CN105753027A - Method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas - Google Patents

Method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas Download PDF

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Publication number
CN105753027A
CN105753027A CN201610049939.6A CN201610049939A CN105753027A CN 105753027 A CN105753027 A CN 105753027A CN 201610049939 A CN201610049939 A CN 201610049939A CN 105753027 A CN105753027 A CN 105753027A
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China
Prior art keywords
additive
specific surface
roasting
carrier
aluminum
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CN201610049939.6A
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Chinese (zh)
Inventor
邱枫
郭冬云
伊晓东
方维平
孙果宋
雷福厚
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Guangxi Research Institute of Chemical Industry
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Guangxi Research Institute of Chemical Industry
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Priority to CN201610049939.6A priority Critical patent/CN105753027A/en
Publication of CN105753027A publication Critical patent/CN105753027A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/308—Thermal decomposition of nitrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/32—Thermal decomposition of sulfates including complex sulfates, e.g. alums
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Abstract

The invention discloses a method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas.Solid-phase reaction is carried out on aluminum salt and additives at the room temperature on the premise that optional solvents are omitted, and then reaction products are roasted to obtain Al2O3.The method includes steps of (1), weighing certain quantities of the aluminum salt and the additives, mixing the aluminum salt and the additives to obtain solid mixtures and grinding the solid mixtures; (2), directly roasting the solid mixtures in air atmosphere to obtain the aluminum oxide carrier.The method has the advantages that the method is easy to implement, short in preparation cycle and high in synthesis efficiency, the optional solvents are omitted, and reaction procedures are easy to control; the aluminum oxide carriers prepared by the aid of the method have the high specific surface areas and large pore volumes and are applicable to hydrotreatment on catalysts.

