JPH08268716A - Method for controlling particle diameter of pseudo-boehmite powder - Google Patents
Method for controlling particle diameter of pseudo-boehmite powderInfo
- Publication number
- JPH08268716A JPH08268716A JP7095928A JP9592895A JPH08268716A JP H08268716 A JPH08268716 A JP H08268716A JP 7095928 A JP7095928 A JP 7095928A JP 9592895 A JP9592895 A JP 9592895A JP H08268716 A JPH08268716 A JP H08268716A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- pseudo
- soln
- boehmite powder
- alkali
- 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 239000000843 powder Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 title claims abstract description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 150000004645 aluminates Chemical class 0.000 claims abstract description 17
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000003929 acidic solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 229910052910 alkali metal silicate Inorganic materials 0.000 abstract description 5
- 239000007858 starting material Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004455 differential thermal analysis Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- -1 aluminum alkoxide Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、触媒担体として使用さ
れる擬ベーマイト粉を中和分解法で作製する際の擬ベー
マイト粉の粒径制御方法に関するものである。ここで言
う粒径とは、一次粒子径のことであり結晶子径と同意で
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for controlling the particle size of pseudo-boehmite powder when the pseudo-boehmite powder used as a catalyst carrier is produced by a neutralization decomposition method. The particle size mentioned here is the primary particle size and is synonymous with the crystallite size.
【０００２】[0002]
【従来の技術】水酸化アルミニウム、オキシ水酸化アル
ミニウム、アルミナ等のアルミニウム化合物は、触媒担
体の原料もしくは製品として広く用いられている。一般
的には、熱安定性に優れ機械的強度に優れるγ−アルミ
ナが、触媒担体としてよく用いられ、これは、一般にベ
ーマイトゲル(擬ベーマイト)を焼成することにより製造
される。この擬ベーマイト粉末の作製には、アルミニウ
ム塩の中和分解法やアルミニウムアルコキシドの加水分
解法が一般的に用いられる。2. Description of the Related Art Aluminum compounds such as aluminum hydroxide, aluminum oxyhydroxide, and alumina are widely used as raw materials or products for catalyst carriers. In general, γ-alumina, which has excellent thermal stability and mechanical strength, is often used as a catalyst carrier, and it is generally produced by firing boehmite gel (pseudo-boehmite). In order to produce this pseudo-boehmite powder, a neutralization decomposition method of an aluminum salt and a hydrolysis method of an aluminum alkoxide are generally used.
【０００３】一般的な中和分解法は、 アルミニウム塩溶液とアルミン酸アルカリ、またはア
ルミニウム塩溶液とアルカリ、またはアルミン酸アルカ
リ溶液と酸を室温以上、pH4〜11の条件になるように混
合する。 により作製されたベーマイトゲルを、必要に応じて
加温、熟成する。 得られたスラリーをフィルタープレス等で濾過し、純
水中に分散させて洗浄する工程を繰り返した後、スプレ
ードライで乾燥し、擬ベーマイト粉末を得る。から成
る。また、アルミニウムアルコキシドの加水分解法は、 アルミニウムアルコキシドに水を添加、混合する。 、上記の上記中和分解法の工程と同様。 である。得られた擬ベーマイト粉は、硝酸、酢酸等の解
こう剤を含む水溶液を添加し、混練後、押出し、乾燥・
焼成工程を経て、アルミナ触媒担体となる。In a general neutralization decomposition method, an aluminum salt solution and an alkali aluminate, an aluminum salt solution and an alkali, or an alkali aluminate solution and an acid are mixed at room temperature or higher and a pH of 4 to 11. The boehmite gel prepared in Step 1 is heated and aged as required. The resulting slurry is filtered by a filter press or the like, dispersed in pure water, and washed to repeat the process, and then dried by spray drying to obtain pseudo-boehmite powder. Consists of. In addition, in the hydrolysis method of aluminum alkoxide, water is added to and mixed with aluminum alkoxide. The same as the steps of the above-mentioned neutralization decomposition method. Is. The obtained pseudo-boehmite powder was added with an aqueous solution containing a peptizer such as nitric acid and acetic acid, kneaded, extruded, and dried.
