JP2000256011A - Boehmite and its production - Google Patents
Boehmite and its productionInfo
- Publication number
- JP2000256011A JP2000256011A JP11063389A JP6338999A JP2000256011A JP 2000256011 A JP2000256011 A JP 2000256011A JP 11063389 A JP11063389 A JP 11063389A JP 6338999 A JP6338999 A JP 6338999A JP 2000256011 A JP2000256011 A JP 2000256011A
- Authority
- JP
- Japan
- Prior art keywords
- ammonium
- boehmite
- sulfate solution
- temperature
- hydrothermal treatment
- 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
- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 89
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 42
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 claims abstract description 42
- 229910001647 dawsonite Inorganic materials 0.000 claims abstract description 42
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 33
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 33
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 33
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 22
- 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 claims abstract description 20
- 238000010304 firing Methods 0.000 claims abstract description 19
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims description 51
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 17
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 19
- 230000000740 bleeding effect Effects 0.000 abstract description 16
- 239000011521 glass Substances 0.000 abstract description 16
- 230000002265 prevention Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 239000012535 impurity Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000003082 abrasive agent Substances 0.000 description 14
- 238000010292 electrical insulation Methods 0.000 description 14
- 238000007796 conventional method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum alkoxide Chemical class 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 101150000715 DA18 gene Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は制御されたＢＥＴ比
表面積、及び、結晶子径を有す高純度ベーマイト、及
び、その製造方法に関するものであり、特に、記録紙の
インキ滲み防止、ガラス、金属表面の防曇、研磨材、合
成樹脂、塗料、ゴム等のフィラー、触媒担体等として用
いられるベーマイト、及び、その製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-purity boehmite having a controlled BET specific surface area and a crystallite diameter, and a method for producing the same. The present invention relates to an antifogging on a metal surface, a boehmite used as an abrasive, a filler such as a synthetic resin, a paint, a rubber, a catalyst carrier and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般にベーマイトは、ジブサイト、バイ
ヤライト等のアルミニウム３水和物を水熱処理すること
によって製造される。ジブサイトはアルミン酸ナトリウ
ムの加水分解等によって得られ、バイヤライトはアルミ
ン酸ナトリウムにＣＯ２を吹き込むこと等によって得ら
れる。このようにして製造されるベーマイト転換物質に
はＮａ等の不純物が残存しており、これらの水熱処理に
よって得られるベーマイトにもＮａ等の不純物が残存す
る。このため、電気用途には絶縁性の低下、触媒担体と
して使用する際には残留元素が触媒機能を低下せしめる
等の問題点が指摘されていた。2. Description of the Related Art Boehmite is generally produced by hydrothermally treating aluminum trihydrate such as gibbsite and bayerite. Gibbsite is obtained by hydrolysis of sodium aluminate or the like, and bayerite is obtained by blowing CO 2 into sodium aluminate or the like. Impurities such as Na remain in the boehmite conversion material thus produced, and impurities such as Na remain in the boehmite obtained by the hydrothermal treatment. For this reason, problems have been pointed out, such as a decrease in insulating properties for electric applications, and a decrease in catalytic function due to residual elements when used as a catalyst carrier.
【０００３】高純度のベーマイトを製造する方法とし
て、中和分解法の洗浄工程で硝酸アンモニウム、炭酸水
素アンモニウム、界面活性剤、高分子のいずれか１つ以
上を添加する方法（特開平８−２６８７１５）が提示さ
れている。これらの添加物は、得られたベーマイトを焼
成処理し、触媒担体等とする過程では飛散するが、ベー
マイト自体の中には不純物として残存し、ベーマイトの
特性を利用する用途には適さない。As a method for producing high-purity boehmite, a method of adding at least one of ammonium nitrate, ammonium hydrogen carbonate, a surfactant, and a polymer in a washing step of a neutralization decomposition method (Japanese Patent Laid-Open No. Hei 8-268715). Is presented. These additives are scattered in the process of calcining the obtained boehmite to form a catalyst support or the like, but remain as impurities in the boehmite itself and are not suitable for applications utilizing the properties of boehmite.
【０００４】水熱処理には通常２００℃以上の温度が必
要とされており、工業的規模で経済的有利にベーマイト
を製造するためには、水熱処理の温度を低減する方法が
要望されている。水熱処理温度を低下する方法として、
カルシウム化合物の存在下で水熱処理を行う方法（特公
平４−５７６１１）等が知られているが、これらの方法
で得られるベーマイト中には不純物としてＣａやＮａが
多く残存するという難点を有している。[0004] Hydrothermal treatment usually requires a temperature of 200 ° C or higher, and in order to produce boehmite on an industrial scale economically and advantageously, there is a demand for a method of reducing the temperature of hydrothermal treatment. As a method of lowering the hydrothermal treatment temperature,
A method of performing a hydrothermal treatment in the presence of a calcium compound (Japanese Patent Publication No. 4-57611) is known, but it has a drawback that a large amount of Ca and Na remain as impurities in boehmite obtained by these methods. ing.
【０００５】記録紙のインキ滲み防止、研磨材、触媒担
体等としてベーマイトを使用する際には、ベーマイトの
結晶性が制御されていることが重要である。結晶性の制
御されたベーマイトを製造する方法として、アルミニウ
ムアルコキシドに対して有機溶媒、反応性を低下せしめ
る化合物を添加して加水分解する方法（特開平７−２６
７６３３）、水中に分散させた水酸化アルミニウムをマ
レイン酸、リンゴ酸の存在下に加熱加圧処理する方法
（特開平２−２３９１１３）、中和分解法においてＣｅ
塩、Ｔｉ塩、Ｓｉ塩を添加した出発原料を用いる方法
（特開平８−２６８７１６）、アルミニウム塩水溶液と
アルミン酸アルカリ水溶液を制御された温度、ｐＨで混
合し、得られた沈殿を制御された温度、ｐＨで熟成し、
乾燥して製造する方法（特開平１０−１０９０３０）等
が知られている。しかし、これらの方法は操作が複雑で
あったり、有機物を含む廃水を発生しその処理に費用と
技術を要する等の問題点を有している。また、上記方法
で得られた結晶性の制御されたベーマイトはその製造過
程において各種の物質が添加されているため、高純度で
なく、用途により問題を有する。[0005] When boehmite is used as an ink bleeding preventive for a recording paper, an abrasive, a catalyst carrier or the like, it is important that the crystallinity of the boehmite is controlled. As a method for producing boehmite with controlled crystallinity, a method of adding an organic solvent and a compound that reduces the reactivity to aluminum alkoxide and hydrolyzing the aluminum alkoxide (JP-A-7-26)
7633), a method in which aluminum hydroxide dispersed in water is heated and pressurized in the presence of maleic acid and malic acid (JP-A-2-239113).
