalyst 50ml prepared by embodiment 1, catalyst bed upper and lower side are loaded
Load inertia bique ball.The temperature of reactor is controlled by outer circulation type conduction oil, and reactor pressure is by being mounted on discharge port pipeline
On counterbalance valve control, reaction mass enters after metering is pumped into static mixer by reactor bottom, flows through catalyst bed
Layer is flowed out by reactor head, flows into reaction product storage tank after cooler is cooling.Timing sampling, gas chromatographic analysis reaction produce
Object composition.60 DEG C of reaction temperature, reaction pressure 0.5MPa, n (DCPD): n (H2O2)=1:3 (molar ratio), V (DCPD): V (third
Ketone)=1:3 (volume), reaction raw materials volume space velocity 0.1h-1, W (H2O2) %=50%, W (DCPD) %=95%, 500 hours
Catalyst activity examination, the experimental results showed that (see Fig. 1), using method provided by the invention, resin heat resistance is good, and catalyst is steady
Surely after running 500h, good reactivity worth is still maintained.
Application Example 2
Catalyst 50ml prepared by embodiment 2 is loaded, experimental facilities and technological operation step are shown in Application Example 1, react
Temperature 70 C, reaction pressure 1.5MPa, n (DCPD): n (H2O2)=1:3 (molar ratio), V (DCPD): V (acetone)=1:3 (body
Product), reaction raw materials volume space velocity 0.1h-1, W (H2O2) %=50%, W (DCPD) %=95%, catalyst activity is examined within 500 hours
It comments.The experimental results showed that being formed from reactor outlet sampling analysis product, titanium dioxide after catalyst continuous and steady operation 500h
Dicyclopentadiene reaction yield 91.9%.
Application Example 3
Catalyst 50ml prepared by embodiment 3 is loaded, experimental facilities and technological operation step are shown in Application Example 1, react
Temperature 60 C, reaction pressure 2.5MPa, n (DCPD): n (H2O2)=1:3 (molar ratio), V (DCPD): V (acetone)=1:3 (body
Product), reaction raw materials volume space velocity 0.1h-1, W (H2O2) %=50%, W (DCPD) %=95%, catalyst activity is examined within 500 hours
It comments.The experimental results showed that being formed from reactor outlet sampling analysis product, titanium dioxide after catalyst continuous and steady operation 500h
Dicyclopentadiene reaction yield 92.1%.
Application Example 4
Catalyst 50ml prepared by embodiment 4 is loaded, experimental facilities and technological operation step are shown in Application Example 1, react
Temperature 70 C, reaction pressure 0.5MPa, n (DCPD): n (H2O2)=1:3 (molar ratio), V (DCPD): V (acetone)=1:3 (body
Product), reaction raw materials volume space velocity 0.1h-1, W (H2O2) %=50%, W (DCPD) %=95%, catalyst activity is examined within 500 hours
It comments.The experimental results showed that being formed from reactor outlet sampling analysis product, titanium dioxide after catalyst continuous and steady operation 500h
Dicyclopentadiene reaction yield 92.6%.
Claims (11)
1. a kind of solid acid catalysts, which is characterized in that the catalyst is loaded catalyst, with heteropoly acid or peroxide
Heteropoly acid is active component, using poly- halogenated styrenes-divinylbenzene quaternary phosphine salt type anion exchange resin as carrier, carrier
Shown in structure such as general formula (1):
Wherein: 1 on phenyl ring, 2,3,4,5,6 be the carbon atoms numbered in phenyl ring, and X indicates that halogen, y indicate whole between 1~10
Number, m, n are positive integer, m:n=1:10~1:100, R5、R6、R7Straight chained alkyl, benzene independently selected from carbon atom number for 1~18
Any one in base or benzyl.
2. solid acid catalysts according to claim 1, which is characterized in that the quality hundred of active component in catalyst
Dividing content is 26.6%~52.4%.
3. solid acid catalysts according to claim 1, which is characterized in that X is selected from any one of F, Cl or Br,
Y indicates the integer between 1~6, R5、R6、R7Independently selected from methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl,
It is any in dodecyl, myristyl, cetyl or octadecyl.
4. solid heteropoly acid agent according to claim 1, which is characterized in that times of X and general formula (1) middle number 2,3,4
One carbon atoms on a benzene ring is connected , quaternary alkylphosphonium salt ionic group R5R6R7P+(CH2) No. 1 carbon atom of phenyl ring and X institute represented by y and general formula (1)
Even any of the four carbon atom except carbon atom is connected.
5. solid acid catalysts according to claim 1, which is characterized in that poly- halogenated styrenes-divinylbenzene
3.5~4.2mmol/g of exchange capacity of quaternary phosphine salt type anion exchange resin carrier.
6. solid acid catalysts according to claim 1, which is characterized in that heteropoly acid is structure with Keggin, choosing
It is any from 12 phosphotungstic acids, 12 silico-tungstic acids, 12 silicomolybdic acid or 12 phosphomolybdate.
7. a kind of preparation method of solid acid catalysts according to claim 1, which is characterized in that specific steps are such as
Under:
A. the carrier of 3 parts by weight general formula (1) structures is taken, the solvent that 3~10 parts by weight are added is swollen；
B. it takes the heteropoly acid of 10~15 parts by weight to be dissolved in polar solvent and is configured to heteropoly acid solution；Or take 10~15 parts of weight
Heteropoly acid dissolution mass concentration be 5%~70% aqueous hydrogen peroxide solution in, 20~30 DEG C at a temperature of, reaction 2~
5h generates peroxide heteropoly acid solution；
C. the step B heteropoly acid generated or peroxide heteropoly acid solution are mixed with the carrier being swollen that step A is obtained, 20~
At a temperature of 60 DEG C, 5~20h is stirred；It filters, washs again, it is dry to constant weight, obtain solid acid catalysts.
8. preparation method according to claim 7, which is characterized in that in step A, the solvent for carrier swelling is selected from first
Any one or a few in alcohol, ethyl alcohol, acetone, chloromethanes, dichloroethanes, tetrahydrofuran or 1,4- dioxane；In step B,
For prepare heteropoly acid solution polar solvent be selected from water, methanol, ethyl alcohol, acetone, chloromethanes, dichloroethanes, tetrahydrofuran or
Any one or a few in 1,4- dioxane.
9. preparation method according to claim 7, which is characterized in that in step B, the heteropoly acid solution concentration of preparation is
0.02~0.3g/ml, when preparing peroxide heteropoly acid solution, m (heteropoly acid): m (H2O2)=1:1~1:3.
10. a kind of application of solid acid catalysts according to claim 1 in epoxidation reaction of olefines.
11. application according to claim 10, which is characterized in that alkene is dicyclopentadiene DCPD.
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