It becomes an alumina catalyst carrier through a firing process.
【０００４】一般に触媒担体としての性状は、大きい比
表面積、適切な細孔径及び細孔分布、大きい細孔容積、
強い機械的強度、活性金属種の分散性が良好なこと、成
形性の良いこと等が挙げられる。これらの条件は、粉体
や触媒担体の製造条件に大きく支配される。特に、沈殿
形成時、沈殿熟成時における溶液のpH、温度、アル
ミニウム濃度、塩濃度、時間等が重要なパラメータであ
る。中和分解法の場合、一般的には、沈殿形成時、沈
殿熟成時とも、pHは4〜11、温度は室温〜100℃、必要
に応じて100℃〜200℃の温度範囲で処理される。しか
し、100℃以上では圧力容器が必要となりコスト的に問
題がある。Generally, the properties as a catalyst carrier are as follows: large specific surface area, appropriate pore size and pore distribution, large pore volume,
It has strong mechanical strength, good dispersibility of active metal species, and good moldability. These conditions are largely controlled by the manufacturing conditions of the powder and the catalyst carrier. In particular, the pH, temperature, aluminum concentration, salt concentration, time, etc. of the solution at the time of precipitation formation and precipitation aging are important parameters. In the case of the neutralization decomposition method, generally, the pH is 4 to 11, the temperature is room temperature to 100 ° C, and the treatment is carried out in the temperature range of 100 ° C to 200 ° C as needed, both at the time of forming the precipitate and at the time of aging the precipitate. . However, if the temperature is 100 ° C or higher, a pressure vessel is required, which causes a cost problem.
【０００５】[0005]
【発明が解決しようとする課題】アルミニウムアルコキ
シドの加水分解法によって得られた擬ベーマイト粉は不
純物が少なく結晶性も良く、粉体として好ましい特性を
有しているが、非常にコストが高いという問題点があ
る。一方、中和分解法はコストは安価である。しかし、
中和分解法により作製された擬ベーマイト粉の粒子径の
制御は上記の沈殿形成時のパラメータ(溶液のpH、温
度、アルミニウム濃度、塩濃度、時間等)の制御により
可能であるが、粒径の大きな擬ベーマイト粉の製造はこ
れらのパラメータの制御では困難であるという欠点があ
った。The pseudo-boehmite powder obtained by the hydrolysis method of aluminum alkoxide has few impurities and good crystallinity, and has desirable characteristics as a powder, but it is very expensive. There is a point. On the other hand, the neutralization decomposition method is inexpensive. But,
The particle size of the pseudo-boehmite powder produced by the neutralization decomposition method can be controlled by controlling the above-mentioned precipitation formation parameters (solution pH, temperature, aluminum concentration, salt concentration, time, etc.) However, the production of large pseudo-boehmite powders with a large number of particles is difficult by controlling these parameters.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者は上記
問題点を解決するために鋭意検討した結果、中和分解法
において、出発原料としてセリウム塩溶液またはチタン
塩溶液を添加したアルミニウム塩溶液または酸性溶液、
または、ケイ酸アルカリ溶液を添加したアルミン酸アル
カリ溶液またはアルカリ溶液を用い、これを水酸化アル
ミニウムと共沈させ、熟成、洗浄、乾燥することによ
り、擬ベーマイト粉の粒子径、結晶性を制御できること
を見出した。The inventors of the present invention have made extensive studies to solve the above problems, and as a result, in the neutralization decomposition method, an aluminum salt solution to which a cerium salt solution or a titanium salt solution was added as a starting material. Or acidic solution,
Alternatively, it is possible to control the particle size and crystallinity of the pseudo-boehmite powder by using an alkaline aluminate solution or an alkaline solution to which an alkaline silicate solution is added, coprecipitating this with aluminum hydroxide, and aging, washing and drying. Found.