A method using a starting material to which a salt, a Ti salt, and a Si salt are added (Japanese Patent Application Laid-Open No. 8-268716), a method in which an aqueous solution of an aluminum salt and an aqueous solution of an alkali aluminate are mixed at a controlled temperature and pH, and the resulting precipitate is controlled. Aged at temperature and pH,
A method of manufacturing by drying (JP-A-10-109030) and the like are known. However, these methods have problems such as complicated operations, generation of wastewater containing organic matter, and cost and technology for the treatment. Further, the boehmite with controlled crystallinity obtained by the above method is not high-purity because various substances are added in the production process, and thus has a problem depending on the application.
【０００６】[0006]
【発明が解決しようとする課題】かかる事情下に鑑み、
本発明者は高純度の結晶性の制御されたベーマイト及び
その製造方法を見出すことを目的として鋭意検討した結
果、アンモニウムドーソナイトを水熱処理、焼成、焼成
後水熱処理することによって、上記目的を全て満足する
ことを見出し、本発明を完成するに至った。In view of such circumstances,
The present inventors have conducted intensive studies with the aim of finding a high-purity crystalline controlled boehmite and a method for producing the same, and found that ammonium dawsonite was hydrothermally treated, calcined, and hydrothermally treated after calcining. They have found that they are all satisfied, and have completed the present invention.
【０００７】[0007]
【課題を解決するための手段】本発明の第１発明は、硫
酸アルミニウムアンモニウム溶液、又は、硫酸アルミニ
ウム溶液と重炭酸アンモニウム溶液との反応で得られる
アンモニウムドーソナイトを９０℃以上の温度で水熱処
理することによって製造されたＢＥＴ比表面積１００〜
２７０ｍ２／ｇ、Ｘ線回折図形の（０２０）ピークより
求めた結晶子径が２０〜９０Åであるベーマイトであ
る。本発明の第４発明は、硫酸アルミニウムアンモニウ
ム溶液、又は、硫酸アルミニウム溶液と重炭酸アンモニ
ウム溶液との反応で得られるアンモニウムドーソナイト
を９０℃以上の温度で水熱処理することによるベーマイ
トの製造方法である。According to a first aspect of the present invention, an aluminum ammonium sulfate solution or an ammonium dawsonite obtained by a reaction between an aluminum sulfate solution and an ammonium bicarbonate solution are treated with water at a temperature of 90 ° C. or more. BET specific surface area 100-
It is a boehmite having a crystallite diameter of 270 m 2 / g and a crystallite diameter of 20 to 90 ° determined from the (020) peak of the X-ray diffraction pattern. The fourth invention of the present invention relates to a method for producing boehmite by hydrothermally treating an ammonium ammonium sulfate solution or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution at a temperature of 90 ° C. or higher. is there.
【０００８】本発明の第１発明、及び、第４発明に用い
るアンモニウムドーソナイトは、硫酸アルミニウムアン
モニウム溶液、又は、硫酸アルミニウム溶液と重炭酸ア
ンモニウム溶液との反応で得られたものであり、製造条
件は特に規定されたものでない。水熱処理は、アンモニ
ウムドーソナイトを水に解膠してスラリーとした状態で
行われる。スラリー濃度は１〜５重量％とするのが好ま
しいが、特に規定するものではない。水熱処理温度を９
０℃以上と限定する理由は、９０℃未満ではベーマイト
を得ることができないためである。水熱処理温度の上限
は特に規定されないが、装置の大型化による設備費の増
大とエネルギーコストの観点から好ましくは２５０℃以
下がよい。水熱処理後、常法に従って、濾過、水洗、乾
燥を行って、ＢＥＴ比表面積１００〜２７０ｍ２／ｇ、
Ｘ線回折図形の（０２０）ピークより求めた結晶子径が
２０〜９０Åであるベーマイトを得ることができる。得
られたベーマイトはＮＨ３以外の不純物を殆ど含有せ
ず、例えば、Ｎａ含有量は１０ｐｐｍ以下であり、触媒
担体、電気絶縁性が要求される用途に好適である。更
に、結晶性が制御されているため、記録紙のインキ滲み
防止、研磨材、ガラス、金属表面の防曇用途に好適であ
る。The ammonium dawsonite used in the first invention and the fourth invention of the present invention is obtained by reacting an aluminum ammonium sulfate solution or an aluminum sulfate solution with an ammonium bicarbonate solution. The conditions are not specified. The hydrothermal treatment is performed in a state where ammonium dawsonite is pulverized into water to form a slurry. The slurry concentration is preferably 1 to 5% by weight, but is not particularly limited. Hydrothermal treatment temperature 9
The reason for limiting the temperature to 0 ° C. or higher is that boehmite cannot be obtained at a temperature lower than 90 ° C. Although the upper limit of the hydrothermal treatment temperature is not particularly limited, it is preferably 250 ° C. or less from the viewpoint of increase in equipment cost due to enlargement of the apparatus and energy cost. After the hydrothermal treatment, filtration, washing with water, and drying are performed according to a conventional method to obtain a BET specific surface area of 100 to 270 m 2 / g,
Boehmite having a crystallite diameter of 20 to 90 ° determined from the (020) peak of the X-ray diffraction pattern can be obtained. The obtained boehmite contains almost no impurities other than NH 3 , and has, for example, a Na content of 10 ppm or less, and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【０００９】本発明の第２発明は、硫酸アルミニウムア
ンモニウム溶液、又は、硫酸アルミニウム溶液と重炭酸
アンモニウム溶液との反応で得られるアンモニウムドー
ソナイトを３００〜４５０℃の温度範囲で焼成すること
によって製造されたＢＥＴ比表面積３７０〜４８０ｍ２
／ｇ、Ｘ線回折図形の（０２０）ピークより求めた結晶
子径が３０〜５０Åであるベーマイトである。本発明の
第５発明は、硫酸アルミニウムアンモニウム溶液、又
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを３００〜
４５０℃の温度範囲で焼成することによるベーマイトの
製造方法である。[0009] The second invention of the present invention is to produce an aluminum ammonium sulfate solution or an ammonium dawsonite obtained by a reaction between an aluminum sulfate solution and an ammonium bicarbonate solution, by calcination in a temperature range of 300 to 450 ° C. BET specific surface area 370-480 m 2
/ G, a boehmite having a crystallite diameter of 30 to 50 ° determined from the (020) peak of the X-ray diffraction pattern. The fifth invention of the present invention relates to an aluminum ammonium sulfate solution, or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution, in an amount of 300 to 300 nm.
