CN103801295A - Catalyst for reaction of preparing aviation kerosene by castor oil and a preparation method of catalyst - Google Patents
Catalyst for reaction of preparing aviation kerosene by castor oil and a preparation method of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for reaction of preparing aviation kerosene by castor oil through hydrogenation and a preparation condition of the catalyst. Modified MCM-41, SBA-15 and the like are used as the carrier of a hydro-de-oxygenation catalyst, and one selected from Ni, Ni2P, Co, CoP and Pt is used as an active component; modified SAPO-11, SAPO-34 and the like are used as the carrier of a hydrogenation isomerism catalyst, and one or two selected from Ni, Ag, Pd and Ru is/are used as the active component; the catalyst for the action of preparing the aviation kerosene by the castor oil through a one-step method is characterized in that with one or more selected from modified USY, a beta-type molecular sieve, an X-type molecular sieve and ZSM-5 as the carrier and Ni and Cu as active components or Ni2P and Cu3P as the active components, under a proper reaction condition, the aviation kerosene which meets the need of the operation conditions is prepared.
Description
Technical field
The present invention proposes catalyst and the preparation condition thereof of castor oil Hydrogenation for aviation kerosine.Wherein hydrogenation deoxidation catalyst is that MCM-41, SBA-15 etc. take modification is as carrier, with Ni, Ni
2one in P, Co, CoP, Pt is as active component; Hydroisomerization catalyst is using modification SAPO-11, SAPO-34 etc. as carrier, using one or both in Ni, Ag, Pd, Ru as active component; The catalyst that castor oil one-step method is prepared aviation kerosine is as carrier, using Ni, Cu as active component or with Ni using one or both in modification USY, beta molecular sieve, X-type molecular sieve, ZSM-5
2p, Cu
3p is as active component, and by suitable reaction condition, preparation meets the aviation kerosine of service condition.
Background technology
The fast development of industry increases the consumption of the energy fast, and then energy shortage becomes the essential condition of restriction industrial development and even social progress.In order to solve especially petroleum-based energy problem of the energy, study reproducible bioenergy and urgently can not treat.In recent years, the research of preparing biodiesel and aviation kerosine by esterification and method of hydrotreating with animal and plant fat constantly occurs rarely having report but prepare aviation kerosine take castor oil as raw material.
Castor oil is the glyceride of 9-thiazolinyl-12-hydroxy octadecadienoic acid, with respect to other vegetable and animals oils, owing to wherein containing hydroxyl and two key, complicated structure, therefore its hydrogenation deoxidation process is more more difficult than palm oil relatively simple for structure (hexadecylic acid glyceride), curcas oil (olein) etc.Castor oil is the plant grease of the non-oil of a kind of non-grain, has wide planting range in China, and output is large and stablize, and is a kind of raw material of good aviation kerosine.
For aviation kerosine, be that carbon number is the branched paraffin of 8-16 and the mixture of linear paraffin, its freezing point is-49 ℃, therefore branched paraffin is by the main component that is aviation kerosine.Castor oil is that carbon number is 18 vegetable fat, preparing aviation kerosine need to be through saturated, the carbon oxygen saturation of double bonds of the removing of perhydroxyl radical, carbon-carbon double bond, removing of carbonyl and removing of glycerine, to carry out in addition carbon chain break and reformation, just can obtain meeting the aviation kerosine of service condition.It is the alkane of 8-16 and to control its content be more difficult that the carbochain that is 17 and 18 by carbon number fragments into carbon number.
CN102676203A discloses a kind of take Jatropha curcas oil, rubber seed oil, palm oil, waste oil as raw material, through the technique of the two key oxidations of grease, hydrolysis, decarboxylic reaction, prepares the alkane of C8-C16, is the method for living beings aviation fuel.CN103320153A discloses one take castor oil as raw material, selects suitable catalyst and reaction condition, through hydrogenation deoxidation reaction and hydroisomerizing reaction, prepares the method for aviation kerosine.CN102482595A discloses a kind of manufacture method of aviation fuel oil base material, take animal and plant fat as raw material, by the catalyst with dehydrogenation and hydride functional, raw material is carried out to hydrogenation treatment, then carries out the processing of hydrogenation isomery as raw material, obtains aviation fuel.CN102719319A discloses a kind of method of preparing biological aviation fuel take wilson dogwood oil as raw material, wilson dogwood oil is carried out after filtering and impurity removing, in fixed bed hydrogenation reactor, through hydrogenation deoxidation reaction and hydroisomerizing reaction, the product obtaining, through distilling and collecting the cut between 150-280 ℃, is the aviation kerosine that meets service condition.CN101952392A disclose a kind of developed prepare the method for aviation fuel for renewable raw materials as vegetable oil and animal tallow, raw material contact hydrogenation and dehydrogenation catalyst are prepared linear paraffin, contact again afterwards isomerization catalyst and carry out isomerization at least a portion linear paraffin and produce branched paraffin, and then contact selective cracking catalyst is to obtain the alkane of C8-C16.CN102719317A discloses a kind of method of utilizing the biological aviation fuel of fruit of a cubeb litsea tree fruit stone oil preparation, refining litsea citrate oil is carried out to hydrogenation deoxidation reaction and hydroisomerizing reaction, the product obtaining is got the cut between 150-280 ℃ through distillation, and it is carried out to the exquisite device of fiber liquid film-composite adsorption combined apparatus and dielectric field and refine, obtain meeting the biological aviation kerosine of service condition.CN103224835A discloses a kind of method that micro-algae is extracted unrighted acid and prepares aviation fuel that contains.CN102994138A discloses a kind of method of preparing biological aviation kerosine take waste oil as raw material.CN103087748A discloses a kind of method of preparing aviation kerosine or diesel oil take lignocellulosic as raw material.
