CN101433863B - Composite oxide carrier and preparation method thereof - Google Patents
Composite oxide carrier and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a compound oxide carrier and a preparation method, and belongs to the filed of catalyst preparation, wherein the compound oxide carrier is prepared by compounding gamma-aluminum oxide, silicon dioxide and zirconium dioxide. The method comprises the following steps: co-precipitating precursors of the aluminum oxide, the silicon dioxide and the zirconium dioxide with alkalisolution, adding surfactant into the mixture to improve the pore structure and acidity and alkaline, then washing, filtering and roasting the obtained sediment at high temperature to obtain compound oxide powder, and finally extruding and molding the compound oxide powder to obtain the carrier. The pore structure and the acidity and the alkaline of the obtained carrier have wide adjustable ranges, the specific surface of the carrier is 200 to 500 m<2> per gram, the pore volume thereof is 0.4 to 1.2 milliliters per gram, and the total acid amount of NH3-TPD is 0.2 to 0.8mmol/g. The carrier prepared by the method is suitable for preparing hydrogenation catalysts of petroleum fractions.
Description
Technical field
The present invention relates to a kind of preparation method of hydrofining catalyst carrier, particularly belong to a kind of composite oxide carrier and preparation method thereof.
Background technology
The preparation technology of alumina support is simple; Specific surface is high, and mechanical strength is good, and the aperture is suitable; Be one of present most widely used catalyst carrier, the preparation and the modification of relevant alumina support, the preparation that contains aluminium composite oxide are the directions that the scientific worker studies always.
Chinese patent CN03 133563.2 has introduced a kind of preparation method who has than the siliceous phosphorus oxidation aluminium of large pore volume and suitable surface acid property.Adopt that meta-aluminic acid is received, silicon-containing compound and carbon dioxide be reacted into glue, filters, promptly gets composite alumina support after the washing, dry, roasting, specific surface is 260～350m
2/ g, pore volume 80～95%, total acid content are 0.43～0.89mmol/g.But phosphorus is to the harmful effect that forms of carrier.
Chinese patent CN03 126434.4 has introduced a kind of preparation method of macropore alumina supporter, and the employing boehmite is a raw material, when extrusion, adds expanding agent, can obtain the macropore alumina supporter of aperture greater than 14nm.
Chinese patent CN01116022.5 has prepared the complex of titanium dioxide and silica or titanium dioxide and aluminium oxide with sol-gel process, though specific surface＞400m
2/ g, pore volume＞0.6ml/g, acid adjustable, but its dry run needs supercritical drying, and cost is higher, does not contain the zirconium that catalytic performance is had facilitation.
Chinese patent CN00123133.2 discloses a kind of alumina carrier containing Zr and preparation method thereof, through in the forming process of carrier, making alumina carrier containing Zr to mix the form adding zirconium-containing compound of pinching; This carrier side pressure strength is improved, and acidity maintains a comparatively stable stage, and infrared acidity is 0.25～0.32mmol/g, and pore distribution concentration is in the mesopore scope, and shortcoming is that the kneading method preparation makes zirconia skewness in carrier.
In sum, at present the preparation method that reports of document exists that complex process, preparation cost are high, made carrier is difficult to satisfy simultaneously requirements such as high-ratio surface, large pore volume and Acidity of Aikalinity be adjustable.
Summary of the invention
To the deficiency of prior art, the composite oxide carrier that the present invention provides a kind of composite oxide carrier and preparation method thereof and this method to obtain, the inventive method is simple, and carrier property is high.
Composite oxide carrier of the present invention contains aluminium oxide 20%～95% by weight, silica 5%～75% and zirconia 1%～15%.The specific surface of carrier is 300～500m
2/ g is preferably 350～480m
2/ g most preferably is 400～450m
2/ g, pore volume is 0.6～1.2ml/g, is preferably 0.8～1.0ml/g, average pore size is 6.0～14.0nm, NH
3-TPD total acid content 0.3～0.8mmol/g.
Composite oxide carrier preparation method of the present invention is following: with aluminium oxide, silica and zirconic precursor solution and aqueous slkali co-precipitation, aging; Sediment obtains composite oxide powder through washing, filtration, drying, and the extruded moulding activation obtains composite oxide carrier again.Wherein add surfactant in co-precipitation and/or aging step.