This is a method for producing boehmite by firing in a temperature range of 450 ° C.
【００１０】本発明の第２発明、及び、第５発明に用い
るアンモニウムドーソナイトは、硫酸アルミニウムアン
モニウム溶液、又は、硫酸アルミニウム溶液と重炭酸ア
ンモニウム溶液との反応で得られたものであり、製造条
件は特に規定されたものでない。焼成は、温度調節機能
を有する炉で行われる。焼成温度を３００〜４５０℃に
限定する理由は、３００℃未満ではアンモニウムドーソ
ナイトからベーマイトへの転換が不十分のためであり、
４５０℃を越える温度では、ベーマイト相が出現せず、
γ−アルミナ相に変化するためである。焼成時間は特に
限定されないが、２〜１２時間が好ましい。焼成後、Ｂ
ＥＴ比表面積３７０〜４８０ｍ２／ｇ、Ｘ線回折図形の
（０２０）ピークより求めた結晶子径が３０〜５０Åで
あるベーマイトを得ることができる。得られたベーマイ
トは不純物を殆ど含有せず、例えば、Ｎａ含有量は１０
ｐｐｍ以下であり、触媒担体、電気絶縁性が要求される
用途に好適である。更に、結晶性が制御されているた
め、記録紙のインキ滲み防止、研磨材、ガラス、金属表
面の防曇用途に好適である。The ammonium dawsonite used in the second and fifth aspects of the present invention is obtained by reacting an aluminum ammonium sulfate solution or an aluminum sulfate solution with an ammonium bicarbonate solution. The conditions are not specified. The firing is performed in a furnace having a temperature control function. The reason for limiting the firing temperature to 300 to 450 ° C. is that if the temperature is lower than 300 ° C., the conversion from ammonium dawsonite to boehmite is insufficient.
At a temperature exceeding 450 ° C., no boehmite phase appears,
This is because it changes to a γ-alumina phase. The firing time is not particularly limited, but is preferably 2 to 12 hours. After firing, B
Boehmite having an ET specific surface area of 370 to 480 m 2 / g and a crystallite diameter of 30 to 50 ° determined from the (020) peak of the X-ray diffraction pattern can be obtained. The obtained boehmite contains almost no impurities, for example, a Na content of 10
ppm or less, which is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００１１】本発明の第３発明は、硫酸アルミニウムア
ンモニウム溶液、又は、硫酸アルミニウム溶液と重炭酸
アンモニウム溶液との反応で得られるアンモニウムドー
ソナイトを３００〜１１００℃の温度範囲で焼成し、そ
の後、２５℃以上の温度で水熱処理することによって製
造されたＢＥＴ比表面積２０〜３６０ｍ２／ｇ、Ｘ線回
折図形の（０２０）ピークより求めた結晶子径が２０〜
３４０Åであるベーマイトである。本発明の第６発明
は、硫酸アルミニウムアンモニウム溶液、又は、硫酸ア
ルミニウム溶液と重炭酸アンモニウム溶液との反応で得
られるアンモニウムドーソナイトを３００〜１１００℃
の温度範囲で焼成し、その後、２５℃以上の温度で水熱
処理することによるベーマイトの製造方法である。[0011] The third invention of the present invention is to sinter an ammonium ammonium sulfate solution or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution in a temperature range of 300 to 1100 ° C, The BET specific surface area produced by hydrothermal treatment at a temperature of 25 ° C. or more is 20 to 360 m 2 / g, and the crystallite diameter determined from the (020) peak in the X-ray diffraction pattern is 20 to 360.
Boehmite is 340 あ る. The sixth invention of the present invention relates to an aluminum ammonium sulfate solution or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution at 300 to 1100 ° C.
And then a hydrothermal treatment at a temperature of 25 ° C. or higher.