Description

A kind of high-specific surface area γ-Al2O3The method for preparing solid phase of carrier
Technical field
The present invention relates to a kind of high-specific surface area γ-Al2O3The preparation method of carrier.
Background technology
γ-Al2O3Due to the specific surface area that it is bigger, porous, surface acidity and good heat stability etc. Feature, can be used as the carrier of catalyst, is widely used in petrochemical industry and field of Environment Protection.Generally, γ-Al2O3 Being to be prepared by boehmite thermal dehydration at a certain temperature, the preparation method of boehmite mainly has carbonization Method, aluminium alcoholates Hydrolyze method, acid system etc..Carbonizatin method is with NaAlO2And CO2For raw material, through gel, aging, Separate, washing and drying and other steps prepare boehmite, the method complex technical process, reaction temperature, The character of product is affected relatively big by the technological parameters such as pH value, and technology stability is poor.Aluminium alcoholates Hydrolyze method is metallic aluminium Under the effect of catalyst, generate aluminium alcoholates with alcohol, then through hydrolysis, aging, filter, dry prepared, the method makes Organic solvent have certain toxicity, and production cost is high.Acid system is with aluminum sulfate, aluminum nitrate or chlorination The aluminium salt such as aluminum are raw material, add NaAlO2、NaOH、Na2CO3Or ammonia neutralize, through plastic, aging, Washing, be dried etc. process prepare.The method complex steps, interference factor are more, and manufacturing cycle is long.
Patent USP4448896 provides in a kind of aluminium oxide preparation process and adds carbon black expanding agent way, by powder The expanding agent of powder and boehmite dry glue powder are mixed together, extruded moulding.In carrier calcination, expanding agent Oxidized, burning after generate gas, leave macropore at carrier surface after volatilization, but this method mechanical strength be low, Pore size distribution disperses and uneven, is extremely difficult to industrial requirements.On this basis, patent CN1768946A is public Having opened that a kind of to use starch be the method that expanding agent prepares alumina support, wherein starch adds in powder form, Addition is the 10-20wt% of aluminium oxide.Treat that boehmite dry glue powder, extrusion aid, water, starch mix together Pinch molding, after drying, roasting, prepare large-pore alumina.The selection of extrusion aid refers to patent CN1289825A proposes to use sesbania powder, methylcellulose, starch, polyvinyl alcohol as extrusion aid, helps crowded Agent consumption is 4-6%.But starch is because of its viscosity greatly, unfavorable to molding, is seldom used as extrusion aid, and in reality Execute in case and the most do not mentioned.Starch expanding agent prepares alumina support relatively carbon black expanding agent method intensity height, hole The features such as footpath is big, pore distribution concentration, and preparation method process is simple, cost of material and production cost are the most relatively low, Suitable high-volume commercial production.
Patent CN102275963A proposes in a kind of aluminium oxide preparation process and adds structure directing agent method, will Inorganic aluminate, carbamide and structure directing agent mixing hydro-thermal 12h, wherein structure directing agent and aluminium ion mol ratio 0-0.4: 1, carbamide and aluminium ion mol ratio 3-12: 1, can prepare respectively after drying roasting bar-shaped, Aloe shape, Lamellar, fusiform aluminium oxide, its specific surface area 190-820m2/g.And patent CN103787394A proposes A kind of be added without the method that structure directing agent prepares alumine with high specific surface area, this method with inorganic aluminate for aluminum source, Carbamide is precipitant, carbamide and aluminium ion mol ratio 2-10: 1, on the premise of not using structure directing agent, Solution is sealed in hydro-thermal reaction 2～12h at 140～200 DEG C, prepares boehmite, it is not necessary to filter and wash Wash, be directly dried, roasting, can be prepared by the aluminium oxide of high specific surface area and larger aperture.Its advantage Being: filtered and washing, ammonium nitrate and ammonium carbonate that reaction generates can well become water and aluminium oxide The supporter of structure, will cause chip architecture to cave in because of dry dehydration so that carrier has higher specific surface Long-pending, these salts are when roasting decomposes simultaneously, produce substantial amounts of gas, thus play good reaming effect Really.
CN101255356A discloses a kind of unsupported catalyst and preparation method thereof, and this catalyst is by several Plant metal component precursor and carbamide mixing and react in the molten state, carbamide and metal molar ratio 1-5: 1, wherein metal component can use the metal precursor such as its metal-oxide, salt, acid, reaction temperature Spending 100-200 DEG C of response time 2-10h, 200-500 DEG C of roasting time 2-8h of sintering temperature, available one is certainly Body has the catalyst particles of nano pore and high specific surface area.This method advantage be to overcome hydro-thermal reaction and The shortcoming of coprecipitation, uses urea melting reactive synthesis technique, and response speed is fast so that prepared metal Compound particle self has more flourishing duct and bigger specific surface area, and himself can provide abundant urging Change hydrogenation activity position.
