CN102120597A - Preparation method of high-purity boehmite - Google Patents
Preparation method of high-purity boehmite Download PDFInfo
- Publication number
- CN102120597A CN102120597A CN 201110021780 CN201110021780A CN102120597A CN 102120597 A CN102120597 A CN 102120597A CN 201110021780 CN201110021780 CN 201110021780 CN 201110021780 A CN201110021780 A CN 201110021780A CN 102120597 A CN102120597 A CN 102120597A
- Authority
- CN
- China
- Prior art keywords
- boehmite
- pseudo
- purity
- aluminium
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a preparation method of high-purity boehmite, belonging to the technical field of synthesis of metallic organic compounds. The preparation method comprises the following steps of: preparing alkoxyl aluminum by adopting metallic aluminum with the purity more than 99.5 percent and mixed alcohol of C5-C8 and n-butyl alcohol under the existence of aluminum choride and alkylbenzene solvents; and hydrolyzing, aging and drying the alkylbenzene to obtain the high-purity boehmite. The invention overcomes the defects that the purification is difficult when the alkoxyl aluminum is prepared with low-carbon alcohol and the reaction efficiency is low when the alkoxyl aluminum is prepared with high-carbon alcohol and can obtain the boehmite with the purity up to 99.9 percent by controlling the proportion of the mixed alcohol and the metallic aluminum and the hydrolysis condition. The method provided by the invention ensures that the preparation process of the high-purity boehmite is simplified, the preparation efficiency is high, and the preparation cost is low.
Description
Technical field
A kind of method for preparing high-purity pseudo-boehmite belongs to the organometallics synthesis technical field.More specifically say so about a kind of high-purity pseudo-boehmite and preparation method thereof.
Background technology
High-purity pseudo-boehmite is the precursor material of catalyst carrier alumina.The grain size of pseudo-boehmite, crystalline phase purity and pattern etc. have material impact to the character such as pore volume, pore distribution, specific surface and stability of aluminum oxide.Pseudo-boehmite mainly contains acid system, alkaline process and three kinds of preparation methods of aluminium alcoholates method.Often using a kind of alkaline process at present is that carborization is produced pseudo-boehmite, and Baeyer stone, the promise that produces in preparation process gets dephasigns such as stone, gibbsite and be difficult for removing, and is difficult to obtain the high pseudo-boehmite of crystalline phase purity.And there is the low shortcoming of degree of crystallinity in the pseudo-boehmite of acid system preparation, and all there is the problem of foreign matter content height and three waste discharge in these two kinds of methods.The aluminium alcoholates method is that aluminium alcoholates is obtained the method for pseudo-boehmite by hydrolysis with wearing out, and this method becomes more readily available the pseudo-boehmite of single crystalline phase, and foreign matter content is low.Germany Condea company produces high-purity pseudo-boehmite (for example US4590289) with metallic aluminium powder and n-hexyl alcohol, has had ten thousand tons/year full scale plant, product situation of selling well countries in the world.By analysis, the m and the n that find this pseudo-boehmite satisfy m=1.56, n=2.15, m=D (140)/D (120) wherein, n=D (200)/D (120), the grain size of the corresponding crystal face in 140 peaks in the XRD spectra of described D (140) expression pseudo-boehmite, the grain size of the corresponding crystal face in 120 peaks in the XRD spectra of described D (120) expression pseudo-boehmite, the grain size of the corresponding crystal face in 200 peaks in the XRD spectra of described D (200) expression pseudo-boehmite.According to
Calculate the grain size of different crystal faces.But this Technology exists metallic aluminium powder preparation difficulty, the expensive shortcoming of n-hexyl alcohol.The present inventor finds, under the single situation of crystalline phase, as long as the m of this pseudo-boehmite and n satisfy 1.4≤m≤1.8,2.0≤n≤2.5, the purity of pseudo-boehmite reaches at 99.5% o'clock, then is fit to do the precursor of catalytic reforming carrier, has very high catalytic activity and selectivity.The objective of the invention is to utilize the ordinary purity metallic aluminium, use the not high alcohol mixture of price, obtain aluminum alkoxide, by high-purity pseudo-boehmite of filtration, hydrolysis, the single crystalline phase of aging, dry preparation.Compare and adopt high-purity 99.9999% aluminium wire and water to prepare high-purity pseudo-boehmite (for example CN1974390A) in High Temperature High Pressure, the shortcoming one of this method is to use expensive high-purity aluminium wire, the 2nd, under high-temperature and high-pressure conditions, carry out, cause the production cost of high-purity pseudo-boehmite to increase, and obtain pseudo-boehmite crystalline phase purity and have only 97%.The advantage of method provided by the invention is not need additionally to add the crystal grain ratio that other reagent just can obtain different product faces, the high purity pseudoboehmite that foreign matter content is low, the alcohol mixture of telling behind the hydrolysising aging reclaims easily and utilizes, the non-environmental-pollution problem, the pseudo-boehmite crystalline phase purity height of preparation, foreign matter content is low.