The Rong of Peking University, Long etc. are with Ni-H
3pW
12o
40/ Al
2o
3for catalyst carries out hydrogenation deoxidation reaction preparation biodiesel to curcas oil, Qian, Eika W etc. with NiMo catalyst cupport at Al
2o
3, SiO
2-Al
2o
3, SAPO-11 and AlSBA-15 carry out to curcas oil the alkane that a step hydrogenation reaction is prepared C11-C18.
Summary of the invention
Based on above content, the present invention proposes hydrogenation deoxidation catalyst and the hydroisomerization catalyst of castor oil Hydrogenation for aviation kerosine, with and the reaction condition of preparation condition and catalyst, catalyst and preparation condition and reaction condition that castor oil one-step method is prepared aviation kerosine have also been proposed simultaneously.By castor oil being carried out to the qualified aviation kerosine of one-step or two-step reaction preparation, expand the source of aviation kerosine, to alleviate the crisis at the petroleum-based energy of current social.
Concrete technical scheme of the present invention is as described below:
1. prepare the hydrogenation deoxidation catalyst of aviation kerosine technique for castor oil, carrier is MCM-41, HMS, SBA-15, γ-Al
2o
3in one, and the ethanolic solution of the 3-aminopropyl triethoxysilane take mass fraction as 5% and mass fraction stir dipping pretreatment as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; With Ni, Ni
2one in P, Co, CoP is active constituent, and its quality accounts for the 20-30% of catalyst gross mass, or take Pt as active constituent, its quality accounts for the 0.1-0.5% of catalyst gross mass.
2. prepare the hydroisomerization catalyst of aviation kerosine technique for castor oil, carrier is one or both in SAPO-11, SAPO-34, ZSM-5, beta molecular sieve, and the aqueous solution of the ethanedioic acid take mass fraction as 5% and mass fraction stir dipping pretreatment to carrier as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; Using one or both of Ni, Ag, Pd, Ru as active component, take one or both in Ni, Ag as active constituent, its quality accounts for the 10-25% of catalyst gross mass, or take one or both in Pd, Ru as active constituent, its quality accounts for the 0.1-0.7% of catalyst gross mass.
3. prepare the catalyst of aviation kerosine technique for castor oil one-step method for one kind, carrier is one or both in USY, beta molecular sieve, X-type molecular sieve, ZSM-5, and the aqueous solution of the ethanedioic acid take mass fraction as 5% and mass fraction stir dipping pretreatment to carrier as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; Using Ni, Cu as active component or with Ni
2p, Cu
3p is as active component, and wherein the mass ratio of Ni and Cu is 1: 0.1-0.1, Ni
2p and Cu
3the mass ratio of P is 1: 0.2-0.2, its quality accounts for the 10-30% of catalyst gross mass.
4. the preparation method for the hydrogenation deoxidation catalyst of aviation kerosine technique for castor oil Hydrogenation, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that carrier is joined to mass fraction, at 50-70 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, at 70-100 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 30-50 ℃ of stirring condition, the one in nickel nitrate, cobalt nitrate, chloroplatinic acid is dissolved in deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in sample C, stir at least 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique;
(4) uploading of active component: under 50-80 ℃ of stirring condition, the one of nickel nitrate, cobalt nitrate is dissolved in deionized water, adds ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards at least 4h, obtain solution F; Then solution F is joined in sample C, stir at least 8h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then at least 5h of roasting under 600 ℃ of air atmospheres, subsequently by the sample obtaining under hydrogen atmosphere 700 ℃ reduce at least 4h, then temperature is down to room temperature, obtain sample G, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, wherein the mol ratio of nickel nitrate and ammonium dihydrogen phosphate (ADP) is 1: 0.75-1.5, the mol ratio of cobalt nitrate and ammonium dihydrogen phosphate (ADP) is 1: 1.5-3.