Among the composite oxide carrier preparation method of the present invention; Comprise two types of surfactant mixtures; One type is selected from polyvinyl alcohol and/or POLYPROPYLENE GLYCOL; Another kind ofly be selected from polyglycerol, polypropylene glycol and the synthetic cellulose (comprising methylcellulose, ethyl cellulose, carboxymethyl cellulose, propyl cellulose or hydroxypropyl methylcellulose etc.) one or more, the part by weight of two types of surfactants is 0.02: 1～50: 1, is preferably 0.1: 1～10: 1.In the surfactant that uses, also can contain other surfactants such as acetylacetone,2,4-pentanedione simultaneously.The use amount of surfactant accounts for 0.1～30% (by weight) of carrier total amount.The mean molecule quantity of polyvinyl alcohol is 20000～300000; The mean molecule quantity of POLYPROPYLENE GLYCOL is 10000～300000; The mean molecule quantity of polyglycerol is 100～20000, and the mean molecule quantity of polypropylene glycol is 500～20000, and the mean molecule quantity of methylcellulose is 20000～400000; The mean molecule quantity of ethyl cellulose is 20000～400000; The mean molecule quantity of carboxymethyl cellulose hydroxyl is 10000～400000, and the mean molecule quantity of propyl cellulose is 10000～1000000, and the mean molecule quantity of hydroxypropyl methylcellulose is 10000～1500000.
Among the composite oxide carrier preparation method of the present invention, the condition of other process can be confirmed by this area general knowledge.
Provide a kind of concrete preparation process below:
(1) makees solvent with water or with the organic aqueous solution that water dissolves each other, gama-alumina, silica and zirconic presoma are made into certain density solution.
(2) with the aqueous slkali be precipitating reagent, add surfactant, with one or more and alkali mixing co-precipitation of presoma, post precipitation can carry out burin-in process under preference temperature, pH value.
(3) sediment is filtered, spend deionised water.
(4) with the filter cake of gained 50～200 ℃ of dryings 2～8 hours.
(5) with dried powder extrusion on banded extruder.
(6) with the carrier of moulding 350～700 ℃ of roastings 2～6 hours, obtain composite oxide carrier.
In the said method, the presoma of aluminium oxide comprises aluminum nitrate, aluminium chloride or aluminum sulfate; Zirconic presoma thing comprises zirconium oxychloride, zirconium nitrate, zirconium chloride or zirconium sulfate; The presoma thing of silica comprises waterglass or silica gel.Described solvent is one or more of water, ethanol, glycerine and methyl alcohol.Described aqueous slkali is that meta-aluminic acid is received, potassium metaaluminate, NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, one or more in the carbonic hydroammonium.Among the composite oxide carrier preparation method of the present invention, the precursor solution of zirconia and/or silica can add in ageing process.The coprecipitation reaction temperature is 20～90 ℃, preferred 30～80 ℃.The pH value of coprecipitation reaction is 6.0～11.0, and preferred pH value is 7.0～10.0.The temperature of ageing process is identical with the scope of co-precipitation neutralization reaction with the pH value.The filtration cakes torrefaction condition is 50～200 ℃ of dryings 2～8 hours.The solid of moulding preferably 350～700 ℃ of roastings 2～6 hours, obtains the composite oxide carrier of activation 200～700 ℃ of roastings 2～10 hours.
The present invention has following advantage compared with prior art:
(1) composite oxide carrier has large pore volume and high-specific surface area, and Acidity of Aikalinity is adjustable, is more suitable for as catalyst carrier for hydrgenating.
(2) production technology is simple, and the preparing carriers cost is low, and is environmentally friendly.
The specific embodiment
Among the composite oxides preparation method of the present invention; The concentration of aluminium oxide, silica and zirconic presoma wiring solution-forming; The concentration of aluminium salt is 0.01～5mol/L; Be preferably 0.1～3mol/L, the concentration of zirconates is 0.01～2mol/L, contains in the silica weight content in the silicon source to be not less than 1%; Said aluminium salt is one or more of aluminum nitrate, aluminum sulfate and aluminium chloride, is preferably aluminum nitrate; Described zirconates is one or more of zirconium oxychloride, zirconium nitrate, zirconium sulfate and zirconium chloride, is preferably zirconium nitrate; The silicon source is waterglass or silica gel.Further describe technical characterstic of the present invention through specific embodiment and comparative example below, but these embodiment can not limit the present invention, the percentage that relates to is weight percentage.