【００１２】本発明の第３発明、及び、第６発明に用い
るアンモニウムドーソナイトは、硫酸アルミニウムアン
モニウム溶液、又は、硫酸アルミニウム溶液と重炭酸ア
ンモニウム溶液との反応で得られたものであり、製造条
件は特に規定されたものでない。焼成は、温度調節機能
を有する炉で行われる。焼成温度を３００〜１１００℃
に限定する理由は、３００℃未満ではアンモニウムドー
ソナイトの分解が不十分であり、水熱処理後に製造され
るベーマイト中に不純物としてＮＨ３が含有される可能
性があるからである。また、１１００℃を越える温度で
は、水熱処理後にベーマイトに転換し得ないα−アルミ
ナ相が出現するためである。水熱処理の方法は温度条件
を除いて特に限定するものではない。焼成物を水に解膠
しスラリー状となし、解放、または、密閉容器中で水熱
処理する方法。焼成物をドライの状態で、水蒸気の発生
している解放、または、密閉容器中に保持し水熱処理す
る方法。焼成物に少量の水を含浸させ、解放、または、
密閉容器中に保持し水熱処理する方法等があげられる。
水熱処理温度を２５℃以上と限定する理由は、２５℃未
満ではベーマイトを得ることができないためであり、ま
た、焼成だけでベーマイト相が出現した場合であって
も、これ以上のベーマイトの結晶性の増大が望めないた
めである。水熱処理温度の下限は好ましくは８０℃であ
る。水熱処理温度の上限は特に規定されないが、装置の
大型化による設備費の増大とエネルギーコストの観点か
ら好ましくは２５０℃以下がよい。水熱処理後、必要に
応じて濾過後、乾燥を行って、ＢＥＴ比表面積２０〜３
６０ｍ２／ｇ、Ｘ線回折図形の（０２０）ピークより求
めた結晶子径が２０〜３４０Åであるベーマイトを得る
ことができる。得られたベーマイトは不純物を殆ど含有
せず、例えば、Ｎａ含有量は１０ｐｐｍ以下であり、触
媒担体、電気絶縁性が要求される用途に好適である。更
に、結晶性が制御されているため、記録紙のインキ滲み
防止、研磨材、ガラス、金属表面の防曇用途に好適であ
る。The ammonium dawsonite used in the third and sixth aspects of the present invention is obtained by reacting an aluminum ammonium sulfate solution or an aluminum sulfate solution with an ammonium bicarbonate solution. The conditions are not specified. The firing is performed in a furnace having a temperature control function. Firing temperature 300 ~ 1100 ℃
The reason is that ammonium dawsonite is insufficiently decomposed at a temperature lower than 300 ° C., and NH 3 may be contained as an impurity in boehmite produced after the hydrothermal treatment. At a temperature exceeding 1100 ° C., an α-alumina phase which cannot be converted to boehmite after hydrothermal treatment appears. The method of hydrothermal treatment is not particularly limited except for the temperature conditions. A method in which a fired product is peptized in water to form a slurry, released, or subjected to hydrothermal treatment in a closed container. A method in which the fired product is released in a dry state in which steam is generated, or is subjected to hydrothermal treatment in a closed container. Impregnate the calcined product with a small amount of water and release, or
A method of holding in a closed container and performing a hydrothermal treatment may be used.
The reason why the hydrothermal treatment temperature is limited to 25 ° C. or higher is that boehmite cannot be obtained at a temperature lower than 25 ° C. Further, even when a boehmite phase appears only by firing, the boehmite crystallinity is higher than that. This is because it is not possible to expect an increase. The lower limit of the hydrothermal treatment temperature is preferably 80 ° C. Although the upper limit of the hydrothermal treatment temperature is not particularly limited, it is preferably 250 ° C. or less from the viewpoint of increase in equipment cost due to enlargement of the apparatus and energy cost. After hydrothermal treatment, if necessary, after filtration, drying is performed to obtain a BET specific surface area of 20 to 3
Boehmite having a crystallite size of 20 to 340 ° obtained from the (020) peak of the X-ray diffraction pattern at 60 m 2 / g can be obtained. The obtained boehmite contains almost no impurities, and has, for example, a Na content of 10 ppm or less, and is suitable for a catalyst carrier and an application requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００１３】[0013]
【発明の実施の形態】以下に実施例を挙げて、更に本発
明を具体的に説明するが本発明はその要旨を越えない限
り、下記実施例によって限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
【００１４】（実施例１）容量５００ｍｌのビーカーに
硫酸アルミニウムアンモニウム溶液と重炭酸アンモニウ
ム溶液との反応で得られたアンモニウムドーソナイト２
０ｇと水４００ｇを採り、スラリーとした後、表１に示
す条件で水熱処理を行った。水熱処理後、常法に従っ
て、濾過、水洗し、１００℃で５時間乾燥を行った。得
られた生成物は表１に示すＢＥＴ比表面積とＸ線回折図
形の（０２０）ピークより求めた結晶子径を有するベー
マイトであった。また、このベーマイトの純度は表１の
通りであった。得られたベーマイトは不純物を殆ど含有
せず、触媒担体、電気絶縁性が要求される用途に好適で
ある。更に、結晶性が制御されているため、記録紙のイ
ンキ滲み防止、研磨材、ガラス、金属表面の防曇用途に
好適である。Example 1 In a beaker having a capacity of 500 ml, ammonium dawsonite 2 obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was used.
After taking 0 g and 400 g of water to obtain a slurry, hydrothermal treatment was performed under the conditions shown in Table 1. After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method. The obtained product was boehmite having a BET specific surface area shown in Table 1 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. The purity of the boehmite was as shown in Table 1. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００１５】（実施例２〜３）容量１００ｍｌのテフロ
ン製オートクレーブに硫酸アルミニウムアンモニウム溶
液と重炭酸アンモニウム溶液との反応で得られたアンモ
ニウムドーソナイト７ｇと水７０ｇを採り、表１に示す
条件で水熱処理を行った。水熱処理後、常法に従って、
濾過、水洗し、１００℃で５時間乾燥を行った。得られ
た生成物は表１に示すＢＥＴ比表面積とＸ線回折図形の
（０２０）ピークより求めた結晶子径を有するベーマイ
トであった。また、このベーマイトの純度は表１の通り
であった。得られたベーマイトは不純物を殆ど含有せ
ず、触媒担体、電気絶縁性が要求される用途に好適であ
る。更に、結晶性が制御されているため、記録紙のイン
キ滲み防止、研磨材、ガラス、金属表面の防曇用途に好
適である。(Examples 2 to 3) In a Teflon-made autoclave having a capacity of 100 ml, 7 g of ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution and 70 g of water were taken and subjected to the conditions shown in Table 1. Hydrothermal treatment was performed. After hydrothermal treatment,
The mixture was filtered, washed with water, and dried at 100 ° C. for 5 hours. The obtained product was boehmite having a BET specific surface area shown in Table 1 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. The purity of the boehmite was as shown in Table 1. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００１６】（比較例１〜２）容量５００ｍｌのビーカ
ーに硫酸アルミニウムアンモニウム溶液と重炭酸アンモ
ニウム溶液との反応で得られたアンモニウムドーソナイ
ト２０ｇと水４００ｇを採り、表１に示す条件で水熱処
理を行った。水熱処理後、常法に従って、濾過、水洗
し、１００℃で５時間乾燥を行った。得られた生成物は
アンモニウムドーソナイトであり、ベーマイト相は確認
されなかった。Comparative Examples 1-2 In a beaker having a capacity of 500 ml, 20 g of ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution and 400 g of water were taken and subjected to hydrothermal treatment under the conditions shown in Table 1. Was done. After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method. The obtained product was ammonium dawsonite, and no boehmite phase was observed.