【０００７】すなわち、本発明は、アルミニウム塩溶液
とアルミン酸アルカリ溶液、またはアルミニウム塩溶液
とアルカリ溶液、またはアルミン酸アルカリ溶液と酸性
溶液を、混合、熟成、洗浄、乾燥することにより擬ベー
マイト粉を合成する方法において、セリウム塩溶液また
はチタン塩溶液を含有したアルミニウム塩溶液または酸
性溶液、または、ケイ酸アルカリ溶液を含有したアルミ
ン酸アルカリ溶液またはアルカリ溶液を用いることを特
徴とする擬ベーマイト粉の粒径制御方法である。That is, according to the present invention, a pseudo-boehmite powder is obtained by mixing, aging, washing and drying an aluminum salt solution and an alkali aluminate solution, an aluminum salt solution and an alkali solution, or an alkali aluminate solution and an acidic solution. In the method of synthesizing, pseudo-boehmite powder particles characterized by using an aluminum salt solution or an acidic solution containing a cerium salt solution or a titanium salt solution, or an alkaline aluminate solution or an alkaline solution containing an alkali silicate solution. This is a diameter control method.
【０００８】[0008]
【発明の具体的説明】本発明は、セリウム塩溶液または
チタン塩溶液を添加したアルミニウム塩溶液または酸性
溶液、ケイ酸アルカリ溶液を添加したアルミン酸アルカ
リ溶液またはアルカリ溶液を出発原料として用いる。こ
こで、セリウム塩としては、硝酸セリウム、塩化セリウ
ムなどを用いることができる。または、チタン塩溶液と
しては、四塩化チタン、硫酸チタン、硝酸チタン、チタ
ンアルコキシドなどを用いることができる。ケイ酸アル
カリ溶液としては、ケイ酸ソーダなどを用いることがで
きる。添加量は目的の粒径、結晶性に応じて適宜調整す
る。DETAILED DESCRIPTION OF THE INVENTION In the present invention, an aluminum salt solution or an acidic solution to which a cerium salt solution or a titanium salt solution is added, and an alkaline aluminate solution or an alkaline solution to which an alkaline silicate solution is added are used as starting materials. Here, as the cerium salt, cerium nitrate, cerium chloride, or the like can be used. Alternatively, titanium tetrachloride, titanium sulfate, titanium nitrate, titanium alkoxide, or the like can be used as the titanium salt solution. Sodium silicate or the like can be used as the alkali silicate solution. The addition amount is appropriately adjusted according to the target particle size and crystallinity.
【０００９】一方、アルミニウム塩溶液、酸性溶液、ア
ルミン酸アルカリ溶液、アルカリ溶液としては一般的に
中和法に用いられる塩を使用する。代表的には、アルミ
ニウム塩溶液としては、塩化アルミニウム、硫酸アルミ
ニウム、硝酸アルミニウム溶液等を、アルミン酸アルカ
リとしてはアルミン酸ソーダ等を、アルカリとしては、
アンモニア、苛性ソーダ等を、酸としては、硫酸、塩
酸、硝酸等を用いる。On the other hand, as the aluminum salt solution, the acidic solution, the alkaline aluminate solution, and the alkaline solution, salts generally used in the neutralization method are used. Typically, the aluminum salt solution is aluminum chloride, aluminum sulfate, an aluminum nitrate solution, etc., the alkali aluminate is sodium aluminate, etc., and the alkali is
Ammonia, caustic soda and the like are used, and as the acid, sulfuric acid, hydrochloric acid, nitric acid and the like are used.
【００１０】尚、熟成、洗浄、乾燥条件は、目的の担体
特性となる操作条件で、一般的な中和分解法の作製方法
が用いられる。The aging, washing, and drying conditions are the operating conditions that give the desired carrier properties, and a general method for preparing a neutralization decomposition method is used.