Experiment sequence number 1: comparative example 1
700ml0.4mol/L aluminum nitrate, 450ml0.1mol/L zirconium nitrate and 80ml (are contained SiO
225%) silica gel mixing, adding ammoniacal liquor adjusting pH value is 8.5, reacts down and wears out 1 hour at 60 ℃ at 80 ℃; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; After adding the extrusion aid extrusion; 600 ℃ of roastings 3 hours, promptly get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 2: comparative example 2
700ml 1mol/L aluminum nitrate, 100ml 0.5mol/L zirconium nitrate, 60ml (are contained SiO
225%) silica gel and 2g polyvinyl alcohol (mean molecule quantity is 1000-2000) mixing, adding ammoniacal liquor adjusting pH value is 8.5, reacts down and wears out 1 hour at 60 ℃ at 80 ℃; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; After adding the extrusion aid extrusion; 600 ℃ of roastings 3 hours, promptly get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 3: comparative example 3
700ml 1mol/L aluminum nitrate, 100ml 0.5mol/L zirconium oxychloride and 60ml (are contained SiO
225%) silica gel mixes, and adding ammoniacal liquor adjusting pH value is 8.5, reacts half an hour down at 80 ℃; Add 2g polyvinyl alcohol (mean molecule quantity is 1000-2000) and wore out 1 hour at 60 ℃, suction filtration spends deionised water 3 times; 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after, 600 ℃ of roastings 3 hours; Promptly get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 4: comparative example 4
200ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium oxychloride and 80ml silica gel (are contained SiO
225%) mixing, the sal volatile adjusting pH value that adds 1mol/L is 7.5, reacts down and wears out 1 hour at 50 ℃ at 80 ℃; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; After adding the extrusion aid extrusion; 600 ℃ of roastings 3 hours, promptly get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 5: comparative example 5
200ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium nitrate and 80ml silica gel (are contained SiO
225%) and 1g polyglycerol 400 (mean molecule quantity is 400) mix, adding ammonium carbonate, to regulate pH value be 9.5,80 ℃ of reactions and wore out 1 hour at 50 ℃ down; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; After adding the extrusion aid extrusion; 600 ℃ of roastings 3 hours, promptly get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 6: comparative example 6
1000ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium nitrate and 120ml silica gel (are contained SiO
225%) mixes, add the mixed liquor of ammoniacal liquor and polyglycerol 2000 (mean molecule quantity is 2000), wherein ammoniacal liquor: polyglycerol 2000=100: 1 (weight ratio); Regulating pH value is 8.5,80 ℃ down reaction and 60 ℃ aging 1 hour, suction filtration spends deionised water 3 times, 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after, 600 ℃ of roastings 3 hours, get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 7: comparative example 7
1000ml 1mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium nitrate and 1000ml silica gel (are contained SiO
225%) mixes, add the mixed liquor of ammoniacal liquor and acetylacetone,2,4-pentanedione, wherein ammoniacal liquor: acetylacetone,2,4-pentanedione=30: 1 (weight ratio); Regulating pH value is 8.5,80 ℃ down reaction and 60 ℃ aging 1 hour, suction filtration spends deionised water 3 times, 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after, 600 ℃ of roastings 3 hours, get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 8: embodiment 1
1000ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium nitrate and 120ml silica gel (are contained SiO
225%) mixes; Mixed surfactant 1 (polyglycerol 200: polyglycerol 2000: polyglycerol 600=1: 1: 1 (weight ratio)); Add ammoniacal liquor and mixed surfactant 1 ' (mixed surfactant 1 and polyvinyl alcohol 50000=30: 1 (weight ratio)) mixture, wherein ammoniacal liquor: mixed surfactant 1 '=20: 1 (weight ratio); Regulating pH value is 8.5,80 ℃ down reaction and 60 ℃ aging 1 hour, suction filtration spends deionised water 3 times, 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after, 600 ℃ of roastings 3 hours, get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 9: embodiment 2
1000ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium oxychloride and 120ml silica gel (are contained SiO
225%) mix, add ammoniacal liquor and mixed surfactant 2 mixed liquor (mixed surfactant 1: polyvinyl alcohol 50000=3: 1 (weight ratio)), ammoniacal liquor wherein: mixed surfactant 2=10: 1 (weight ratio); Regulating pH value is 8.5,80 ℃ down reaction and 60 ℃ aging 1 hour, suction filtration spends deionised water 3 times, 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after, 600 ℃ of roastings 3 hours, get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 10: embodiment 3