【００１７】[0017]
【表１】 [Table 1]
【００１８】（実施例４〜７）硫酸アルミニウムアンモ
ニウム溶液と重炭酸アンモニウム溶液との反応で得られ
たアンモニウムドーソナイトを内容積１８００ｍｌのア
ルミナ製容器に詰め、温度調節機能を有する電気炉で、
表２に示す条件で焼成した。得られた焼成物は表２に示
すＢＥＴ比表面積とＸ線回折図形の（０２０）ピークよ
り求めた結晶子径を有するベーマイトであった。また、
このベーマイトの純度は表２の通りであった。得られた
ベーマイトは不純物を殆ど含有せず、触媒担体、電気絶
縁性が要求される用途に好適である。更に、結晶性が制
御されているため、記録紙のインキ滲み防止、研磨材、
ガラス、金属表面の防曇用途に好適である。(Examples 4 to 7) Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function.
It was fired under the conditions shown in Table 2. The fired product obtained was boehmite having a BET specific surface area shown in Table 2 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. Also,
The purity of the boehmite was as shown in Table 2. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, the prevention of ink bleeding of the recording paper, the abrasive,
Suitable for anti-fog use on glass and metal surfaces.
【００１９】（比較例３）硫酸アルミニウムアンモニウ
ム溶液と重炭酸アンモニウム溶液との反応で得られたア
ンモニウムドーソナイトを内容積１８００ｍｌのアルミ
ナ製容器に詰め、温度調節機能を有する電気炉で、表２
に示す条件で焼成した。得られた焼成物はアンモニウム
ドーソナイトであり、ベーマイト相は確認されなかっ
た。Comparative Example 3 Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml.
It baked on conditions shown in. The obtained fired product was ammonium dawsonite, and no boehmite phase was confirmed.
【００２０】（比較例４）硫酸アルミニウムアンモニウ
ム溶液と重炭酸アンモニウム溶液との反応で得られたア
ンモニウムドーソナイトを内容積１８００ｍｌのアルミ
ナ製容器に詰め、温度調節機能を有する電気炉で、表２
に示す条件で焼成した。得られた焼成物はγ−アルミナ
であり、ベーマイト相は確認されなかった。Comparative Example 4 Ammonium dawsonite obtained by the reaction between an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function.
It baked on conditions shown in. The obtained fired product was γ-alumina, and no boehmite phase was confirmed.
【００２１】[0021]
【表２】 [Table 2]
【００２２】（実施例８）硫酸アルミニウムアンモニウ
ム溶液と重炭酸アンモニウム溶液との反応で得られたア
ンモニウムドーソナイトを内容積１８００ｍｌのアルミ
ナ製容器に詰め、温度調節機能を有する電気炉で、３０
０〜１１００℃の範囲の任意温度で２時間焼成した。次
いで、得られた焼成物７ｇと水７０ｇを、容量１００ｍ
ｌのテフロン製オートクレーブに採り、１５０℃で６時
間水熱処理を行った。水熱処理後、常法に従って、濾
過、水洗し、１００℃で５時間乾燥を行った。得られた
生成物は、ＢＥＴ比表面積２０〜３６０ｍ２／ｇ、Ｘ線
回折図形の（０２０）ピークより求めた結晶子径が２０
〜３４０Åであるベーマイトであった。焼成温度とＢＥ
Ｔ比表面積の関係を図１に示す。また、焼成温度とＸ線
回折図形の（０２０）ピークより求めた結晶子径の関係
を図２示す。図１及び図２から、生成されるベーマイト
はアンモニウムドーソナイトの焼成温度によってそのＢ
ＥＴ比表面積とＸ線回折図形の（０２０）ピークより求
めた結晶子径を任意に制御できることがわかる。また、
ベーマイト中のＮａ含有量は１０ｐｐｍ以下であった。
得られたベーマイトは不純物を殆ど含有せず、触媒担
体、電気絶縁性が要求される用途に好適である。更に、
結晶性が制御されているため、記録紙のインキ滲み防
止、研磨材、ガラス、金属表面の防曇用途に好適であ
る。Example 8 Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function for 30 minutes.
It was baked at an arbitrary temperature in the range of 0 to 1100 ° C. for 2 hours. Next, 7 g of the obtained fired product and 70 g of water were put into a 100 m capacity.
1 Teflon-made autoclave and subjected to hydrothermal treatment at 150 ° C. for 6 hours. After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method. The obtained product had a BET specific surface area of 20 to 360 m 2 / g and a crystallite diameter of 20 determined from the (020) peak of the X-ray diffraction pattern.
It was boehmite which was ~ 340 °. Firing temperature and BE
FIG. 1 shows the relationship between the T specific surface areas. FIG. 2 shows the relationship between the firing temperature and the crystallite diameter obtained from the (020) peak of the X-ray diffraction pattern. From FIG. 1 and FIG. 2, the boehmite produced depends on the calcination temperature of ammonium dawsonite.
It can be seen that the crystallite diameter determined from the ET specific surface area and the (020) peak of the X-ray diffraction pattern can be arbitrarily controlled. Also,
The Na content in the boehmite was 10 ppm or less.
The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Furthermore,
Since the crystallinity is controlled, it is suitable for use in preventing ink bleeding of recording paper, antifogging on abrasives, glass, and metal surfaces.
【００２３】（実施例９〜１２）硫酸アルミニウムアン
モニウム溶液と重炭酸アンモニウム溶液との反応で得ら
れたアンモニウムドーソナイトを内容積１８００ｍｌの
アルミナ製容器に詰め、温度調節機能を有する電気炉
で、表３に示す条件で焼成した。次いで、得られた焼成
物２０ｇと水４００ｇを採り、スラリーとした後、表３
に示す条件で水熱処理を行った。水熱処理後、常法に従
って、濾過、水洗し、１００℃で５時間乾燥を行った。
得られた生成物は表３に示すＢＥＴ比表面積とＸ線回折
図形の（０２０）ピークより求めた結晶子径を有するベ
ーマイトであった。また、このベーマイトの純度は表３
の通りであった。得られたベーマイトは不純物を殆ど含
有せず、触媒担体、電気絶縁性が要求される用途に好適
である。更に、結晶性が制御されているため、研磨材、
記録紙のインキ滲み防止、ガラス、金属表面の防曇用途
に好適である。(Examples 9 to 12) Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function. It was fired under the conditions shown in Table 3. Next, 20 g of the obtained baked product and 400 g of water were taken to obtain a slurry.
