CN100369667C - Nanometer titanium dioxide forming substances and preparation thereof - Google Patents
Nanometer titanium dioxide forming substances and preparation thereof Download PDFInfo
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- CN100369667C CN100369667C CNB2005100948024A CN200510094802A CN100369667C CN 100369667 C CN100369667 C CN 100369667C CN B2005100948024 A CNB2005100948024 A CN B2005100948024A CN 200510094802 A CN200510094802 A CN 200510094802A CN 100369667 C CN100369667 C CN 100369667C
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Abstract
The present invention discloses a nanometer titanium dioxide forming composition and a preparation method thereof. The present invention solves the problem of difficult compatibility of compression strength and specific surface area existing in the prior art; the prepared nanometer titanium dioxide forming composition has certain compression strength and simultaneously has large specific surface area; when the specific surface area is from 100 to 175m<2>/g, the edgewise compressive strength of the nanometer titanium dioxide forming composition is not lower than 30 n/cm, and simultaneously, the crystal form structure and the pore structure of the forming composition are easy to control; the forming composition can be used as a catalyst carrier for catalytic hydrogenation reaction, oxidation reaction, etc. under the environment of strong acid or strong alkali or can be directly used as a catalyst, and the application prospects of the forming composition are broad. The preparation method of the present invention has the advantages of convenient and simple manufacturing process, low cost, no pollution in the preparation process and obvious economic benefit; the specific surface area of the forming composition of the present invention is from 5 to 170m<2>/g, the pore volume is from 0.1 to 0.5 ml/g, the most probable hole diameter is from 10 to 120 nm, and the compression strength is from 30 to 150 N/cm.
Description
Technical field
The present invention relates to a kind of preparation method of article shaped, more specifically to a kind of preparation method of nanometer titanium dioxide forming substances.
Background technology
Titanium dioxide is used as catalyst or catalyst carrier usually as a kind of chemicals with property in the whole bag of tricks.Because it has excellent catalytic performance, anti-carbon deposit and anti-poisoning capability, has with carried metal " strong interaction ", can significantly improve some activity of such catalysts and selectivity.But the described in the prior art catalyst system that contains titanium dioxide is mostly based on titania powder, and needs the TiO of definite shape in some field
2Article shaped is as catalytic carrier or other application.Because TiO
2There are problems such as the little and bad mechanical strength of specific area in powder in moulding, limited it in industrial application, therefore prepares bigger serface, high-intensity TiO
2Article shaped becomes the emphasis of people's research.
The more existing both at home and abroad researchs of method that prepare titanium dioxide forming substances.Chinese patent CN1186774A discloses the method that a kind of so-gel prepares large mass TiO 2 mesohole solid, and the solid mass of preparation has bigger voidage and " medium " specific area; It is the method for feedstock production TiO 2-based catalyst carrier that Chinese patent CN1149261, CN1348834 propose to adopt metatitanic acid, and after the employing metatitanic acid was raw material, its performance of prepared titanium dioxide forming substances had had improvement in various degree.In the titanic oxide shaping process, selection of binder has also been done number of research projects, and the binding agent that uses as US4388283 is polyacrylamide.Method about titanic oxide shaping has been reported compression molding technology in US5002917, US5366938, addressing in the method for making the catalyst contain titanium dioxide the also slightly explanation of moulding to carrier in CN1255405, CN1154271, CN1212992, CN1178483 etc.
In various commercial Application titanium dioxide forming substances is had different requirements, some catalyst carrier need possess enough porositys to carry catalyst; The hope titanium dioxide forming substances that has preferably has quite high compression strength and wear-resistant ability, and specific area is less important, as the catalytic hydrogenation of aromatic aldehyde under the HTHP operating condition; The titanium dioxide forming substances that requires that has preferably has sufficiently high specific area, and compression strength is less important, as catalytic oxidation under the normal temperature and pressure or catalytic hydrogenation; Also must have bigger specific area and not only require titanium dioxide forming substances to have certain compression strength in the application that has, specific system also will have requirement to crystal phase structure.Prepared titanium dioxide forming substances still can not satisfy in the above-mentioned prior art should have high compression strength also will have bigger specific area and to the crystalline structure requirement.