5. the preparation method for the hydroisomerization catalyst of aviation kerosine technique for castor oil Hydrogenation, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that carrier is joined to mass fraction, stirs at least 24h at 60-80 ℃, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres; Afterwards the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, at 60-80 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 30-50 ℃ of stirring condition, one or both of nickel nitrate, silver nitrate, palladium chloride, rhodium chloride are dissolved in water, obtain solution D after fully dissolving; Afterwards sample C is joined in solution D, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique.
6. the preparation method who prepares the catalyst of aviation kerosine for castor oil one-step method, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that carrier is joined to mass fraction, at 100 ℃, stir at least 24h, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, afterwards the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, (at ℃, stir at least 24h 100, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample ℃ afterwards;
(3) uploading of active component: under 60-90 ℃ of stirring condition, nickel nitrate and copper nitrate are dissolved in water, obtain solution D after fully dissolving; Afterwards sample C is joined in solution D, stir at least 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil one-step method the catalyst of aviation kerosine technique;
(4) uploading of active component: under 100 ℃ of stirring conditions, nickel nitrate and copper nitrate are dissolved in deionized water, add ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards sample C is joined in solution D, stir at least 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, obtain preparing for castor oil one-step method the catalyst of aviation kerosine technique.
7. the using method for the hydrogenation deoxidation catalyst of aviation kerosine technique for castor oil Hydrogenation, comprises following steps:
(1) filling of catalyst: use high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 250-480 ℃, Hydrogen Vapor Pressure 1.0-5.5MPa, the liquid hourly space velocity (LHSV) 0.1-6.0/h of castor oil, the volume ratio 500-3000 of hydrogen and castor oil.
8. the using method for the hydrogenation deoxidation catalyst of aviation kerosine technique for castor oil Hydrogenation, comprises following steps:
(1) filling of catalyst: adopt high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 300-500 ℃, Hydrogen Vapor Pressure 1.0-6.0MPa, the liquid hourly space velocity (LHSV) 0.1-5.0/h of n-alkane, the volume ratio of hydrogen and n-alkane is 600-3500, and wherein n-alkane is the product of castor oil hydrogenation deoxidation.
9. the using method of preparing the catalyst of aviation kerosine technique for castor oil one-step method, comprises following steps:
(1) filling of catalyst: use high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 350-550 ℃, Hydrogen Vapor Pressure 1.0-5.5MPa, the liquid hourly space velocity (LHSV) 0.1-6.0/h of castor oil, the volume ratio 500-2500 of hydrogen and castor oil.
Compared with existing Catalysts and its preparation method, the present invention has following significantly innovation:
(1) for hydrogenation deoxidation catalyst, use silane coupler 3-aminopropyl triethoxysilane to stir pretreatment to carrier, the effectively distribution of dispersed activity component on carrier, the size of reduction particle diameter, can improve liquid yield simultaneously; Use citric acid to carry out pretreatment to carrier, can regulate the acidity of carrier, improve the conversion ratio of castor oil in course of reaction; Using Fe as auxiliary agent, can significantly improve the stability of catalyst, the life-span of extending catalyst.
(2) for hydroisomerization catalyst, use the aqueous solution of ethanedioic acid to carrier pretreatment, can regulate the acidity of carrier, increase the conversion ratio that linear paraffin tautomerizes to branched paraffin, simultaneously, with citric acid, carrier is carried out to further pretreatment, further adjust the acidity of carrier, making alkane cracking is the selective raising of C8-C16; Using Fe as auxiliary agent, can significantly improve the stability of catalyst, the life-span of extending catalyst.
(3) prepare the catalyst of aviation kerosine for one-step method, use the aqueous solution of ethanedioic acid to carry out pretreatment to carrier, regulate the acidity of carrier, increase the conversion ratio that linear paraffin isomery turns to branched paraffin, simultaneously, with lemon aqueous acid, carrier is carried out to further pretreatment, further regulate the acidity of carrier, improve the selective of kerosene component; Using Fe as auxiliary agent, can improve the stability of catalyst, the life-span of extending catalyst.
(4) the present invention proposes catalyst and the reaction condition that castor oil one-step method is prepared aviation kerosine, shortened the production cycle of biological aviation fuel, reduced hydrogen consumption, the cost of reduction aviation kerosine that can be larger.
Accompanying drawing explanation
Accompanying drawing 1 is the x-ray diffractogram of powder of the Ni/SAPO-11 catalyst of synthesized.
