CN107497497A - A kind of resin catalyst and its method of modifying applied to Etherification of Light FCC Gasoline reaction - Google Patents
A kind of resin catalyst and its method of modifying applied to Etherification of Light FCC Gasoline reaction Download PDFInfo
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- CN107497497A CN107497497A CN201710879433.2A CN201710879433A CN107497497A CN 107497497 A CN107497497 A CN 107497497A CN 201710879433 A CN201710879433 A CN 201710879433A CN 107497497 A CN107497497 A CN 107497497A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4025—Yield
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The present patent application provides a kind of strong-acid type modified cation resin catalyst and its method of modifying.Strong-acid type modified cation resin catalyst therein, it is modified to obtain through heteropoly acid by cation resin catalyzing agent, the heteropoly acid adsorbed in the modified bead of cation resin catalyzing agent accounts for the 0.1~2% of total catalyst weight, and described heteropoly acid is H4Xn+M12O40Or H3Xn+M12O40In it is one of any.Its method of modifying is that cation resin catalyzing agent obtains through methanol elution after dipping modification in heteropoly acid maceration extract, and active high, the stability height of modified catalyst, active constituent be not easy to be lost, the technological merit of service life length.
Description
Technical field
Present patent application is related to modified cation resin catalyzing agent and its method of modifying, more particularly to is applied to
The modified cation resin catalyst and its method of modifying of Etherification of Light FCC Gasoline reaction.
Background technology
Etherification of Light FCC Gasoline is including the iso-amylene and different by the alkene in light FCC gasoline, predominantly active olefin
Hexene etc., generation ether is reacted with methanol, to produce the effective technology means of low olefin-content, High-octane mogas.Light vapour
The catalyst of oily etherification reaction is storng-acid cation exchange resin, is solid macromolecule acid, is total to by styrene and divinylbenzene
Poly- obtained bead, then it is sulfonated obtained.This storng-acid cation exchange resin is also widely used in alkene hydration, ethers
It is one of important catalyst of petrochemical industry, fine chemistry industry and pharmaceutical field in the reactions such as hydrolysis, esterification, condensation.
The technique processing method of Etherification of Light FCC Gasoline is a lot.Mainly there is the Etherification of Light FCC Gasoline technique that CDTECH companies of the U.S. release
Method, it is that catalytically cracked gasoline is first entered into catalytic hydroprocessing reactive distillation column, the diene hydrogenation in gasoline is removed, simultaneously will
Gasoline be separated into it is light, weigh two components, light petrol therein is etherified instead through fixed bed reactors and methanol in the presence of catalyst
Should, most of Tertiary olefin in light petrol is converted into ether compound, enter back into catalytic rectifying tower depth etherificate.It is another kind of light
Etherification technology of gasoline, as Mobil companies release, it is to mix the lower alcohol of excess and light petrol, first carries out first time catalysis
Etherificate, then be fractionated, methanol and below C5 hydro carbons are contained in light fraction, ether and more than C5 hydro carbons are contained in heavy distillat, light fraction is again
It is etherified；First time etherificate therein uses acidic catalyst, and second of etherificate uses metal silicate catalysts, so as to drop
Olefin(e) centent in low gasoline, improve octane number.The catalyst that existing process method uses is cation resin catalyzing
Agent, existing cation resin catalyzing agent generally existing poor activity, the technical problem of the different loss of active component, it is above-mentioned the former can
It is 60% or so to be etherified light dydrocarbon conversion ratio, the technical deficiency of existing cation resin catalyzing agent also existence and stability deficiency, is used
Life-span is one year.
The content of the invention
The goal of the invention of present patent application is to overcome the existing cation resin catalyzing applied to Etherification of Light FCC Gasoline reaction
Activity is low existing for agent, active constituent is easy to run off, the technical problem of stability deficiency, there is provided a kind of activity is high, it is excellent steady to have
It is qualitative, and than surface and specific pore volume suitably as Etherification of Light FCC Gasoline application, there is provided it is a kind of to be applied to what Etherification of Light FCC Gasoline reacted
Resin catalyst and its method of modifying.