The hydrothermal treatment was performed under the conditions shown in (1). After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method.
The obtained product was boehmite having a BET specific surface area shown in Table 3 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. Table 3 shows the purity of this boehmite.
It was as follows. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Furthermore, since the crystallinity is controlled, abrasives,
It is suitable for prevention of ink bleeding of recording paper and for antifogging of glass and metal surfaces.
【００２４】（実施例１３〜１５）硫酸アルミニウムア
ンモニウム溶液と重炭酸アンモニウム溶液との反応で得
られたアンモニウムドーソナイトを内容積１８００ｍｌ
のアルミナ製容器に詰め、温度調節機能を有する電気炉
で、表３に示す条件で焼成した。次いで、得られた焼成
物７ｇと水７０ｇを、容量１００ｍｌのテフロン製オー
トクレーブに採り、表３に示す条件で水熱処理を行っ
た。水熱処理後、常法に従って、濾過、水洗し、１５０
℃で５時間乾燥を行った。得られた生成物は表３に示す
ＢＥＴ比表面積とＸ線回折図形の（０２０）ピークより
求めた結晶子径を有するベーマイトであった。また、こ
のベーマイトの純度は表３の通りであった。得られたベ
ーマイトは不純物を殆ど含有せず、触媒担体、電気絶縁
性が要求される用途に好適である。更に、結晶性が制御
されているため、記録紙のインキ滲み防止、研磨材、ガ
ラス、金属表面の防曇用途に好適である。(Examples 13 to 15) An ammonium dawsonite obtained by a reaction between an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was charged with an internal volume of 1800 ml.
And baked in an electric furnace having a temperature control function under the conditions shown in Table 3. Next, 7 g of the obtained fired product and 70 g of water were placed in a Teflon-made autoclave having a capacity of 100 ml, and subjected to hydrothermal treatment under the conditions shown in Table 3. After the hydrothermal treatment, filtration and washing with water are performed according to a conventional method.
Drying was performed at 5 ° C. for 5 hours. The obtained product was boehmite having a BET specific surface area shown in Table 3 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. The purity of the boehmite was as shown in Table 3. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００２５】（実施例１６）硫酸アルミニウムアンモニ
ウム溶液と重炭酸アンモニウム溶液との反応で得られた
アンモニウムドーソナイトを内容積１８００ｍｌのアル
ミナ製容器に詰め、温度調節機能を有する電気炉で、表
３に示す条件で焼成した。次いで、得られた焼成物２０
ｇを解放容器中の沸騰水から発生している１００℃の水
蒸気中に３時間保持し、水熱処理を行った。水熱処理
後、１５０℃で５時間乾燥を行った。得られた生成物は
表３に示すＢＥＴ比表面積とＸ線回折図形の（０２０）
ピークより求めた結晶子径を有するベーマイトであっ
た。また、このベーマイトの純度は表３の通りであっ
た。得られたベーマイトは不純物を殆ど含有せず、触媒
担体、電気絶縁性が要求される用途に好適である。更
に、結晶性が制御されているため、記録紙のインキ滲み
防止、研磨材、ガラス、金属表面の防曇用途に好適であ
る。Example 16 Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function. It baked on conditions shown in. Next, the obtained fired product 20
g was held in steam at 100 ° C. generated from boiling water in the open container for 3 hours to perform hydrothermal treatment. After the hydrothermal treatment, drying was performed at 150 ° C. for 5 hours. The obtained product had a BET specific surface area and an X-ray diffraction pattern (020) shown in Table 3.
It was a boehmite having a crystallite diameter determined from the peak. The purity of the boehmite was as shown in Table 3. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００２６】（実施例１７）硫酸アルミニウム溶液と重
炭酸アンモニウム溶液との反応で得られたアンモニウム
ドーソナイトを内容積１８００ｍｌのアルミナ製容器に
詰め、温度調節機能を有する電気炉で、表３に示す条件
で焼成した。次いで、得られた焼成物１０ｇを底部に水
１０ｇを入れた容量１００ｍｌのテフロン製オートクレ
ーブに水と接しないように入れ、１５０℃で６時間水熱
処理を行った。水熱処理後、１５０℃で５時間乾燥を行
った。得られた生成物は表３に示すＢＥＴ比表面積とＸ
線回折図形の（０２０）ピークより求めた結晶子径を有
するベーマイトであった。また、このベーマイトの純度
は表３の通りであった。得られたベーマイトは不純物を
殆ど含有せず、触媒担体、電気絶縁性が要求される用途
に好適である。更に、結晶性が制御されているため、記
録紙のインキ滲み防止、研磨材、ガラス、金属表面の防
曇用途に好適である。Example 17 Ammonium dawsonite obtained by a reaction between an aluminum sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function. It baked on the conditions shown. Next, 10 g of the obtained calcined product was placed in a Teflon-made autoclave having a capacity of 100 g at the bottom and containing 10 g of water so as not to come in contact with water, and subjected to hydrothermal treatment at 150 ° C. for 6 hours. After the hydrothermal treatment, drying was performed at 150 ° C. for 5 hours. The obtained product had a BET specific surface area and X shown in Table 3.
It was a boehmite having a crystallite diameter determined from the (020) peak in the line diffraction pattern. The purity of the boehmite was as shown in Table 3. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing bleeding of ink on recording paper and for defogging abrasives, glass, and metal surfaces.