【００１１】[0011]
【実施例１】濃度0.5mol/ｌの塩化アルミニウム水溶液
に四塩化チタン水溶液を乾燥後の粉末中にTiが0.1wt％
となるように添加混合し、さらに濃度0.5mol/ｌの水酸
化ナトリウム溶液を添加してpHを9.0に調整した。その
後、80℃に加温し20時間熟成した後、フィルタープレス
で濾過洗浄した。スラリーの電気伝導度が、0.05mS/cm
以下となった時点で、得られたスラリーをスプレードラ
イで乾燥して擬ベーマイト粉を得た。擬ベーマイト粉の
Ｘ線回折図形の(020)ピークより求めた結晶子径、及び
示差熱分析(DTA)より求めた擬ベーマイトからγ−アル
ミナへの相転移温度を表１に示す。結晶子径は33Å、相
転移温度は450℃であった。Example 1 Ti was 0.1 wt% in the powder after drying an aqueous solution of titanium tetrachloride in an aqueous solution of aluminum chloride having a concentration of 0.5 mol / l.
The mixture was added and mixed so that the concentration became 0.5 mol / l, and a sodium hydroxide solution having a concentration of 0.5 mol / l was added to adjust the pH to 9.0. Then, the mixture was heated to 80 ° C. and aged for 20 hours, and then filtered and washed with a filter press. The electrical conductivity of the slurry is 0.05 mS / cm
When the following was obtained, the obtained slurry was dried by spray drying to obtain pseudo-boehmite powder. Table 1 shows the crystallite size obtained from the (020) peak of the X-ray diffraction pattern of the pseudo-boehmite powder and the phase transition temperature from pseudo-boehmite to γ-alumina obtained by the differential thermal analysis (DTA). The crystallite size was 33Å and the phase transition temperature was 450 ℃.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【実施例２】実施例１の四塩化チタン水溶液の代わりに
塩化セリウムを用い、濃度0.5mol/ｌの塩化アルミニウ
ム水溶液に乾燥後粉末中にCeが0.1wt％となるように添
加混合し、実施例１と同様に擬ベーマイト粉を得た。擬
ベーマイト粉のＸ線回折図形の(020)ピークより求めた
結晶子径、及び示差熱分析(DTA)より求めた擬ベーマイ
トからγ−アルミナへの相転移温度を表１に示す。結晶
子径は35Å、相転移温度は455℃であった。[Example 2] Cerium chloride was used in place of the titanium tetrachloride aqueous solution of Example 1, and an aluminum chloride aqueous solution having a concentration of 0.5 mol / l was added and mixed so that Ce was 0.1 wt% in the powder after drying, Pseudo-boehmite powder was obtained in the same manner as in Example 1. Table 1 shows the crystallite size obtained from the (020) peak of the X-ray diffraction pattern of the pseudo-boehmite powder and the phase transition temperature from pseudo-boehmite to γ-alumina obtained by the differential thermal analysis (DTA). The crystallite size was 35Å and the phase transition temperature was 455 ° C.
【００１４】[0014]
【実施例３】濃度0.5mol/ｌのアルミン酸ソーダ溶液に
ケイ酸ソーダ水溶液を乾燥後の粉末中にSiが0.1wt％と
なるように添加混合し、塩酸を添加してpHを9.0に調整
した。その後、80℃に加温し20時間熟成した後、フィル
タープレスで濾過洗浄した。スラリーの電気伝導度が、
0.05mS/cm以下となった時点で、得られたスラリーをス
プレードライで乾燥して擬ベーマイト粉を得た。擬ベー
マイト粉のＸ線回折図形の(020)ピークより求めた結晶
子径、及び示差熱分析(DTA)より求めた擬ベーマイトか
らγ−アルミナへの相転移温度を表１に示す。結晶子径
は30Å、相転移温度は440℃であった。Example 3 A sodium aluminate solution having a concentration of 0.5 mol / l was mixed with an aqueous solution of sodium silicate so that Si in the powder after drying was 0.1 wt%, and hydrochloric acid was added to adjust the pH to 9.0. did. Then, the mixture was heated to 80 ° C. and aged for 20 hours, and then filtered and washed with a filter press. The electrical conductivity of the slurry is
When it became 0.05 mS / cm or less, the obtained slurry was dried by spray drying to obtain pseudo-boehmite powder. Table 1 shows the crystallite size obtained from the (020) peak of the X-ray diffraction pattern of the pseudo-boehmite powder and the phase transition temperature from pseudo-boehmite to γ-alumina obtained by the differential thermal analysis (DTA). The crystallite size was 30Å and the phase transition temperature was 440 ℃.