Accompanying drawing 2 is x-ray diffractogram of powder of the Ni/USY catalyst of synthesized.
Specific implementation method
The object of following examples is in order to make those skilled in the art understand in more detail the present invention; or content according to the present invention makes some nonessential improvement and adjustment, but illustrated embodiment is as the claims in the present invention technical scheme scope required for protection is made to any limit
Fixed, be contained in but do not comprise the scope that all requests are protected.
Embodiment 1, the preparation of hydrogenation deoxidation catalyst, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10gMCM-41 is joined to 100g mass fraction, at 60 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining being joined to 100g mass fraction is in 10% lemon aqueous acid, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.47g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.0g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active constituent: under 40 ℃ of stirring conditions, 8.99g nickel nitrate is dissolved in 45g deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in 7.7g sample C, stir 36h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 8h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, be denoted as cat1.
Embodiment 2, the preparation of hydrogenation deoxidation catalyst, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10gMCM-41 is joined to 100g mass fraction, at 60 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining being joined to 100g mass fraction is in 10% lemon aqueous acid, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 1.12g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.5g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active constituent: under 40 ℃ of stirring conditions, 6.69g nickel nitrate is dissolved in 45g deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in 7.1g sample C, stir 36h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 8h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, be denoted as cat2.
Embodiment 3, as the preparation of the load type metal phosphide catalyst of hydrogenation deoxidation catalyst, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10g SBA-15 is joined to 100g mass fraction, at 50 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining being joined to 100g mass fraction is in 10% lemon aqueous acid, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.86g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.5g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 80 ℃ of stirring conditions, 5.67g nickel nitrate is dissolved in 45g deionized water, adds 3.56g ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards 6h, obtain solution F; Then solution F is joined in 7.7g sample C, stir 12h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then roasting 8h under 600 ℃ of air atmospheres, by the sample obtaining 700 ℃ of reduction 6h under hydrogen atmosphere, then temperature is down to room temperature, obtains sample G subsequently, the hydrogenation deoxidation catalyst that obtains preparing for castor oil aviation kerosine technique, is denoted as cat3.
Embodiment 4, the using method of hydrogenation deoxidation catalyst, comprises the following steps:
(1) filling of catalyst: adopt high pressure fixed bed reactors, the filling of catalyst adopts the general filling process of fixed bed reactors;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein 350 ℃ of reaction temperatures, Hydrogen Vapor Pressure 3.30MPa, the liquid hourly space velocity (LHSV) 2.5/h of castor oil, the volume ratio 800 of hydrogen and castor oil.
Embodiment 5, the preparation of hydroisomerization catalyst, comprises the following steps:
(1) pretreatment of carrier: 10g SAPO-11 is joined in the aqueous solution that 50g mass fraction is 5% ethanedioic acid, stir 48h at 70 ℃, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres; Afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 80 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 13.5g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.79g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 50 ℃ of stirring conditions, 1.73g silver nitrate is dissolved in 13.5g deionized water, obtains solution D after fully dissolving; Afterwards 8.9g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 5h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique, be denoted as cat4.
Embodiment 6, the preparation of hydroisomerization catalyst, comprises the following steps:
(1) pretreatment of carrier: 10g SAPO-11 is joined in the aqueous solution that 50g mass fraction is 5% ethanedioic acid, stir 48h at 70 ℃, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres; Afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 80 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 1.12g ferric nitrate is dissolved in 11g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.3g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 50 ℃ of stirring conditions, 3.7g silver nitrate is dissolved in 11g deionized water, obtains solution D after fully dissolving; Afterwards 7.65g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 5h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique, be denoted as cat5.
Embodiment 7, the using method of hydroisomerization catalyst, comprises the following steps:
(1) filling of catalyst: adopt high pressure fixed bed reactors, the filling of catalyst adopts the general filling process of fixed bed reactors;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 800/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein 380 ℃ of reaction temperatures, Hydrogen Vapor Pressure 3.5MPa, the liquid hourly space velocity (LHSV) 1.5/h of n-alkane, the volume ratio of hydrogen and n-alkane is 1000, and wherein n-alkane is the product of castor oil hydrogenation deoxidation.
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that 10g USY is joined to 50g mass fraction, at 100 ℃, stir 48h, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 100 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 12.88g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.59g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 100 ℃ of stirring conditions, 2.46g nickel nitrate and 0.75g copper nitrate are dissolved in deionized water, add 1.95g ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards 8.7g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, the catalyst that obtains preparing for castor oil one-step method aviation kerosine technique, is denoted as cat6.