Summary of the invention
With alcohol mixture and metallic aluminium in the presence of the anhydrous chlorides of rase Al catalysts, 110-180 ℃ of reaction 1～10h obtains aluminum alkoxide after the filtration, described metallic aluminium, the mol ratio of alcohol mixture and Aluminum chloride anhydrous is 1: 5～8: 0.01～0.02.Reaction equation is as follows:
Al+3C
nH
2n+1OH→Al(OC
nH
2n+1)
3+3/2H
2 (1)
2. the aluminum alkoxide that obtains in (1) step is splashed in the deionized water,, obtain hydrolysate, tell alcohol mixture that hydrolysis produces and return (1) step and recycle at 80-110 ℃ of following hydrolysis 1-6h.At 90～130 ℃ of down aging 10-48h,, obtain pseudo-boehmite 110～130 ℃ of oven dry.The equation in these two steps is as follows:
Al(OC
nH
2n+1)
3+3H
2O→Al(OH)
3+3C
nH
2n+1OH
Obtain the 100%AlOOH phase, obtain 100% γ-Al at 400～600 ℃ of roasting 4-6h
2O
3
Major advantage of the present invention:
The present invention is a kind of novel method for preparing high-purity pseudo-boehmite, becomes liquid state utilizing alcohol mixture to prepare under the intermediate product aluminum alkoxide room temperature under the excessive situation of metallic aluminium, does not need heating, and saving equipment drops into and energy expenditure, filters easily; Filtrate is colourless, preparation intermediate product purity height.Being hydrolyzed under greater than 80 ℃ need not washing after aging, obtains the high-purity pseudo-boehmite of single crystalline phase after the drying.Two kinds of crystal face grain sizes that obtain pseudo-boehmite by control hydrolysis aging temperature and time satisfy 1.4≤m≤1.8,2.0≤n≤2.5.The alcohol and water that obtains in the hydrolysising aging process can recycle, and reaction does not need washing, belongs to the production technique of low carbon emission reduction, meet the environmental protection theory, and the high-purity pseudo-boehmite physico-chemical parameter that obtains can be regulated.
Specific implementation method
The present invention uses purity greater than 99.5% metallic aluminium and alcohol mixture, in the presence of the anhydrous chlorides of rase Al catalysts, 110-180 ℃ of reaction 1～10h, obtain aluminum alkoxide after the filtration, aluminum alkoxide is at 80-110 ℃ of following hydrolysis 1-6h, at 100～130 ℃ of down aging 10-48h, behind 110～130 ℃ of oven dry 1-6h, obtain high-purity pseudo-boehmite.The alcohol and water that produces behind the hydrolysising aging can recycle, this method non-environmental-pollution and toxic residue.
Further illustrate technology characteristics of the present invention with embodiment below.
Embodiment 1
Put into the 27g aluminium ingot in the 1L four-hole boiling flask of band prolong, 1.33g aluminum trichloride (anhydrous) and 50g propyl carbinol (water content is less than 0.2%) behind the back flow reaction 1h, add 260g n-Octanol and 24g propyl carbinol alcohol mixture, back flow reaction 1h, filtered while hot.Filtrate putting into taken back the 2L four-hole boiling flask of stream prolong and water trap, after temperature reached 80 ℃, the adding temperature was 80 ℃ deionized water 400g, hydrolysis reaction 4h, tell alcohol, add the 500g deionized water again, be warmed up to 95 ℃, reflux digestion 14h, steam the pure and mild portion water of residue, 120 ℃ of oven dry, time 6h obtains 60g white pseudo-boehmite.Through XRD, differential thermal and ICP-MS analyze, and proving crystalline phase purity is 100%, and foreign matter content is listed in the table 1 through the n and the m value that calculate less than high-purity pseudo-boehmite of 0.01%.