【００１５】[0015]
【比較例１】実施例１の四塩化チタン水溶液を添加せず
実施例１と同様に擬ベーマイト粉を得た。擬ベーマイト
粉のＸ線回折図形の(020)ピークより求めた結晶子径、
及び示差熱分析(DTA)より求めた擬ベーマイトからγ−
アルミナへの相転移温度を表１に示す。結晶子径は26
Å、相転移温度は420℃であった。Comparative Example 1 A pseudo-boehmite powder was obtained in the same manner as in Example 1 without adding the titanium tetrachloride aqueous solution of Example 1. Crystallite diameter obtained from the (020) peak of the X-ray diffraction pattern of pseudo-boehmite powder,
And γ − from pseudoboehmite obtained by differential thermal analysis (DTA)
Table 1 shows the phase transition temperatures to alumina. Crystallite size is 26
Å The phase transition temperature was 420 ℃.
【００１６】このように、セリウム塩溶液またはチタン
塩溶液を添加したアルミニウム塩溶液、ケイ酸アルカリ
溶液を添加したアルミン酸アルカリ溶液を出発原料とし
て用いることで、擬ベーマイト粉末の結晶子径が大きく
なり、また擬ベーマイトからγ−アルミナへの相転移温
度が高くなっていることがわかる。従って、擬ベーマイ
ト粉末の粒径、結晶性の制御が可能であることがわか
る。As described above, by using the aluminum salt solution added with the cerium salt solution or the titanium salt solution and the alkali aluminate solution added with the alkali silicate solution as the starting materials, the crystallite diameter of the pseudo-boehmite powder is increased. It is also seen that the phase transition temperature from pseudo-boehmite to γ-alumina is high. Therefore, it is understood that the particle size and crystallinity of the pseudo-boehmite powder can be controlled.
【００１７】[0017]
【発明の効果】本発明により、中和分解法においてセリ
ウム塩溶液またはチタン塩溶液を添加したアルミニウム
塩溶液または酸性溶液、ケイ酸アルカリ溶液を添加した
アルミン酸アルカリ溶液またはアルカリ溶液を出発原料
として用いることにより、擬ベーマイト粉の粒径、結晶
性を制御できる。INDUSTRIAL APPLICABILITY According to the present invention, an aluminum salt solution or an acidic solution added with a cerium salt solution or a titanium salt solution, or an alkaline aluminate solution or an alkaline solution added with an alkali silicate solution is used as a starting material in the neutralization decomposition method. This makes it possible to control the particle size and crystallinity of the pseudo-boehmite powder.
Claims (1)
溶液、またはアルミニウム塩溶液とアルカリ溶液、また
はアルミン酸アルカリ溶液と酸性溶液を、混合、熟成、
洗浄、乾燥することにより擬ベーマイト粉を合成する方
法において、セリウム塩溶液またはチタン塩溶液を含有
したアルミニウム塩溶液または酸性溶液、または、ケイ
酸アルカリ溶液を含有したアルミン酸アルカリ溶液また
はアルカリ溶液を用いることを特徴とする擬ベーマイト
粉の粒径制御方法。1. An aluminum salt solution and an alkali aluminate solution, an aluminum salt solution and an alkali solution, or an alkali aluminate solution and an acidic solution are mixed and aged.