Patent CN1727063A discloses the preparation method of a kind of alumina supporter, and this method is by water Mix with aluminium carbonate ammonium with aluminium oxide, molding roasting, wherein water and aluminium oxide and aluminium carbonate ammonium Mixing ratio by weight For 20-90: 10-80, sintering temperature is 450-1000 DEG C of time 1-8h.And patent CN102849763A is public Open a kind of Gradient distribution hole γ-Al2O3Method for preparing solid phase, the method be by aluminum nitrate, ammonium hydrogen carbonate with Derivant Polyethylene Glycol at room temperature grinds, through ageing obtain aluminium carbonate ammonium, then at 50～180 DEG C be dried 1～ 20h, prepares aluminium oxide in 350～900 DEG C of roastings.Aluminium carbonate ammonium, in catabolic process, produces gas, such as ammonia With carbon dioxide, the generation of these gases and effusion can manufacture some macropores.Intensification speed slower in roasting process Rate is conducive to gaseous matter to escape slowly, does not easily cause carrier and caves in.The method advantage is simple to operate, is not required to Add any expanding agent.Both the above method is all to use Solid phase synthesis alumina support, and this method separately wards off footpath Footpath, compared with conventional hydrothermal synthetic method, simple to operation.
In sum, prior art prepares γ-Al2O3Method have: boehmite roasting method, Hydrothermal Synthesis Method, solid phase method.Hydrothermal synthesis method is utilized first to prepare the intermediate such as boehmite or aluminium carbonate ammonium, then drying Roasting prepares carrier, this preparation method complex steps, and interference factor is many, and manufacturing cycle is long, uses solvent, right Environment has certain pollution, and prepares the specific surface area of alumina support and pore volume under Template-free method relatively Little.Utilize solid phase method, simple to operate, solvent-free pollution, and obtain relatively large specific surface area and pore volume.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of solid phase method to prepare high-specific surface area γ-Al2O3Carrier Method, the method does not use any solvent in preparation process, and preparation method is simple, with short production cycle, system The aluminium oxide obtained has bigger specific surface area and pore volume aperture, it is adaptable to Hydrobon catalyst.
The present invention is that a kind of solid phase method prepares γ-Al2O3The method of carrier, including step in detail below:
(1) a certain proportion of aluminium salt and additive are weighed respectively；
Preferably, in described step (1), aluminium salt chooses aluminum chloride, aluminum nitrate, aluminum sulfate or aluminum isopropylate.；
Preferably, in described step (1), additive takes from carbamide, starch and citric acid and Polyethylene Glycol；
Preferably, in described step (1), the relative molecular mass of additives polyethylene glycol is 2000,6000, 20000；
Preferably, in described step (1), two kinds of matched combined that additive is chosen, one be only choose carbamide, The single component of starch, citric acid or Polyethylene Glycol is as additive, and two is to choose carbamide, starch, Fructus Citri Limoniae In acid and Polyethylene Glycol, two or more components are as additive；
Preferably, described additive carbamide, starch, one or more of citric acid and the weight of Polyethylene Glycol Ratio is 0.2～1；
Preferably, in described step (1), the total consumption of additive and synthesis Al2O3Mass ratio be 0.5～9；
(2) a certain proportion of aluminium salt and additive are mixed, grind；
Preferably, in described step (2), milling time is 20min～2h；
(3) by solid mixture directly roasting in air atmosphere obtained in step (2), desirable oxidation is i.e. obtained Alumina supporter.
Preferably, in described step (3), solid mixture being carried out roasting, sintering temperature is 400～600 DEG C, Roasting time is 2～5h.
The additive used in the present invention, during roasting, decomposes, and effusion produces CO2And NH3。
Compared with existing Hydrothermal Synthesis law technology, γ-Al prepared by the present invention2O3Carrier has the advantage that
(1) the inventive method is to directly utilize aluminium salt and additive carries out mixed grinding between solid phase, more fired prepares Carrier, the most so-called solid phase method, this method eliminate in intermediate boehmite preparation process aging, washing, The series of steps such as filtration, drying, operating procedure is simple, and a step completes, and substantially reduces the production cycle.
(2) the whole preparation process of the present invention does not use any solvent, decrease environmental pollution, the aluminum used Salt and additive belong to environmental friendliness shaped material, environmental sound own, and roasting produces gaseous volatilization the most afterwards, Free from admixture remains, and meets the requirement of Green Chemistry.