Embodiment 9, castor oil one-step method is prepared aviation kerosine catalyst, comprises the following steps:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that 10g USY is joined to 50g mass fraction, at 100 ℃, stir 48h, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 100 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 1.12g ferric nitrate is dissolved in 10.2g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 6.8g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 100 ℃ of stirring conditions, 1.28g nickel nitrate and 5.62g copper nitrate are dissolved in deionized water, add 4.25g ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards 7.15g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, the catalyst that obtains preparing for castor oil one-step method aviation kerosine technique, is denoted as cat7.
(1) filling of catalyst: adopt high pressure fixed bed reactors, the filling of catalyst adopts the general filling process of fixed bed reactors:
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 700/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein 360 ℃ of reaction temperatures, Hydrogen Vapor Pressure 3.70MPa, the liquid hourly space velocity (LHSV) 2.0/h of castor oil, the volume ratio 700 of hydrogen and castor oil.
Comparative example 1, object is that explanation is not used the preparation process of Fe as the hydrogenation deoxidation catalyst of auxiliary agent:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10gMCM-41 is joined to 100g mass fraction, at 60 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining being joined to 100g mass fraction is in 10% lemon aqueous acid, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of active constituent: under 40 ℃ of stirring conditions, 8.99g nickel nitrate is dissolved in 45g deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in 7.7g sample ℃, stir 36h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 8h under 600 ℃ of air atmospheres, obtains sample E afterwards, obtains preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique,, be denoted as cat8.
Comparative example 2, object is that explanation is not used the preparation process of Fe as the hydrogenation deoxidation catalyst using metal phosphide as active component of auxiliary agent:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10g SBA-15 is joined to 100g mass fraction, at 50 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining is joined to 100g mass fraction and be in 10% lemon aqueous acid, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(3) uploading of active component: under 80 ℃ of stirring conditions, 5.67g nickel nitrate is dissolved in 45g deionized water, adds 3.56g ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards 6h, obtain solution F; Then solution F is joined in 7.7g sample A, stir 12h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then roasting 8h under 600 ℃ of air atmospheres, by the sample obtaining 700 ℃ of reduction 6h under hydrogen atmosphere, then temperature is down to room temperature, obtains sample G subsequently, the hydrogenation deoxidation catalyst that obtains preparing for castor oil aviation kerosine technique, is denoted as cat9.
Comparative example 3, object is that explanation is not used the preparation process of Fe as the hydroisomerization catalyst of auxiliary agent:
(1) pretreatment of carrier: 10g SAPO-11 is joined in the aqueous solution that 50g mass fraction is 5% ethanedioic acid, stir 48h at 70 ℃, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres; Afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 80 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(3) uploading of active component: under 50 ℃ of stirring conditions, 1.73g silver nitrate is dissolved in 13.5g deionized water, obtains solution D after fully dissolving; Afterwards 8.9g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 5h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain the hydroisomerization catalyst that recruitment castor oil is prepared aviation kerosine technique, be denoted as cat10.
Comparative example 4, object is that explanation is not used Fe to prepare the preparation process of aviation kerosine catalyst as the castor oil one-step method of auxiliary agent:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that 10g USY is joined to 50g mass fraction, at 100 ℃, stir 48h, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, afterwards the sample obtaining is joined to 50g mass fraction and be in 10% lemon aqueous acid, at 100 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(3) uploading of active component: under 100 ℃ of stirring conditions, 2.46g nickel nitrate and 0.75g copper nitrate are dissolved in deionized water, add 1.95g ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards 8.7g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, the catalyst that obtains preparing for castor oil one-step method aviation kerosine technique, is denoted as cat11.
Comparative example 5, object is that explanation is not used 3-aminopropyl triethoxysilane carrier to be carried out to the preparation process of pretreated hydrogenation deoxidation catalyst:
(1) pretreatment of carrier: it is in 10% lemon aqueous acid that 10gMCM-41 is joined to 100g mass fraction, at 90 ℃, feel and mix 36h, then by the mixture suction filtration, the separation that obtain, will obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.47g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.0g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active constituent: under 40 ℃ of stirring conditions, 8.99g nickel nitrate is dissolved in 45g deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in 7.7g sample C, stir 36h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 8h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, be denoted as cat12.