Summary of the invention
The objective of the invention is to solve the compression strength and difficult compatibling problem of specific area and the deficiency that exist in the above-mentioned prior art, provide a kind of preparation to have the method for the nanometer titanium dioxide forming substances of high-specific surface area and high compressive strength and crystal with controllable crystal forms.
The present invention is achieved by the following technical solutions:
The preparation method of nanometer titanium dioxide forming substances of the present invention may further comprise the steps:
(1), takes by weighing nano titanium oxide binding agent, auxiliary agent and water, through kneading after the mixing;
(2), be extruded into the column type bar that diameter is 1.5～3mm after mediating, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain;
(3) be under 80～120 ℃ of conditions with particle in temperature, dry 10～24 hours;
(4) then under 350～1000 ℃ of temperature conditions, roasting 1～10 hour makes this nanometer titanium dioxide forming substances.
The percentage by weight of each component is as follows in the preparation method's of the nanometer titanium dioxide forming substances of the present invention raw material:
Nano titanium oxide 40～60%
Binding agent 1～10%
Auxiliary agent 1～10%
Water 30～55%
Wherein said auxiliary agent is a kind of or its combination of pore creating material, hole modifier; Described nano titanium dioxide powder grain diameter is 100～250m more than or equal to 10nm and less than 80nm, specific area
2/ g, crystalline structure are anatase titanium dioxide, rutile-type or both mixing crystal formations; Described water is deionized water; In described binding agent preferably polyethylene alcohol, poly-hexylene glycol, carboxymethyl cellulose or the methylcellulose one or more; Described pore creating material preferably glycerine, starch, urea, wet metatitanic acid or ammonium carbonate; Described hole modifier is organic acid or inorganic acid, and organic acid is citric acid or lactic acid, and inorganic acid is sulfuric acid or nitric acid.
The nanometer titanium dioxide forming substances of the present invention's preparation, the specific area of its article shaped is 5～170m
2/ g, pore volume are 0.1～0.5ml/g, and the most probable aperture is 10～120nm, and its compression strength is 30～150N/cm; Described article shaped crystalline structure is anatase titanium dioxide, rutile-type or both mixing crystal formations.
The invention has the beneficial effects as follows: prepared nanometer titanium dioxide forming substances has bigger specific area again when possessing certain compression strength, when specific area is 100～175m
2During/g, its side pressure strength is not less than 30N/cm, and the crystalline structure and the pore structure of article shaped are controlled easily simultaneously; Article shaped can be used under strong acid or the strong alkali environment catalyst for reaction carrier such as catalytic hydrogenation, oxidation or directly uses as catalyst, has a extensive future; Preparation method's technology of the present invention is simple and convenient, and cost is lower, and preparation process is not polluted, and economic benefit is obvious.
Description of drawings
Fig. 1 is preparation method's process flow diagram of the present invention
The specific embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment.
Embodiment one
(particle diameter＜20nm, specific area is 250m to get the 50g nano titanium dioxide powder
2/ g, Detitanium-ore-type), 5g polyvinyl alcohol (PVA) mixes, and adds 5g glycerine, the 50g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain, 120 ℃ of dryings 15 hours, slowly be warming up to 400 ℃ of roastings and make titanium dioxide forming substances of the present invention after 2 hours again.Record compression strength 35N/cm, the specific area 175m of this article shaped as a result
2/ g, the most probable aperture is 100nm, and pore volume is 0.35ml/g, and crystalline structure is an anatase titanium dioxide.
Embodiment two
Other step after 15 hours, slowly is warming up to 800 ℃ of roastings after 2 hours through 120 ℃ of dryings with embodiment one, makes titanium dioxide forming substances of the present invention.Recording as a result, the compression strength of this article shaped is that 150N/cm, specific area are 5m
2/ g, the most probable aperture is 40nm, and pore volume is 0.15ml/g, and crystalline structure is a rutile-type.
Embodiment three
(particle diameter＜20nm, specific area is 250m to get the 50g nano titanium dioxide powder
2/ g, Detitanium-ore-type), 5g carboxymethyl cellulose (CMC), 3g citric acid mix, and adds 5g glycerine, the 50g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain, 120 ℃ of dryings 12 hours, slowly be warming up to 600 ℃ of roastings 2 hours again, make titanium dioxide forming substances of the present invention.Recording as a result, the compression strength of this article shaped is that 50N/cm, specific area are 50m
2/ g, crystalline structure are anatase titanium dioxide, and most probable aperture 50nm, pore volume are 0.28ml/g.