(3) most of raw material that the inventive method is used is cheap and easy to get, and production cost and technology maturation all can be grasped Control, to producing, equipment requirements is the highest, is applicable to industrial mass production.
(4) carrier that the alumina support obtained by the inventive method is prepared compared with hydrothermal synthesis method, has higher ratio Surface area, pore volume and aperture.High aperture size and the characteristic of high-specific surface area that this carrier is provided can be applicable to Hydrofinishing treatment technology is such as: hydrodesulfurization reaction or HDM reaction.
Accompanying drawing explanation
Fig. 1 is the adsorption desorption curve of the alumina support of embodiment 1 preparation.
Fig. 2 is the graph of pore diameter distribution of the alumina support of embodiment 1 preparation.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
The concrete preparation method of the alumina support that the present invention provides is: weigh a certain amount of aluminium salt and additive, Aluminium salt is for the one in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminum isopropylate., additive be carbamide, starch, One in citric acid and Polyethylene Glycol, two or more, the consumption of additive and synthesis Al2O3Quality Ratio is 0.5～9.Aluminium salt and additive are carried out mixed grinding, and milling time is 20min～2h.Again by solid Mixture under air atmosphere, roasting 2～5h at 400～600 DEG C, prepare alumina support.
Embodiment 1
The method preparing aluminium oxide: weighing 7.95g aluminum chloride respectively, additives polyethylene glycol (M=2000) adds Dosage is 15g, mixes and grinds 30min.Again solid mixture is placed under air atmosphere, 500 DEG C of roastings Burn 3h, prepare alumina support numbering 1.The character of carrier is shown in Table 1.
Embodiment 2
The method preparing aluminium oxide: weigh 11.9g aluminum nitrate, the addition of additives polyethylene glycol (M=6000) For 0.85g, mix and grind 60min.Again solid mixture is placed under air atmosphere, 400 DEG C of roastings 5h, prepares alumina support numbering 2.The character of carrier is shown in Table 1.
Embodiment 3
The method preparing aluminium oxide: weigh 7.3g aluminum isopropylate., the interpolation of additives polyethylene glycol (M=20000) Amount is 6g, mixes and grinds 2h.Again solid mixture is placed under air atmosphere, at 600 DEG C of roasting 2h, Prepare alumina support numbering 3.The character of carrier is shown in Table 1.
Embodiment 4
The method preparing aluminium oxide: weigh 7.95g aluminum chloride, additive carbamide, citric acid, the interpolation of starch Amount is 1g respectively, mixes and grinds 90min.Again solid mixture is placed under air atmosphere, at 580 DEG C Roasting 140min, prepares alumina support numbering 4.The character of carrier is shown in Table 1.
Embodiment 5
The method preparing aluminium oxide: weigh 10.8g aluminum sulfate, additive is Polyethylene Glycol (M=6000) and carbamide Mixture, its quality is 7.5g, mixes and grinds 45min.Again solid mixture is placed under air atmosphere, At 450 DEG C of roasting 4h, prepare alumina support numbering 5.The character of carrier is shown in Table 1.
Embodiment 6
The method preparing aluminium oxide: weigh 11.9g aluminum nitrate, additive is Polyethylene Glycol (M=20000) and urine Element, citric acid mixture, its quality is respectively 1g, 0.1g, 0.1g, mixes and grinds 75min.Again will be solid Body mixture is placed under air atmosphere, at 550 DEG C of roasting 2.5h, prepares alumina support numbering 6.Carrier Character is shown in Table 1.
Embodiment 7
The method preparing aluminium oxide: weigh 7.3g aluminum isopropylate., the addition of additive starch is 2g, mixing And grind 20min.Again solid mixture is placed under air atmosphere, at 480 DEG C of roasting 140min, prepares oxygen Change alumina supporter numbering 7.The character of carrier is shown in Table 1.
Embodiment 8
The method preparing aluminium oxide: weigh 10.8g aluminum sulfate, additive is Polyethylene Glycol (M=2000) and starch Mixture, its quality is respectively 5g and 1g, mixes and grinds 60min.Again solid mixture is placed in air Under atmosphere, at 550 DEG C of roasting 3h, prepare alumina support numbering 9.The character of carrier is shown in Table 1.
Embodiment 9
The method preparing aluminium oxide: weigh 7.95g aluminum chloride, additive is Polyethylene Glycol (M=20000) and lemon Lemon acid blend, its quality is respectively 5g and 3g, mixes and grinds 60min.Again solid mixture is placed in Under air atmosphere, at 450 DEG C of roasting 4h, prepare alumina support numbering 10.The character of carrier is shown in Table 1.
Embodiment 10
The method preparing aluminium oxide: weigh 7.95g aluminum chloride, without any additive, is directly placed on Under air atmosphere, at 500 DEG C of roasting 3h, prepare alumina support numbering 8.The character of carrier is shown in Table 1.
The sign data of above carrier are by Tristar II 3020 apparatus measures.First by sample cell in 300 DEG C of pre-places Reason 3h, then hangs installation by sample cell, i.e. can get following data.
The character of the alumina support prepared by table 1 examples detailed above