Comparative example 6, object is that explanation is not used 3-aminopropyl triethoxysilane carrier to be carried out to the preparation process of the pretreated hydrogenation deoxidation catalyst using metal phosphide as active component:
(1) pretreatment of carrier: it is in 10% lemon aqueous acid that 10g SBA-15 is joined to 100g mass fraction, at 90 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, will obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.86g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.5g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 80 ℃ of stirring conditions, 5.67g nickel nitrate is dissolved in 45g deionized water, adds 3.56g ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards 6h, obtain solution F; Then solution F is joined in 7.7g sample C, stir 12h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then roasting 8h under 600 ℃ of air atmospheres, by the sample obtaining 700 ℃ of reduction 6h under hydrogen atmosphere, then temperature is down to room temperature, obtains sample G subsequently, the hydrogenation deoxidation catalyst that obtains preparing for castor oil aviation kerosine technique, is denoted as cat13.
Comparative example 7, object is that explanation is not used the ethanedioic acid aqueous solution carrier to be carried out to the preparation process of pretreated hydroisomerization catalyst:
(1) pretreatment of carrier: it is in 10% lemon aqueous acid that 10g SAPO-11 is joined to 50g mass fraction, at 80 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 13.5g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.79g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 50 ℃ of stirring conditions, 1.73g silver nitrate is dissolved in 13.5g deionized water, obtains solution D after fully dissolving; Afterwards 8.9g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 5h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique, be denoted as cat14.
Comparative example 8, object is that explanation is not used the ethanedioic acid aqueous solution to carry out to carrier the preparation process that pretreated castor oil one-step method is prepared aviation kerosine catalyst:
(1) pretreatment of carrier: it is in 10% lemon aqueous acid that 10g USY is joined to 50g mass fraction, at 100 ℃, stir 48h, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 12.88g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.59g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 100 ℃ of stirring conditions, 2.46g nickel nitrate and 0.75g copper nitrate are dissolved in deionized water, add 1.95g ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards 8.7g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, the catalyst that obtains preparing for castor oil one-step method aviation kerosine technique, is denoted as cat15.
Comparative example 9, object is that explanation is not used aqueous citric acid solution carrier to be carried out to the preparation process of pretreated hydrogenation deoxidation catalyst:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10gMCM-41 is joined to 100g mass fraction, at 60 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, obtains sample A:
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.47g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.0g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active constituent: the uploading of active constituent: under 40 ℃ of stirring conditions, 8.99g nickel nitrate is dissolved in 45g deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in 7.7g sample C, stir 36h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 8h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, be denoted as cat16.
Comparative example 10, object is that explanation is not used aqueous citric acid solution to carry out and the preparation process of the hydrogenation deoxidation catalyst using metal phosphide as active component of processing carrier:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that 10g SBA-15 is joined to 100g mass fraction, at 50 ℃, stir 36h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.86g ferric nitrate is dissolved in 45g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 7.5g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 6h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 80 ℃ of stirring conditions, 5.67g nickel nitrate is dissolved in 45g deionized water, adds 3.56g ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards 6h, obtain solution F; Then solution F is joined in 7.7g sample C, stir 12h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then roasting 8h under 600 ℃ of air atmospheres, by the sample obtaining 700 ℃ of reduction 6h under hydrogen atmosphere, then temperature is down to room temperature, obtains sample G subsequently, the hydrogenation deoxidation catalyst that obtains preparing for castor oil aviation kerosine technique, is denoted as cat17.
Comparative example 11, object is that explanation is not used aqueous citric acid solution carrier to be carried out to the preparation process of pretreated hydroisomerization catalyst:
(1) pretreatment of carrier: 10g SAPO-11 is joined in the aqueous solution that 50g mass fraction is 5% ethanedioic acid, at 70 ℃, stir 48h, by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres afterwards, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 13.5g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.79g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 50 ℃ of stirring conditions, 1.73g silver nitrate is dissolved in 13.5g deionized water, obtains solution D after fully dissolving; Afterwards 8.9g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 5h under 600 ℃ of air atmospheres afterwards, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique, be denoted as cat18.
Comparative example 12, object is to illustrate that aqueous citric acid solution carries out to carrier the preparation process that pretreated castor oil one-step method is prepared aviation kerosine catalyst:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that 10g USY is joined to 50g mass fraction, at 100 ℃, stir 48h, by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres afterwards, obtain sample A;
(2) uploading of auxiliary agent: under 60 ℃ of stirring conditions, 0.35g ferric nitrate is dissolved in 12.88g deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in 8.59g sample A, stir 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 100 ℃ of stirring conditions, 2.46g nickel nitrate and 0.75g copper nitrate are dissolved in deionized water, add 1.95g ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards 8.7g sample C is joined in solution D, stir 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, roasting 4h under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, the catalyst that obtains preparing for castor oil one-step method aviation kerosine technique, is denoted as cat19.