【００２７】（実施例１８）硫酸アルミニウム溶液と重
炭酸アンモニウム溶液との反応で得られたアンモニウム
ドーソナイトを内容積１８００ｍｌのアルミナ製容器に
詰め、温度調節機能を有する電気炉で、表３に示す条件
で焼成した。次いで、得られた焼成物２００ｇに水８０
０ｇを添加し混練りした物を、容量１０００ｍｌのガラ
ス製オートクレーブに入れ１５０℃で６時間水熱処理を
行った。水熱処理後、１５０℃で５時間乾燥を行った。
得られた生成物は表３に示すＢＥＴ比表面積とＸ線回折
図形の（０２０）ピークより求めた結晶子径を有するベ
ーマイトであった。また、このベーマイトの純度は表３
の通りであった。得られたベーマイトは不純物を殆ど含
有せず、触媒担体、電気絶縁性が要求される用途に好適
である。更に、結晶性が制御されているため、記録紙の
インキ滲み防止、研磨材、ガラス、金属表面の防曇用
途、研磨材に好適である。(Example 18) Ammonium dawsonite obtained by the reaction of an aluminum sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml. It baked on the conditions shown. Next, water 80 was added to 200 g of the obtained fired product.
The mixture obtained by adding 0 g and kneading was placed in a glass autoclave having a capacity of 1000 ml and subjected to a hydrothermal treatment at 150 ° C. for 6 hours. After the hydrothermal treatment, drying was performed at 150 ° C. for 5 hours.
The obtained product was boehmite having a BET specific surface area shown in Table 3 and a crystallite diameter determined from the (020) peak of the X-ray diffraction pattern. Table 3 shows the purity of this boehmite.
It was as follows. The obtained boehmite contains almost no impurities and is suitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, since the crystallinity is controlled, it is suitable for use in preventing ink bleeding of recording paper, antifogging for abrasives, glass and metal surfaces, and abrasives.
【００２８】（比較例５）硫酸アルミニウムアンモニウ
ム溶液と重炭酸アンモニウム溶液との反応で得られたア
ンモニウムドーソナイトを内容積１８００ｍｌのアルミ
ナ製容器に詰め、温度調節機能を有する電気炉で２５０
℃で２時間焼成した。次いで、得られた焼成物７ｇと水
７０ｇを、容量１００ｍｌのテフロン製オートクレーブ
に採り、表３に示す条件で水熱処理を行った。水熱処理
後、常法に従って、濾過、水洗し、１００℃で５時間乾
燥を行った。得られた生成物にはベーマイト相の他にア
ンモニウムドーソナイト相が確認された。(Comparative Example 5) Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml and placed in an electric furnace having a temperature control function for 250 minutes.
Calcination was performed at 2 ° C. for 2 hours. Next, 7 g of the obtained fired product and 70 g of water were placed in a Teflon-made autoclave having a capacity of 100 ml, and subjected to hydrothermal treatment under the conditions shown in Table 3. After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method. An ammonium dawsonite phase was confirmed in the obtained product in addition to the boehmite phase.
【００２９】（比較例６）硫酸アルミニウムアンモニウ
ム溶液と重炭酸アンモニウム溶液との反応で得られたア
ンモニウムドーソナイトを内容積１８００ｍｌのアルミ
ナ製容器に詰め、温度調節機能を有する電気炉で１１５
０℃で２時間焼成した。次いで、得られた焼成物７ｇと
水７０ｇを、容量１００ｍｌのテフロン製オートクレー
ブに採り、表３に示す条件で水熱処理を行った。水熱処
理後、常法に従って、濾過、水洗し、１００℃で５時間
乾燥を行った。得られた生成物にはベーマイト相の他に
θ−アルミナ相、α−アルミナ相の存在が確認された。(Comparative Example 6) Ammonium dawsonite obtained by the reaction of an ammonium ammonium sulfate solution and an ammonium bicarbonate solution was packed in an alumina container having an internal volume of 1800 ml, and was placed in an electric furnace having a temperature control function.
It was baked at 0 ° C. for 2 hours. Next, 7 g of the obtained fired product and 70 g of water were placed in a Teflon-made autoclave having a capacity of 100 ml, and subjected to hydrothermal treatment under the conditions shown in Table 3. After the hydrothermal treatment, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours according to a conventional method. The obtained product was confirmed to have a θ-alumina phase and an α-alumina phase in addition to the boehmite phase.
【００３０】[0030]
【表３】 [Table 3]
【００３１】（比較例７〜９）容量１００ｍｌのテフロ
ン製オートクレーブにバイヤー法で製造された結晶形が
ギブサイトの水酸化アルミニウム７ｇと水７０ｇを採
り、表４に示す条件で水熱処理を行った。水熱処理後、
常法に従って、濾過、水洗し、１００℃で５時間乾燥を
行った。得られた生成物の結晶形、ＢＥＴ比表面積、ベ
ーマイトのＸ線回折図形の（０２０）ピークより求めた
結晶子径を表４に示す。また、このベーマイトの純度は
表４の通りであった。得られたベーマイトは多量の不純
物を含有し、触媒担体、電気絶縁性が要求される用途に
は不適である。更に、結晶子径は粗大であり、記録紙の
インキ滲み防止、研磨材、ガラス、金属表面の防曇の用
途には不適である。(Comparative Examples 7 to 9) In a Teflon autoclave having a capacity of 100 ml, 7 g of aluminum hydroxide having a gibbsite crystal form and 70 g of water produced by the Bayer method were taken and subjected to hydrothermal treatment under the conditions shown in Table 4. After hydrothermal treatment,
According to a conventional method, the resultant was filtered, washed with water, and dried at 100 ° C. for 5 hours. Table 4 shows the crystal form, BET specific surface area, and crystallite diameter of the obtained product obtained from the (020) peak of the X-ray diffraction pattern of boehmite. The purity of the boehmite was as shown in Table 4. The obtained boehmite contains a large amount of impurities, and is unsuitable for use as a catalyst carrier and for applications requiring electrical insulation. Further, the crystallite diameter is coarse, which is unsuitable for use in preventing bleeding of ink on recording paper, antifogging of abrasives, glass, and metal surfaces.