Embodiment 2
Put into the 27g aluminium ingot in the 1L four-hole boiling flask of band prolong, 1.33g aluminum trichloride (anhydrous) and 50g propyl carbinol (water content is less than 0.2%) behind the back flow reaction 0.5h, add 234g n-Octanol and 24g propyl carbinol alcohol mixture, backflow 1h, and below operation is with example 1.
Embodiment 3
Put into the 27g aluminium wire in the 2L four-hole boiling flask, 1.33g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 0.5h, add 260g n-Octanol and 24g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.80 ℃ of hydrolysis temperatures, time 4h, 100 ℃ of aging temperatures, time 12h, 120 ℃ of bake out temperatures, time 6h.
Embodiment 4
Put into the 27g aluminium flake in the 1L four-hole boiling flask, 0.2g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 0.5h, add 176g Pentyl alcohol and 24g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.95 ℃ of hydrolysis temperatures, time 4h, 95 ℃ of aging temperatures, time 12h, 120 ℃ of bake out temperatures, time 6h.
Embodiment 5
Put into the 27g aluminium powder in the 1L four-hole boiling flask, 0.2g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 0.5h, add 260g n-Octanol and 24g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.100 ℃ of hydrolysis temperatures, time 4h, 110 ℃ of aging temperatures, time 10h, 120 ℃ of bake out temperatures, time 6h.
Embodiment 6
Put into the 27g aluminium ingot in the 1L four-hole boiling flask, 0.2g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 1h, add 204g n-hexyl alcohol and 74g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.95 ℃ of hydrolysis temperatures, time 4h, 110 ℃ of aging temperatures, time 10h, 120 ℃ of bake out temperatures, time 5h.
Embodiment 7
Put into the 27g aluminium flake in the 1L four-hole boiling flask, 2.6g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 0.5h, add 204g n-hexyl alcohol and 74g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.90 ℃ of hydrolysis temperatures, time 4h, 98 ℃ of aging temperatures, time 12h, 110 ℃ of bake out temperatures, time 6h.
Embodiment 8
Put into the 27g aluminium flake in the 1L four-hole boiling flask, 2.6g aluminum trichloride (anhydrous) and 50g propyl carbinol behind the reaction 0.5h, add 232g n-Heptyl alcohol and 74g propyl carbinol alcohol mixture, backflow 2h, and below operation is with example 1.98 ℃ of hydrolysis temperatures, time 4h, 98 ℃ of aging temperatures, time 14h, 120 ℃ of bake out temperatures, time 5h.
Pseudo-boehmite grain size and ratio that above embodiment obtains see Table 1.
Table 1 pseudo-boehmite grain size and ratio
Claims (9)
1. high-purity pseudo-boehmite, it is characterized in that, the m of this pseudo-boehmite and n satisfy 1.4≤m≤1.8,2.0≤n≤2.5, m=D (140)/D (120) wherein, n=D (200)/D (120), the grain size of the corresponding crystal face in 140 peaks in the XRD spectra of described D (140) expression pseudo-boehmite, the grain size of the corresponding crystal face in 120 peaks in the XRD spectra of described D (120) expression pseudo-boehmite, the grain size of the corresponding crystal face in 200 peaks in the XRD spectra of described D (200) expression pseudo-boehmite, according to Scherrer grain size determination formula:
Calculate the grain size of different crystal faces, D
HklThe mean thickness of-vertical crystal plane hkl direction; K-diffraction peak shape constant, the Scherrer derivation formula is defined as 0.89; β
Hkl-diffraction peak halfwidth, β
Hkl=B-b, the sample diffraction peak halfwidth that the B-experiment records; B-instrumental broadening degree, with grain fineness number greater than the width of the diffraction peak that records under 200nm sample and the same experiment condition (measuring b=0.1559 when 28.2751 ° with the standard silicon of 99%325mesh in this experiment).λ---diffracted ray wavelength (0.15046nm).