Embodiment four
(particle diameter＜20nm, specific area is 250m to get the 40g nano titanium dioxide powder
2/ g, Detitanium-ore-type), the wet metatitanic acid (loss on drying 40wt%) of 10g, 5g carboxymethyl cellulose (CMC) mix, and adds the rare nitric acid of 5g (0.015mol/L), the 30g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain, 120 ℃ of dryings 15 hours, slowly be warming up to 750 ℃ of roastings 2 hours again, make titanium dioxide forming substances of the present invention.Recording as a result, the compression strength of this article shaped is that 50N/cm, specific area are 80m
2/ g, the most probable aperture is 50nm, and pore volume is 0.24ml/g, and Detitanium-ore-type and rutile-type ratio are 4: 1.
Embodiment five
(particle diameter＜20nm, specific area is 250m to get the 50g nano titanium dioxide powder
2/ g, Detitanium-ore-type), 5g methylcellulose (MC) mixes, and adds 5g glycerine, the 50g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain, 120 ℃ of dryings 10 hours, slowly be warming up to 500 ℃ of roastings 2 hours more again, make titanium dioxide forming substances of the present invention.The compression strength of this article shaped is that 42N/cm, specific area are 105m
2/ g, the most probable aperture is 70nm, and pore volume is 0.32ml/g, and crystalline structure is an anatase titanium dioxide.
Embodiment six
(particle diameter＜80nm, specific area is 30m to get the 50g nano titanium dioxide powder
2/ g, rutile-type), 2g methylcellulose (MC) mixes, and adds 8g glycerine, the 30g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into the 3-4mm long grain, 80 ℃ of dryings 24 hours, slowly be warming up to 700 ℃ of roastings 1 hour more again, make titanium dioxide forming substances of the present invention.The compression strength 30N/cm of this article shaped, specific area are 23m
2/ g, the most probable aperture is 60nm, and pore volume is 0.27ml/g, and crystalline structure is a rutile-type.
Embodiment seven
(particle diameter＜20nm, specific area is 250m to get the 50g nano titanium dioxide powder
2/ g, Detitanium-ore-type), 10g starch mixes, and adds 5g glycerine, the 50g deionized water is mediated; Be extruded into diameter then and be about 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain, 120 ℃ of dryings 15 hours, slowly be warming up to 350 ℃ of roastings again and make titanium dioxide forming substances of the present invention after 10 hours again.The compression strength of this article shaped is that 30N/cm, specific area are 23m
2/ g, the most probable aperture is 120nm, and pore volume is 0.50ml/g, and crystalline structure is an anatase titanium dioxide.
Embodiment eight
(particle diameter＜20nm, specific area is 250m to get the 40g nano titanium dioxide powder
2/ g, Detitanium-ore-type), 2g methylcellulose (MC) mixes, and adds 3g glycerine, the 55g deionized water is mediated; Be extruded into diameter then and be 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into the 3-4mm long grain, 80 ℃ of dryings 24 hours, slowly be warming up to 1000 ℃ of roastings 1 hour more again, make titanium dioxide forming substances of the present invention.The compression strength 150N/cm of this article shaped, specific area are 5m
2/ g, the most probable aperture is 10nm, and pore volume is 0.12ml/g, and crystalline structure is a rutile-type.
Claims (5)
1. the preparation method of a nanometer titanium dioxide forming substances may further comprise the steps:
(1), takes by weighing nano titanium oxide, binding agent, auxiliary agent and water, through kneading after the mixing;
(2), be extruded into the column type bar that diameter is 1.5～3mm after mediating, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain;
(3) be under 80～120 ℃ of conditions with particle in temperature, dry 10～24 hours;
(4) then under 350～1000 ℃ of temperature conditions, roasting 1～10 hour makes nanometer titanium dioxide forming substances;
Wherein the percentage by weight of each component is as follows in the raw material:
Nano titanium oxide 40～60%
Binding agent 1～10%
Auxiliary agent 1～10%
Water 30～55%
Described auxiliary agent is a kind of or its combination of pore creating material, hole modifier; Described nano titanium dioxide powder grain diameter is 100～250m more than or equal to 10nm and less than 80nm, specific area
2/ g, crystalline structure are anatase titanium dioxide, rutile-type or both mixing crystal formations; Described water is deionized water; Prepared article shaped specific area is 5～170m
2/ g, pore volume are 0.1～0.5ml/g, and the most probable aperture is 10～120nm, and its compression strength is 30～150N/cm.