In the method of synthesizing pseudo-boehmite powder by washing and drying, an aluminum salt solution or an acidic solution containing a cerium salt solution or a titanium salt solution, or an alkaline aluminate solution or an alkaline solution containing an alkaline silicate solution is used. A particle size control method for pseudo-boehmite powder, which is characterized by the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7095928A JPH08268716A (en) | 1995-03-30 | 1995-03-30 | Method for controlling particle diameter of pseudo-boehmite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7095928A JPH08268716A (en) | 1995-03-30 | 1995-03-30 | Method for controlling particle diameter of pseudo-boehmite powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08268716A true JPH08268716A (en) | 1996-10-15 |
Family
ID=14150942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7095928A Pending JPH08268716A (en) | 1995-03-30 | 1995-03-30 | Method for controlling particle diameter of pseudo-boehmite powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08268716A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999003783A1 (en) * | 1997-07-15 | 1999-01-28 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| WO2001012553A1 (en) * | 1999-08-11 | 2001-02-22 | Akzo Nobel N.V. | Process for the preparation of quasi-crystalline boehmites from inexpensive precursors |
| JP2003507299A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing pseudocrystalline boehmite |
| JP2003507297A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Microcrystalline boehmite containing additives and shaped particles and catalyst composition containing such microcrystalline boehmite |
| JP2003507296A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Pseudocrystalline boehmite with additives |
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| JP2007167842A (en) * | 2004-03-12 | 2007-07-05 | Saint-Gobain Ceramics & Plastics Inc | Method of forming spray dried alumina catalyst carrier material |
| JP2015500788A (en) * | 2011-12-20 | 2015-01-08 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Method for producing spheroidal alumina particles |
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| CN105271331A (en) * | 2015-10-22 | 2016-01-27 | 中国海洋石油总公司 | Method for preparing pseudo-boehmite by taking waste silicon-aluminum molecular sieve as raw material |
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| JP2019507087A (en) * | 2016-01-29 | 2019-03-14 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Method for producing alumina gel having high dispersibility and specific crystallite size |
-
1995
- 1995-03-30 JP JP7095928A patent/JPH08268716A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999003783A1 (en) * | 1997-07-15 | 1999-01-28 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| US6174511B1 (en) | 1997-07-15 | 2001-01-16 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| US6689333B1 (en) * | 1999-08-11 | 2004-02-10 | Akzo Nobel N.V. | Process for the preparation of quasi-crystalline boehmites from inexpensive precursors |
| WO2001012553A1 (en) * | 1999-08-11 | 2001-02-22 | Akzo Nobel N.V. | Process for the preparation of quasi-crystalline boehmites from inexpensive precursors |
| JP2003507297A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Microcrystalline boehmite containing additives and shaped particles and catalyst composition containing such microcrystalline boehmite |
| JP2003507296A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Pseudocrystalline boehmite with additives |
| JP2003507298A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Process for producing pseudocrystalline boehmite from inexpensive precursors |
| JP2003507299A (en) * | 1999-08-11 | 2003-02-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing pseudocrystalline boehmite |
| US6919294B2 (en) | 2002-02-06 | 2005-07-19 | Japan Energy Corporation | Method for preparing hydrogenation purification catalyst |
| WO2003066215A1 (en) * | 2002-02-06 | 2003-08-14 | Japan Energy Corporation | Method for preparing hydrogenation purification catalyst |
| KR100895632B1 (en) * | 2002-02-06 | 2009-05-07 | 쟈판에나지 덴시자이료 가부시키가이샤 | Method for preparing hydrogenation purification catalyst |
| JP2007167842A (en) * | 2004-03-12 | 2007-07-05 | Saint-Gobain Ceramics & Plastics Inc | Method of forming spray dried alumina catalyst carrier material |
| JP2015500788A (en) * | 2011-12-20 | 2015-01-08 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Method for producing spheroidal alumina particles |
| CN104671265A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A method of preparing pseudoboehmite |
| JP2016028993A (en) * | 2014-07-25 | 2016-03-03 | Dic株式会社 | α-ALUMINA FINE PARTICLE AND PRODUCTION METHOD OF THE SAME |
| CN105271331A (en) * | 2015-10-22 | 2016-01-27 | 中国海洋石油总公司 | Method for preparing pseudo-boehmite by taking waste silicon-aluminum molecular sieve as raw material |
| JP2019507087A (en) * | 2016-01-29 | 2019-03-14 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Method for producing alumina gel having high dispersibility and specific crystallite size |
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