2. the preparation method of the described pseudo-boehmite of claim 1, preparation process comprises:
(1) alcohol mixture (mol ratio is 1: 2～3) with propyl carbinol and C5-C8 alcohol reacts in the presence of catalyzer aluminum chloride and alkyl benzene solvent with metallic aluminium, obtains aluminum alkoxide after the filtered while hot.
(2) add the deionized water hydrolysis in the aluminum alkoxide, obtain high-purity pseudo-boehmite after the aging and drying of hydrolysate.
3. the described method of claim 2, the temperature of reaction that it is characterized in that described metallic aluminium, alcohol mixture, aluminum chloride and alkylbenzene is 110-180 ℃, and the reaction times is 1～10h, and mol ratio is 1: 2～3: 0.01～0.02: 2.
4. the described method of claim 2 is characterized in that used metallic aluminium can be an aluminium ingot, aluminium flake, aluminium wire, aluminium powder, the purity requirement of aluminium＞99.5%.
5. the pure and mild propyl carbinol of the described C5-C8 of claim 2 is characterized in that water content＜0.2% of used alcohol.
6. the described method of claim 2 is characterized in that used aluminum chloride is an aluminum trichloride (anhydrous).
7. the described method of claim 2 is characterized in that the described filtered while hot temperature of step (1) is 90-120 ℃, depresses or 100～760mmHg carries out adding.
8. the described method of claim 2, the hydrolysis temperature that it is characterized in that step (2) is 80-110 ℃, the time is 1-6h; Aging temperature is 90～130 ℃, and the time is 10-48h, and the alcohol and water that obtains behind the hydrolysising aging can recycle.
9. the described method of claim 1 is characterized in that the product drying temperature is 110-130 ℃, and be 3-6h time of drying, and the pseudo-boehmite purity that obtains is greater than 99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110021780 CN102120597A (en) | 2011-01-14 | 2011-01-14 | Preparation method of high-purity boehmite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110021780 CN102120597A (en) | 2011-01-14 | 2011-01-14 | Preparation method of high-purity boehmite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102120597A true CN102120597A (en) | 2011-07-13 |
Family
ID=44249283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110021780 Pending CN102120597A (en) | 2011-01-14 | 2011-01-14 | Preparation method of high-purity boehmite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102120597A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192880A (en) * | 2014-07-18 | 2014-12-10 | 大连理工大学 | Method for preparing high-purity pseudo-boehmite |
| CN104338563A (en) * | 2013-08-02 | 2015-02-11 | 天津润沃供水安装工程有限公司 | Preparation technology for hydrogenation catalyst carrier and method for controlling pore diameter |
| CN105084397B (en) * | 2014-05-13 | 2017-01-25 | 中国石油化工股份有限公司 | Strip-shaped crystal grain boehmite preparation method |
| CN106629795A (en) * | 2016-10-13 | 2017-05-10 | 山东允能催化技术有限公司 | Preparation method of high-purity monohydrate diaspore |
| CN106629794A (en) * | 2016-10-13 | 2017-05-10 | 北京工商大学 | Preparation method of high-gum-solubility pseudoboehmite |
| CN106946280A (en) * | 2016-10-13 | 2017-07-14 | 北京工商大学 | A kind of preparation method of boehmite and aluminum oxide |
| CN109721088A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of aluminium hydroxide and preparation method thereof |
| CN111807396A (en) * | 2019-04-10 | 2020-10-23 | 吉林省氢汇新能源有限公司 | Production method of high-purity pseudo-boehmite and produced high-purity pseudo-boehmite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590289A (en) * | 1982-12-04 | 1986-05-20 | Condea Chemie Gmbh | Process and apparatus for producing aluminium alkoxides |
| US6174511B1 (en) * | 1997-07-15 | 2001-01-16 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| CN1974390A (en) * | 2006-12-18 | 2007-06-06 | 天津理工大学 | Prepn process of high purity pseudoboehmite |
-
2011
- 2011-01-14 CN CN 201110021780 patent/CN102120597A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590289A (en) * | 1982-12-04 | 1986-05-20 | Condea Chemie Gmbh | Process and apparatus for producing aluminium alkoxides |