Claims (7)

1. a high-specific surface area γ-Al2O3The method for preparing solid phase of carrier, comprises the following steps:
(1) a certain amount of aluminium salt and additive are weighed, mixing, grind；
(2) by solid mixture directly roasting in air atmosphere obtained in step (1), γ-Al is i.e. obtained2O3Carrier；
Aluminium salt in described step (1) is the one in aluminum chloride, aluminum sulfate, aluminum nitrate or aluminum isopropylate.；
Additive in described step (1) is one or more in carbamide, starch, citric acid or Polyethylene Glycol.
Method the most according to claim 1, it is characterised in that: the molecular weight of described Polyethylene Glycol is 2000,6000 or 20000.
Method the most according to claim 1, it is characterised in that: described additive carbamide, starch, one or more of citric acid are 0.2～1 with the weight ratio of Polyethylene Glycol.
4. according to the method described in any one of claims 1 to 3, it is characterised in that: the addition of additive is 0.5～9 with the Al2O3 mass ratio of synthesis.
5. according to the method described in any one of claims 1 to 3, it is characterised in that: milling time controls at 20min～2h.
6. according to the method described in any one of claims 1 to 3, it is characterised in that: described roasting refers to roasting 2～5h at 400～600 DEG C.
7. γ-the Al obtained according to the method described in any one of claims 1 to 32O3Carrier application in hydrodesulfurization reaction or HDM react.
CN201610049939.6A 2016-01-26 2016-01-26 Method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas Pending CN105753027A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106348326A (en) * 2016-08-23 2017-01-25 山东国瓷功能材料股份有限公司 Gamma alumina, preparation method and application thereof and device
CN106747591A (en) * 2016-11-15 2017-05-31 中国海洋石油总公司 A kind of preparation method of big pore volume alumina support
CN108975362A (en) * 2018-09-02 2018-12-11 兰州大学 A kind of preparation method of fully decentralized aluminum oxide nanoparticle
CN109420483A (en) * 2017-08-31 2019-03-05 中国石油化工股份有限公司 One kind alumina supporter containing char combustion and preparation method thereof
CN109420529A (en) * 2017-08-31 2019-03-05 中国石油化工股份有限公司 A kind of preparation method of alumina support
CN113233484A (en) * 2021-06-02 2021-08-10 西南石油大学 Preparation method of high-temperature-resistant high-specific-surface-activity alumina
CN113426437A (en) * 2021-07-16 2021-09-24 广西化工研究院有限公司 Catalyst for preparing propylene by gallium-based propane dehydrogenation and preparation method thereof
CN114275740A (en) * 2020-09-17 2022-04-05 中国科学院大连化学物理研究所 Preparation method of porous oxide

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Publication number Priority date Publication date Assignee Title
CN1727063A (en) * 2004-07-29 2006-02-01 中国石油化工股份有限公司 Method for preparing alumina supporter in structure of double peak holes
CN1768946A (en) * 2004-10-29 2006-05-10 中国石油化工股份有限公司 Method for preparing alumina supporter
CN102849763A (en) * 2012-09-07 2013-01-02 中国石油天然气股份有限公司 Solid phase preparation method for gamma-alumina with gradient distribution holes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1727063A (en) * 2004-07-29 2006-02-01 中国石油化工股份有限公司 Method for preparing alumina supporter in structure of double peak holes
CN1768946A (en) * 2004-10-29 2006-05-10 中国石油化工股份有限公司 Method for preparing alumina supporter
CN102849763A (en) * 2012-09-07 2013-01-02 中国石油天然气股份有限公司 Solid phase preparation method for gamma-alumina with gradient distribution holes

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106348326A (en) * 2016-08-23 2017-01-25 山东国瓷功能材料股份有限公司 Gamma alumina, preparation method and application thereof and device
CN106747591A (en) * 2016-11-15 2017-05-31 中国海洋石油总公司 A kind of preparation method of big pore volume alumina support
CN106747591B (en) * 2016-11-15 2019-07-19 中国海洋石油集团有限公司 A kind of macropore holds the preparation method of alumina support
CN109420483A (en) * 2017-08-31 2019-03-05 中国石油化工股份有限公司 One kind alumina supporter containing char combustion and preparation method thereof
CN109420529A (en) * 2017-08-31 2019-03-05 中国石油化工股份有限公司 A kind of preparation method of alumina support
CN109420483B (en) * 2017-08-31 2021-03-05 中国石油化工股份有限公司 Carbon-containing alumina carrier and preparation method thereof
CN108975362A (en) * 2018-09-02 2018-12-11 兰州大学 A kind of preparation method of fully decentralized aluminum oxide nanoparticle
CN114275740A (en) * 2020-09-17 2022-04-05 中国科学院大连化学物理研究所 Preparation method of porous oxide
CN113233484A (en) * 2021-06-02 2021-08-10 西南石油大学 Preparation method of high-temperature-resistant high-specific-surface-activity alumina
CN113426437A (en) * 2021-07-16 2021-09-24 广西化工研究院有限公司 Catalyst for preparing propylene by gallium-based propane dehydrogenation and preparation method thereof

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Application publication date: 20160713