1000ml 2mol/L aluminum nitrate, 1000ml 0.05mol/L zirconium nitrate and 120ml silica gel (are contained SiO
225%) mix, add ammoniacal liquor and mixed surfactant 3 mixed liquor (mixed surfactant 1: POLYPROPYLENE GLYCOL 150000=1: 1 (weight ratio)), ammoniacal liquor wherein: mixed surfactant 3=10: 1 (weight ratio); Regulating the pH value is 8.5, wears out suction filtration 1 hour 80 ℃ of following reactions and at 60 ℃; Spend deionised water 3 times, 120 ℃ of dryings 3 hours, add the extrusion aid extrusion after; 600 ℃ of roastings 3 hours, get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 11: embodiment 4
By experiment sequence number 1 support material proportioning and operating condition, when becoming glue, add mixed surfactant 4, it consists of: mixed surfactant 2: polyvinyl alcohol 150000=1: 1 (weight ratio), wherein ammoniacal liquor: mixed surfactant 4=5: 1 (weight ratio).Get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 12: embodiment 5
By experiment sequence number 2 support material proportioning and operating conditions; When becoming glue, add mixed surfactant 5; It consists of: mixed surfactant 1: polyvinyl alcohol 20000: polyvinyl alcohol 50000: polyvinyl alcohol 150000=1: 1: 1: 1 (weight ratio), wherein ammoniacal liquor: mixed surfactant 5=20: 1 (weight ratio).Obtain composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 13: embodiment 6
By experiment sequence number 2 support material proportioning and operating conditions; When becoming glue, add mixed surfactant 6; It consists of: mixed surfactant 2: methylcellulose 50000: methylcellulose 100000=5: 1: 1 (weight ratio), wherein ammoniacal liquor: mixed surfactant 5=20: 1 (weight ratio).Obtain composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 14: embodiment 7
By experiment sequence number 2 support material proportioning and operating conditions; When becoming glue, add mixed surfactant 7; It consists of: mixed surfactant 2: hydroxypropyl methylcellulose 150000: hydroxypropyl methylcellulose 100000: propyl cellulose 100000=3: 1: 1: 1 (weight ratio), wherein ammoniacal liquor: mixed surfactant 5=20: 1 (weight ratio).Obtain composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 15: embodiment 8
By experiment sequence number 4 support material proportioning and operating conditions; When becoming glue, add mixed surfactant 8; It consists of: mixed surfactant 1: polyvinyl alcohol 20000: methylcellulose 50000: hydroxypropyl methylcellulose 150000=1: 3: 1: 1 (weight ratio), wherein ammoniacal liquor: mixed surfactant 5=100: 1 (weight ratio).Get composite oxide carrier, its main character is listed in table 1,2.
Experiment sequence number 16: embodiment 9
By experiment sequence number 7 support material proportioning and operating conditions; When aging, add mixed surfactant 9; It consists of: mixed surfactant 1: polyvinyl alcohol 20000: acyl acetone=1: 25: 5 (weight ratio), wherein the addition of surfactant is 10% (weight ratio) of ammoniacal liquor.Obtain composite oxide carrier, its main character is listed in table 1,2.
The shared ratio (quality percentage composition) of each oxide in table 1 composite oxide carrier
The physical property of table 2 composite oxide carrier
Explain: 1, DA is an average pore diameter, and unit does
, promptly 10
-10Rice.
2,150-250 ℃, 250-400 ℃, 400-500 ℃ is the desorption temperature of ammonia, respectively corresponding weak acid, middle strong acid and strong acid.
Claims (11)
1. a composite oxide carrier contains aluminium oxide 20%～95% by weight, silica 5%～75% and zirconia 1%～15%, and the specific surface of carrier is 300～500m
2/ g, pore volume are 0.8～1.2ml/g, and average pore size is 6.0～14.0nm, NH
3-TPD total acid content 0.3～0.8mmol/g.
2. according to the described carrier of claim 1, the specific surface that it is characterized in that said carrier is 350～480m
2/ g, pore volume are 0.8～1.0ml/g.
3. the preparation method of the said composite oxide carrier of claim 1; The preparation method is following: with aluminium oxide, silica and zirconic precursor solution and aqueous slkali co-precipitation, aging; Sediment obtains composite oxide powder through washing, filtration, drying, and the extruded moulding activation obtains composite oxide carrier again; It is characterized in that adding surfactant in said co-precipitation step;
Said surfactant is two types of surfactant mixtures; One type is selected from polyvinyl alcohol and/or POLYPROPYLENE GLYCOL; Another kind ofly be selected from polyglycerol, polypropylene glycol and the synthetic cellulose one or more, the part by weight of two types of surfactants is 0.02: 1～50: 1.