2. the preparation method of nanometer titanium dioxide forming substances according to claim 1 is characterized in that described binding agent is one or more in polyvinyl alcohol, poly-hexylene glycol, carboxymethyl cellulose or the methylcellulose.
3. the preparation method of nanometer titanium dioxide forming substances according to claim 1 is characterized in that described pore creating material is glycerine, starch, urea, wet metatitanic acid or ammonium carbonate.
4. the preparation method of nanometer titanium dioxide forming substances according to claim 1 is characterized in that described hole modifier is organic acid or inorganic acid, and wherein said organic acid is citric acid or lactic acid, and inorganic acid is sulfuric acid or nitric acid.
5. the preparation method of nanometer titanium dioxide forming substances according to claim 1 is characterized in that may further comprise the steps:
(1) take by weighing the 50g nano titanium dioxide powder, wherein nano titanium oxide particle diameter＜20nm, specific area are 250m
2/ g, Detitanium-ore-type, 5g carboxymethyl cellulose, 3g citric acid mix, and adding 5g glycerine, 50g deionized water are mediated;
(2) being extruded into diameter is 2 millimeters column type bar, be placed on tentatively dry under the room temperature after, be cut into 3～4mm long grain;
(3) with particle under 120 ℃ of conditions of temperature, dry 12 hours;
(4) slowly be warming up to 600 ℃ of roastings 2 hours then, make titanium dioxide forming substances;
Prepared article shaped specific area is 50m
2/ g, pore volume are 0.28ml/g, most probable aperture 50nm, and compression strength is 50N/cm.
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| CNB2005100948024A CN100369667C (en) | 2005-10-14 | 2005-10-14 | Nanometer titanium dioxide forming substances and preparation thereof |
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| CNB2005100948024A CN100369667C (en) | 2005-10-14 | 2005-10-14 | Nanometer titanium dioxide forming substances and preparation thereof |
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| CN100369667C true CN100369667C (en) | 2008-02-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101195087B (en) * | 2007-12-21 | 2010-08-25 | 中国石化扬子石油化工有限公司 | Method for producing titanium dioxide preformed catalyst carrier with titanium dioxide aqua compound |
| CN104909405B (en) * | 2014-03-14 | 2017-03-15 | 中国科学院过程工程研究所 | Spindle nano titanium oxide based on cellulose base template and preparation method thereof |
| CN105126930B (en) * | 2015-08-28 | 2017-12-12 | 烟台大学 | A kind of preparation method of catalyst carrier and its application in the catalytic oxidation of hydrogen chloride |
| CN110201656A (en) * | 2019-06-10 | 2019-09-06 | 西安向阳航天材料股份有限公司 | A kind of preparation method of TiO 2-based catalyst carrier |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5395893A (en) * | 1977-02-03 | 1978-08-22 | Mizusawa Industrial Chem | Titanium oxide catalyst carrier and manufacture thereof |
| CN1131058A (en) * | 1995-03-16 | 1996-09-18 | 中国石化齐鲁石油化工公司 | Catalyst for recovering TiO2 base sulfur and preparing method thereof |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
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2005
- 2005-10-14 CN CNB2005100948024A patent/CN100369667C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5395893A (en) * | 1977-02-03 | 1978-08-22 | Mizusawa Industrial Chem | Titanium oxide catalyst carrier and manufacture thereof |
| CN1131058A (en) * | 1995-03-16 | 1996-09-18 | 中国石化齐鲁石油化工公司 | Catalyst for recovering TiO2 base sulfur and preparing method thereof |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
Non-Patent Citations (2)
| Title |
|---|
| 二氧化钛载体强度和孔结构的关系. 沈平生，李大东，闵恩泽.催化学报，第5卷第4期. 1984 * |
| 二氧化钛载体的制备及其表征. 安志强，周立进，陈洪龄.第一届全国化学工程与生物化工年会论文摘要集(上). 2004 * |
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