| US6174511B1 (en) * | 1997-07-15 | 2001-01-16 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| CN1974390A (en) * | 2006-12-18 | 2007-06-06 | 天津理工大学 | Prepn process of high purity pseudoboehmite |
Non-Patent Citations (1)
| Title |
|---|
| 《催化学报》 20030731 高建峰 等 用偏铝酸钠直接制取高纯拟薄水铝石 505-508 1 第24卷, 第7期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104338563A (en) * | 2013-08-02 | 2015-02-11 | 天津润沃供水安装工程有限公司 | Preparation technology for hydrogenation catalyst carrier and method for controlling pore diameter |
| CN105084397B (en) * | 2014-05-13 | 2017-01-25 | 中国石油化工股份有限公司 | Strip-shaped crystal grain boehmite preparation method |
| CN104192880A (en) * | 2014-07-18 | 2014-12-10 | 大连理工大学 | Method for preparing high-purity pseudo-boehmite |
| CN106629795A (en) * | 2016-10-13 | 2017-05-10 | 山东允能催化技术有限公司 | Preparation method of high-purity monohydrate diaspore |
| CN106629794A (en) * | 2016-10-13 | 2017-05-10 | 北京工商大学 | Preparation method of high-gum-solubility pseudoboehmite |
| CN106946280A (en) * | 2016-10-13 | 2017-07-14 | 北京工商大学 | A kind of preparation method of boehmite and aluminum oxide |
| CN106629794B (en) * | 2016-10-13 | 2018-10-16 | 北京工商大学 | A kind of preparation method of high peptization boehmite |
| CN109721088A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of aluminium hydroxide and preparation method thereof |
| CN109721088B (en) * | 2017-10-27 | 2021-02-05 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
| CN111807396A (en) * | 2019-04-10 | 2020-10-23 | 吉林省氢汇新能源有限公司 | Production method of high-purity pseudo-boehmite and produced high-purity pseudo-boehmite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102120597A (en) | Preparation method of high-purity boehmite | |
| CN101920979A (en) | Preparation method of highly pure alpha-aluminum oxide | |
| CN104355967B (en) | The method of autocatalysis one-step synthesis high puring aluminium isopropoxide | |
| CN103833780B (en) | A kind of continuous reaction rectification prepares the processing method of trimethyl borate | |
| CN102320638A (en) | Preparation method of low-sodium fine grain alumina | |
| JP5716669B2 (en) | Methanol synthesis catalyst | |
| CN102120599A (en) | Preparation method of alumina with intensive mesopore diameter distribution | |
| CN106946280B (en) | A kind of preparation method of boehmite and aluminium oxide | |
| CN102285867B (en) | Synthesis method of 3-hexyne-2,5-diol | |
| Hajipour et al. | Acetylation of alcohols and phenols under solvent-free conditions using copper zirconium phosphate | |
| CN102992367B (en) | Technology for producing high-purity ultrafine powder alumina with spherical or fibrous crystal form | |
| Lu et al. | Preparation and Properties of Pseudo-boehmite Obtained from High-Alumina Fly Ash by a Sintering–CO 2 Decomposition Process | |
| CN1117031C (en) | Process for preparing high-purity superfine alumina powder by aluminium alkoxide hydrolysis | |
| CN109369342B (en) | Preparation method of high-purity aluminum isopropoxide | |
| CN102161493A (en) | Method for preparing macroporous high-purity hydrated alumina | |
| CN102120598A (en) | Preparation method of high-purity hydrated alumina | |
| CN102491391A (en) | Preparation method for high-purity alumina | |
| CN103738989B (en) | A kind of middle-low bauxite produces the method for aluminum oxide | |
| CN106938851B (en) | A kind of preparation method of high-purity boehmite | |
| JP2911244B2 (en) | Method for producing lower olefins | |
| CN103724210B (en) | The production method of N-ethyl-n-butylamine | |
| CN102139232A (en) | Method for preparing alumina carrier suitable for catalytic cracking of heavy oil | |
| CN102814160A (en) | Cleaning agent for removing iron carbonyl and nickel carbonyl in synthesis gas and preparation method and application of cleaning agent | |
| CN104829455B (en) | A kind of method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate | |
| CN103011219A (en) | Mesoporous alumina and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110713 |