4. according to the described method of claim 3, the part by weight that it is characterized in that said two types of surfactants is 0.1: 1～10: 1.
5. according to the described method of claim 3, it is characterized in that described amount of surfactant accounts for 0.1%～30% of carrier total amount by weight.
6. according to the described method of claim 3, the mean molecule quantity that it is characterized in that described polyvinyl alcohol is 20000～300000, and the mean molecule quantity of POLYPROPYLENE GLYCOL is 10000～300000, and the mean molecule quantity of polypropylene glycol is 500～20000; Synthetic cellulose comprises methylcellulose, ethyl cellulose, carboxymethyl cellulose, propyl cellulose or hydroxypropyl methylcellulose; The mean molecule quantity of methylcellulose is 20000～400000; The mean molecule quantity of ethyl cellulose is 20000～400000; The mean molecule quantity of carboxymethyl cellulose hydroxyl is 10000～400000, and the mean molecule quantity of propyl cellulose is 10000～1000000, and the mean molecule quantity of hydroxypropyl methylcellulose is 10000～1500000.
7. according to the described method of claim 3, it is characterized in that a kind of concrete preparation process is following:
(1) makees solvent with water or with the organic aqueous solution that water dissolves each other, gama-alumina, silica and zirconic presoma are made into certain density solution;
(2) with the aqueous slkali be precipitating reagent, add surfactant, with one or more and alkali mixing co-precipitation of presoma, post precipitation can carry out burin-in process under preference temperature, pH value;
(3) sediment is filtered, spend deionised water;
(4) with the filter cake of gained 50～200 ℃ of dryings 2～8 hours;
(5) with dried powder extrusion on banded extruder;
(6) with the carrier of moulding 350～700 ℃ of roastings 2～6 hours, obtain composite oxide carrier.
8. according to the described method of claim 7, the presoma that it is characterized in that said aluminium oxide is aluminum nitrate, aluminium chloride or aluminum sulfate; Zirconic presoma thing is zirconium oxychloride, zirconium nitrate, zirconium chloride or zirconium sulfate; The presoma thing of silica is waterglass or silica gel; Described aqueous slkali is that meta-aluminic acid is received, in potassium metaaluminate, NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate and the carbonic hydroammonium one or more.
9. according to the described method of claim 7, it is characterized in that described coprecipitation reaction temperature is 20～90 ℃, the pH value of coprecipitation reaction is 6.0～11.0, and the temperature of ageing process is identical with the scope of co-precipitation neutralization reaction with the pH value.
10. according to the described method of claim 7, it is characterized in that described coprecipitation reaction temperature is 30～80 ℃, the pH value of coprecipitation reaction is 7.0～10.0.
11., it is characterized in that described filtration cakes torrefaction condition is for 50～200 ℃ of dryings 2～8 hours according to the described method of claim 7.
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| CN102125849B (en) * | 2010-12-15 | 2013-03-20 | 新奥新能(北京)科技有限公司 | Method for preparing synthetic methane catalyst and catalyst precursor |
| EP2667968A2 (en) * | 2011-01-25 | 2013-12-04 | Basf Se | Catalyst support produced by flame spray pyrolysis and catalyst for autothermal propane dehydrogenation |
| CN102908971B (en) * | 2011-08-04 | 2014-12-31 | 中国石油化工股份有限公司 | Titanium-containing silicon oxide-aluminum oxide forming composition and preparation method thereof |
| CN102909027A (en) * | 2012-09-19 | 2013-02-06 | 中国海洋石油总公司 | Preparation method of catalyst by ultralow-sulfur hydrofining |
| CN102935373A (en) * | 2012-11-13 | 2013-02-20 | 中国海洋石油总公司 | Method for preparing catalyst refined through hydrogenation pretreatment of wax oil |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| CN107282055B (en) * | 2016-04-13 | 2020-11-03 | 中国石油化工股份有限公司 | Catalyst for producing acrolein and acrylic acid |
| EP3444225A4 (en) * | 2017-06-30 | 2020-02-19 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Alumina-based composite oxide and method for producing same |
| CN110935434A (en) * | 2019-12-09 | 2020-03-31 | 北京石油化工学院 | Catalyst for preparing nonene and dodecene by propylene oligomerization and preparation method and application thereof |
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| CN1063426A (en) * | 1991-01-22 | 1992-08-12 | 诺顿公司 | Catalyst carrier |
| CN1350888A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Alumina carrier containing Zr and its preparing process |
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