The evaluation result of catalyst cat1, cat2, cat3, cat8, cat9, cat12, cat13, cat16, cat17, appreciation condition as described in Example 4:
The evaluation result of catalyst cat4, cat5, cat10, cat14, cat18, appreciation condition as described in Example 7:
The evaluation result of catalyst cat6, cat7, cat11, cat15, cat19, appreciation condition as described in Example 10:
Claims (9)
1. a hydrogenation deoxidation catalyst of preparing aviation kerosine technique for castor oil, is characterized in that: carrier is MCM-41, HMS, SBA-15, γ-Al
2o
3in one, and the ethanolic solution of the 3-aminopropyl triethoxysilane take mass fraction as 5% and mass fraction stir dipping pretreatment as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; With Ni, Ni
2one in P, Co, CoP is as active constituent, and its quality accounts for the 20-30% of catalyst gross mass, or using Pt as active constituent, its quality accounts for the 0.1-0.5% of catalyst gross mass.
2. prepare the hydroisomerization catalyst of aviation kerosine technique for castor oil for one kind, it is characterized in that: carrier is one or both in SAPO-11, SAPO-34, ZSM-5, beta molecular sieve, and the aqueous solution of the ethanedioic acid take mass fraction as 5% and mass fraction stir dipping pretreatment to carrier as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; Using one or both in Ni, Ag as active constituent, its quality accounts for the 10-25% of catalyst gross mass, or using one or both in Pd, Ru as active constituent, its quality accounts for the 0.1-0.7% of catalyst gross mass.
3. prepare the catalyst of aviation kerosine technique for castor oil one-step method for one kind, it is characterized in that: carrier is one or both in USY, beta molecular sieve, X-type molecular sieve, ZSM-5, and the aqueous solution of the ethanedioic acid take mass fraction as 5% and mass fraction stir dipping pretreatment to carrier as 10% lemon aqueous acid successively; Using Fe as auxiliary agent, its quality accounts for the 1-4% of catalyst gross mass; Using Ni and Cu as active component or with Ni
2p and Cu
3p is as active component, and wherein the mass ratio of Ni and Cu is 1: 0.1-1: 10, Ni
2p and Cu
3the mass ratio of P is 1: 0.2-1: 5, and its quality accounts for the 10-30% of catalyst gross mass.
4. a preparation method for hydrogenation deoxidation catalyst claimed in claim 1, is characterized in that comprising the following steps:
(1) pretreatment of carrier: it is in 5% the ethanolic solution of 3-aminopropyl triethoxysilane that carrier is joined to mass fraction, at 50-70 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, afterwards obtained filter cake is dried under 120 ℃ of air atmospheres, then be cooled to room temperature, then the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, at 70-100 ℃, stir afterwards at least 24h, then by the mixture suction filtration, the separation that obtain, to obtain afterwards filter cake and dry at 120 ℃, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 30-50 ℃ of stirring condition, the one in nickel nitrate, cobalt nitrate, chloroplatinic acid is dissolved in deionized water, obtains solution D after fully stirring; Afterwards solution D is joined in sample C, stir at least 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique;
(4) uploading of active component: under 50-80 ℃ of stirring condition, the one in nickel nitrate, cobalt nitrate is dissolved in deionized water, adds ammonium dihydrogen phosphate (ADP) after fully stirring, stir afterwards at least 4h, obtain solution F; Then solution F is joined in sample C, stir at least 8h, afterwards the mixture obtaining is dried under 120 ℃ of air atmospheres, then at least 5h of roasting under 600 ℃ of air atmospheres, subsequently by the sample obtaining under hydrogen atmosphere 700 ℃ reduce at least 4h, then temperature is down to room temperature, obtain sample G, obtain preparing for castor oil the hydrogenation deoxidation catalyst of aviation kerosine technique, wherein the mol ratio of nickel nitrate and ammonium dihydrogen phosphate (ADP) is 1: 0.75-1: 1.5, and the mol ratio of cobalt nitrate and ammonium dihydrogen phosphate (ADP) is 1: 1.5-1: 3.
5. a preparation method for hydroisomerization catalyst claimed in claim 2, is characterized in that comprising the following steps:
(1) pretreatment of carrier: carrier is joined in the aqueous solution that mass fraction is 5% ethanedioic acid, stir at least 24h at 60-80 ℃, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres; Afterwards the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, at 60-80 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 30-50 ℃ of stirring condition, one or both in nickel nitrate, silver nitrate, palladium chloride, rhodium chloride are dissolved in deionized water, obtain solution D after fully dissolving; Afterwards sample C is joined in solution D, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil the hydroisomerization catalyst of aviation kerosine technique.