A kind of resin catalyst technical scheme applied to Etherification of Light FCC Gasoline reaction that present patent application provides, its main skill
Art content is：A kind of resin catalyst applied to Etherification of Light FCC Gasoline reaction, it is modified by cation resin catalyzing agent through heteropoly acid
Obtain, the heteropoly acid adsorbed in the modified bead of cation resin catalyzing agent accounts for the 0.1~2% of total catalyst weight, described
Heteropoly acid is H4Xn+M12O40Or H3Xn+M12O40In it is one of any, and,
H4Xn+M12O40In X be Si or Ge, M are Mo or W；
H3Xn+M12O40In X be P or As, M are Mo or W.
The preference of above-mentioned technical proposal, its heteropoly acid account for the 0.5~1.0% of total catalyst weight.
Present patent application additionally provides a kind of modification based on the resin catalyst applied to Etherification of Light FCC Gasoline reaction
Method, its main technical content are：A kind of method of modifying of resin catalyst applied to Etherification of Light FCC Gasoline reaction：Drenched by methanol
Cation resin catalyzing agent is washed, the water content to discharge liquor is less than 5%, and it is dried 3~8 hours after 60-90 DEG C, then is impregnated in
In maceration extract, standing is not shorter than 12 hours, takes out dry at a temperature of 60-90 DEG C and obtains, and described maceration extract is containing active
Component H4Xn+M12O40Or H3Xn+M12O40In one of any, aqueous solution that concentration is 0.1~2%.
The preference of above-mentioned method of modifying scheme, described maceration extract are H containing active component4Xn+M12O40Or H3Xn+
M12O40In one of any, aqueous solution that concentration is 0.5~1.0%.
The preference of above-mentioned method of modifying scheme, described methanol are industrial primes and the methanol of above rank.
A kind of resin catalyst applied to Etherification of Light FCC Gasoline reaction disclosed in present patent application is applied to Etherification of Light FCC Gasoline
In production, by taking the etherification reaction that typical fixed bed reactors implement light petrol and methanol as an example, light petrol and methanol metering are mixed
Together in head tank, the fixed bed reactors with water-bath structure are pumped into by measuring pump, reactant is sent into collecting tank, and fixed bed is anti-
Answering the reaction condition of device is：Reaction temperature is 40 DEG C~60 DEG C, operating pressure is 0.1~0.5MPa, light petrol passes through catalyst
The air speed of bed is 0.5h-1~3h-1.After testing, the tertiary amylene conversion ratio of its light petrol reaches more than 75%, it was demonstrated that this patent
The active high technological merit of resin catalyst for being applied to Etherification of Light FCC Gasoline reaction of application offer, practice is it is also shown that originally
Resin catalyst stability applied to Etherification of Light FCC Gasoline reaction is high, and active constituent is not easy to be lost, and normal service life can reach
18 months.
Embodiment
In following embodiment, what the cation resin catalyzing agent that is modified was selected is the limited public affairs of Dandong jewel Special Resin
The s cation resin catalyzing agent products of D005- II of department, but present patent application is not limited by embodiment content, is equally applicable to it
Its cation resin catalyzing agent, and there is same technique effect.
Embodiment 1
The obtained resin catalyst applied to Etherification of Light FCC Gasoline reaction, by weight percentage, the s resin cations of D005- II
The heteropoly acid adsorbed in bead after catalyst modification is H4SiMo12O40, account for the 0.5% of total catalyst weight., its method of modifying
For：Spherical D006 types cation resin catalyzing agent, its particle size range are 0.3~1.2mm, with industrial primes and above rank first
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 3 hours by 60 DEG C of temperature of drying box thereafter, dry resin cation
Catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component4SiMo12O40Concentration is 0.5%
The aqueous solution, static 12 hours are impregnated, take out to dry in 60 DEG C of temperature and obtain.Its physical performance index, including specific pore volume, ratio
Surface and strength conditions are shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm fixed bed
In reactor, methanol is with light petrol weight than 1:8, reaction temperature is 40 DEG C, operating pressure 0.2MPa, liquid air speed（LHSV）For
2h-1, the product of etherification reaction, sampling result：The conversion ratio of iso-amylene is 77.81% in its light petrol.
Embodiment 2
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H4SiW12O40, account for the 0.5% of total catalyst weight.Its method of modifying is：It is spherical
The s type cation resin catalyzing agent of D005- II, its particle size range is 0.3~1.2mm, with industrial primes and the first of above rank
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 4 hours in 70 DEG C of temperature in drying box thereafter, take dry sun from
Sub- resin catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component4SiW12O40Concentration is
0.5% aqueous solution, static 12 hours are impregnated, take out to dry at a temperature of 90 DEG C and obtain.Its physical performance index, including
Specific pore volume, than surface and strength conditions it is shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol is with light petrol weight than 1:8, reaction temperature is 50 DEG C, operating pressure 0.4MPa, liquid air speed
（LHSV）For 0.5h-1, the product of etherification reaction, sampling：The conversion ratio of tertiary amylene is 80.27% in its light petrol.
Embodiment 3
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H3PW12O40, account for the 1% of total catalyst weight.Its method of modifying is：Spherical D005-
II s type cation resin catalyzing agent, its particle size range are 0.3~1.2mm, are drenched with industrial primes and the methanol of above rank
Wash, the water content to discharge liquor is less than 5%, is dried 7 hours by 80 DEG C of temperature of drying box thereafter, takes dry resin cation to urge
Agent is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component3PW12O40Concentration be 1.0% it is water-soluble
Liquid, static 12 hours, take out and dry to obtain in 80 DEG C of temperature.Its physical performance index, including specific pore volume, than surface and intensity
Situation is shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol is with light petrol weight than 1:8, reaction temperature is 60 DEG C, operating pressure 0.5MPa, liquid air speed
（LHSV）For 3h-1, the product of etherification reaction, sampling result：The conversion ratio of tertiary amylene is 79.55% in its light petrol.
Embodiment 4
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H3PMo12O40, account for the 1.0% of total catalyst weight.Its method of modifying is：It is spherical
The s type cation resin catalyzing agent of D005- II, its particle size range is 0.3~1.2mm, with industrial primes and the first of above rank
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 8 hours by 60 DEG C of temperature of drying box thereafter, takes dry cation tree
Fat catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component3PW12O40Concentration is 1.0%
The aqueous solution, static 12 hours are impregnated, take out to dry in 70 DEG C of temperature and obtain.Its physical performance index, including specific pore volume, ratio
Surface and strength conditions are shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol is with light petrol weight than 1:8, reaction temperature is 40 DEG C, operating pressure 0.1MPa, liquid air speed
（LHSV）For 1h-1, the product of etherification reaction, sampling result：The conversion ratio of tertiary amylene is 81.34% in its light petrol.
Embodiment 5
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H3PMo12O40, account for the 2.0% of total catalyst weight.Its method of modifying is：It is spherical
The s type cation resin catalyzing agent of D005- II, its particle size range is 0.3~1.2mm, with industrial primes and the first of above rank
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 4 hours by 90 DEG C of temperature in drying box thereafter, takes dry cation
Resin catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component3PW12O40Concentration is 2.0%
The aqueous solution, impregnate static 12 hours, take out and dry to obtain after 60 DEG C of temperature.Its physical performance index, including specific pore volume,
1 is shown in Table than surface and strength conditions.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol and light petrol weight ratio, reaction temperature is 50 DEG C, operating pressure 0.5MPa, liquid air speed
（LHSV）For 2h-1, the product of etherification reaction, sampling result：The conversion ratio of tertiary amylene is 78.19% in its light petrol.
Embodiment 6
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H4GeW12O40, account for the 2.0% of total catalyst weight.Its method of modifying is：It is spherical
The s type cation resin catalyzing agent of D005- II, its particle size range is 0.3~1.2mm, with industrial primes and the first of above rank
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 6 hours by 70 DEG C of temperature of drying box thereafter, takes dry cation tree
Fat catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component4GeW12O40Concentration is 2.0%
The aqueous solution, static 12 hours are impregnated, takes out and dries to obtain after 60 DEG C of temperature.Its physical performance index, including specific pore volume, ratio
Surface and strength conditions are shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol and light petrol weight ratio, reaction temperature is 60 DEG C, operating pressure 0.3MPa, liquid air speed
（LHSV）For 0.5h-1, the product of etherification reaction, sampling result：The conversion ratio of tertiary amylene is 79.22% in its light petrol.