6. a preparation method for catalyst claimed in claim 3, its feature comprises the following steps:
(1) pretreatment of carrier: it is in 5% the aqueous solution of ethanedioic acid that carrier is joined to mass fraction, at 100 ℃, stir at least 24h, afterwards by the mixture suction filtration, the separation that obtain, then the filter cake obtaining is dried under 120 ℃ of air atmospheres, afterwards the sample obtaining is joined to mass fraction and be in 10% lemon aqueous acid, at 100 ℃, stir at least 24h, then by the mixture suction filtration, the separation that obtain, afterwards the filter cake obtaining is dried under 120 ℃ of air atmospheres, obtain sample A;
(2) uploading of auxiliary agent: under 40-60 ℃ of stirring condition, ferric nitrate is dissolved in deionized water, obtains solution B after fully stirring; Afterwards solution B is joined in sample A, stir at least 12h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres, obtains sample C afterwards;
(3) uploading of active component: under 60-90 ℃ of stirring condition, nickel nitrate and copper nitrate are dissolved in deionized water, obtain solution D after fully dissolving; Afterwards sample C is joined in solution D, stir at least 24h, then the mixture obtaining is dried under 120 ℃ of air atmospheres, afterwards at least 4h of roasting under 600 ℃ of air atmospheres, obtain sample E, obtain preparing for castor oil one-step method the catalyst of aviation kerosine technique;
(4) uploading of active component: under 100 ℃ of stirring conditions, nickel nitrate and copper nitrate are dissolved in deionized water, add ammonium dihydrogen phosphate (ADP) after fully dissolving, stir afterwards 4h and obtain solution D; Afterwards sample C is joined in solution D, stir at least 24h, then the mixture obtaining is dried in 120 ℃ of air atmospheres, at least 4h of roasting under 600 ℃ of air atmospheres afterwards, be cooled to after room temperature, under 750 ℃ of hydrogen atmospheres, reduce 5h, be cooled to room temperature, obtain preparing for castor oil one-step method the catalyst of aviation kerosine technique.
7. an operation for hydrogenation deoxidation catalyst claimed in claim 1, is characterized in that comprising the following steps:
(1) filling of catalyst: use high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 250-480 ℃, Hydrogen Vapor Pressure 1-5.5MPa, the liquid hourly space velocity (LHSV) 0.1-6/h of castor oil, the volume ratio 500-3000 of hydrogen and castor oil.
8. an operation for hydroisomerization catalyst claimed in claim 2, is characterized in that comprising the following steps:
(1) filling of catalyst: adopt high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 300-500 ℃, Hydrogen Vapor Pressure 1-6MPa, the liquid hourly space velocity (LHSV) 0.1-5/h of n-alkane, the volume ratio of hydrogen and n-alkane is 600-3500, and wherein n-alkane is the product of castor oil hydrogenation deoxidation.
9. one-step method claimed in claim 3 is prepared an operation for aviation kerosine catalyst, it is characterized in that comprising the following steps:
(1) filling of catalyst: use high pressure fixed bed reactors, the filling of catalyst adopts general fixed bde catalyst filling process;
(2) use of catalyst: catalyst need the hydrogen atmosphere that be 500/h in air speed before using under 600 ℃ of reduction 3h, be adjusted to afterwards reaction condition, wherein reaction temperature 350-550 ℃, Hydrogen Vapor Pressure 1-5.5MPa, the liquid hourly space velocity (LHSV) 0.1-6/h of castor oil, the volume ratio 500-2500 of hydrogen and castor oil.
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| CN109395772A (en) * | 2017-08-18 | 2019-03-01 | 中国石油大学(华东) | A kind of isomerization catalyst and its preparation method and application |
| CN109395772B (en) * | 2017-08-18 | 2021-05-11 | 中国石油大学(华东) | Isomerization catalyst and preparation method and application thereof |
| CN107812534A (en) * | 2017-11-15 | 2018-03-20 | 上海应用技术大学 | A kind of preparation method of adipic dinitrile hydrogenation catalyst |
| CN108144629A (en) * | 2017-12-08 | 2018-06-12 | 东北农业大学 | A kind of Ni-Ag/PVP-DB-171/SiO2/Fe3O4The preparation method of catalyst |
| CN109364982B (en) * | 2018-10-19 | 2020-06-16 | 浙江大学 | Method for preparing aviation oil by catalyzing algae oil with nickel-based molecular sieve loaded with phosphotungstic acid |
| CN109364982A (en) * | 2018-10-19 | 2019-02-22 | 浙江大学 | The method for preparing aviation fuel using the Ni-based molecular sieve catalytic algae oil for having loaded phosphotungstic acid |
| CN114522716A (en) * | 2022-03-10 | 2022-05-24 | 福州大学 | Bimetal supported catalyst, preparation method thereof and application of bimetal supported catalyst in preparation of biological aviation kerosene through palm oil hydro-conversion |
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