Embodiment 7
Obtained strong-acid type modified cation resin catalyst, by weight percentage, the s cation resin catalyzing agent of D005- II
The heteropoly acid adsorbed in modified bead is H3AsMo12O40, account for the 1.0% of total catalyst weight.Its method of modifying is：It is spherical
The s type cation resin catalyzing agent of D005- II, its particle size range is 0.3~1.2mm, with industrial primes and the first of above rank
Alcohol elutes, and the water content to discharge liquor is less than 5%, is dried 6 hours by 60 DEG C of temperature of drying box thereafter, takes dry cation tree
Fat catalyst is immersed in heteropoly acid maceration extract, and described heteropoly acid maceration extract is H containing active component3AsMo12O40Concentration is 1.0%
The aqueous solution, impregnate static 12 hours, take out and obtained after drying at 90 DEG C.Its physical performance index, including specific pore volume, ratio
Surface and strength conditions are shown in Table 1.
Made strong-acid type modified cation resin catalyst 40ml is taken, is filled in Φ 25mm × 2.5mm's
In fixed bed reactors, methanol is 1 with light petrol weight ratio:8, reaction temperature is 40 DEG C, operating pressure 0.2MPa, liquid air speed
（LHSV）For 3h-1, the product of etherification reaction, sampling result：The conversion ratio of tertiary amylene is 80.49% in its light petrol.
Table 1
Claims (5)
1. a kind of strong-acid type modified cation resin catalyst, it is characterised in that be modified by cation resin catalyzing agent through heteropoly acid
Obtain, the heteropoly acid adsorbed in the modified bead of cation resin catalyzing agent accounts for the 0.1~2% of total catalyst weight, described
Heteropoly acid is H4Xn+M12O40Or H3Xn+M12O40In it is one of any, and,
H4Xn+M12O40In X be Si or Ge, M are Mo or W；
H3Xn+M12O40In X be P or As, M are Mo or W.
2. strong-acid type modified cation resin catalyst according to claim 1, it is characterised in that heteropoly acid accounts for catalyst
The 0.5~1.0% of gross weight.
3. a kind of method of modifying for preparing the strong-acid type modified cation resin catalyst of claim 1 or 2, its feature exist
In：Its method is：Cation resin catalyzing agent is eluted by methanol, the water content to discharge liquor is less than 5%, and it is dry after 60-90 DEG C
Dry 3~8 hours, then be impregnated in maceration extract, standing was not shorter than 12 hours, takes out to dry at a temperature of 60-90 DEG C and obtains, institute
The maceration extract stated is H containing active component4Xn+M12O40Or H3Xn+M12O40In one of any, aqueous solution that concentration is 0.1~2%.
4. method of modifying according to claim 3, it is characterised in that described maceration extract is H containing active component4Xn+M12O40
Or H3Xn+M12O40In one of any, aqueous solution that concentration is 0.5~1.0%.
5. the method for modifying according to claim 3 or 4, it is characterised in that described methanol is for industrial primes and with higher level
Other methanol.
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| CN201710879433.2A CN107497497A (en) | 2017-09-26 | 2017-09-26 | A kind of resin catalyst and its method of modifying applied to Etherification of Light FCC Gasoline reaction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07265711A (en) * | 1994-03-31 | 1995-10-17 | Cosmo Oil Co Ltd | Catalyst for etherification reaction of tertiary olefin |
| CN1390643A (en) * | 2002-06-17 | 2003-01-15 | 中国科学院大连化学物理研究所 | Application method of heteropoly acid type catalyst |
| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| CN1727323A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for preparing alkyl salicylic acid |
| CN103773479A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing clean gasoline |
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| JPH07265711A (en) * | 1994-03-31 | 1995-10-17 | Cosmo Oil Co Ltd | Catalyst for etherification reaction of tertiary olefin |
| CN1390643A (en) * | 2002-06-17 | 2003-01-15 | 中国科学院大连化学物理研究所 | Application method of heteropoly acid type catalyst |
| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| CN1727323A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for preparing alkyl salicylic acid |
| CN103773479A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing clean gasoline |
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