【００３２】[0032]
【表４】 [Table 4]
【００３３】[0033]
【発明の効果】本発明により、硫酸アルミニウムアンモ
ニウム溶液、又は、硫酸アルミニウム溶液と重炭酸アン
モニウム溶液との反応で得られるアンモニウムドーソナ
イトを使用して、ＢＥＴ比表面積、結晶子径で指標され
る結晶性の制御された高純度のベーマイトを容易に得る
ことができる。本発明で得られたベーマイトは、触媒担
体、電気絶縁性が要求される用途に好適である。更に、
結晶性が制御されているため、記録紙のインキ滲み防
止、研磨材、ガラス、金属表面の防曇の用途に好適であ
る。According to the present invention, the BET specific surface area and the crystallite diameter are indicated by using an ammonium ammonium sulfate solution or ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution. High-purity boehmite with controlled crystallinity can be easily obtained. The boehmite obtained by the present invention is suitable for a catalyst carrier and applications requiring electrical insulation. Furthermore,
Since the crystallinity is controlled, it is suitable for use in the prevention of ink bleeding of recording paper, the use of abrasives, glass, and metal surfaces to prevent fogging.
【図１】焼成温度とＢＥＴ比表面積の関係を示すグラフ
である。FIG. 1 is a graph showing a relationship between a firing temperature and a BET specific surface area.
【図２】焼成温度とＸ線解析図形の（０２０）ピークよ
り求めた結晶子径の関係を示すグラフである。FIG. 2 is a graph showing a relationship between a firing temperature and a crystallite diameter obtained from a (020) peak in an X-ray analysis pattern.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 3/18 Ｃ０４Ｂ 35/10 Ｂ // Ｂ０１Ｊ 21/04 Ｃ Ｆターム(参考） 4G030 AA36 BA12 BA19 BA34 CA04 GA27 4G069 AA01 AA08 AA09 BA01A BA01B BA01C EB18X EC03X EC22X FB05 FB10 FB30 FC02 FC07 4G076 AA02 AB08 AB10 AC02 BA12 BA43 BC07 BD02 CA26 CA28 CA33 CA36 DA01 DA02 DA18 DA30 FA08 4H020 AA01 AB02 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09K 3/18 C04B 35/10 B // B01J 21/04 C F-term (Reference) 4G030 AA36 BA12 BA19 BA34 CA04 GA27 4G069 AA01 AA08 AA09 BA01A BA01B BA01C EB18X EC03X EC22X FB05 FB10 FB30 FC02 FC07 4G076 AA02 AB08 AB10 AC02 BA12 BA43 BC07 BD02 CA26 CA28 CA33 CA36 DA01 DA02 DA18 DA30 FA08 4H020 AA01 AB02
Claims (12)
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを９０℃以
上の温度で水熱処理することによって製造されたＢＥＴ
比表面積１００〜２７０ｍ２／ｇ、Ｘ線回折図形の（０
２０）ピークより求めた結晶子径が２０〜９０Åである
ベーマイト。1. A BET manufactured by hydrothermally treating an ammonium ammonium sulfate solution or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution at a temperature of 90 ° C. or higher.
Specific surface area 100 to 270 m 2 / g, X-ray diffraction pattern (0
20) Boehmite having a crystallite diameter of 20 to 90 ° determined from the peak.
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを３００〜
４５０℃の温度範囲で焼成することによって製造された
ＢＥＴ比表面積３７０〜４８０ｍ２／ｇ、Ｘ線回折図形
の（０２０）ピークより求めた結晶子径が３０〜５０Å
であるベーマイト。2. An ammonium aluminum sulfate solution, or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution, is used in an amount of 300 to 300.
A BET specific surface area of 370 to 480 m 2 / g produced by firing in a temperature range of 450 ° C., and a crystallite diameter of 30 to 50 ° determined from a (020) peak in an X-ray diffraction pattern.
Boehmite.
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを３００〜
１１００℃の温度範囲で焼成し、その後、２５℃以上の
温度で水熱処理することによって製造されたＢＥＴ比表
面積２０〜３６０ｍ２／ｇ、Ｘ線回折図形の（０２０）
ピークより求めた結晶子径が２０〜３４０Åであるベー
マイト。3. An aluminum ammonium sulfate solution, or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution, is used in an amount of 300 to 300.
Baking at a temperature range of 1100 ° C., followed by hydrothermal treatment at a temperature of 25 ° C. or more, BET specific surface area of 20 to 360 m 2 / g, X-ray diffraction pattern (020)
Boehmite having a crystallite diameter of 20 to 340 ° determined from the peak.
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを９０℃以
上の温度で水熱処理することを特徴とするベーマイトの
製造方法。4. A method for producing boehmite, comprising hydrothermally treating an ammonium ammonium sulfate solution or ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution at a temperature of 90 ° C. or higher.
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを３００〜
４５０℃の温度範囲で焼成することを特徴とするベーマ
イトの製造方法。5. An aluminum ammonium sulfate solution, or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution, is used in an amount of 300 to 300.
A method for producing boehmite, comprising firing at a temperature of 450 ° C.
は、硫酸アルミニウム溶液と重炭酸アンモニウム溶液と
の反応で得られるアンモニウムドーソナイトを３００〜
１１００℃の温度範囲で焼成し、その後、２５℃以上の
温度で水熱処理することを特徴とするベーマイトの製造
方法。6. An ammonium aluminum sulfate solution, or an ammonium dawsonite obtained by reacting an aluminum sulfate solution with an ammonium bicarbonate solution, in an amount of 300 to 300.
A method for producing boehmite, comprising firing at a temperature in the range of 1100 ° C. and then performing hydrothermal treatment at a temperature of 25 ° C. or higher.
請求項１記載のベーマイト。7. The boehmite according to claim 1, wherein the hydrothermal treatment temperature is 90 ° C. to 250 ° C.
請求項４記載のベーマイトの製造方法。8. The method for producing boehmite according to claim 4, wherein the hydrothermal treatment temperature is 90 ° C. to 250 ° C.
３５０〜９００℃である請求項３記載のベーマイト。9. The boehmite according to claim 3, wherein the firing temperature of the ammonium dawsonite is 350 to 900 ° C.
る請求項３記載のベーマイト。10. The boehmite according to claim 3, wherein the temperature of the hydrothermal treatment is from 80 ° C. to 250 ° C.
が３５０〜９００℃である請求項６記載のベーマイトの
製造方法。11. The method for producing boehmite according to claim 6, wherein the firing temperature of ammonium dawsonite is 350 to 900 ° C.
る請求項６記載のベーマイトの製造方法。12. The method for producing boehmite according to claim 6, wherein the hydrothermal treatment temperature is 80 ° C. to 250 ° C.
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|---|---|---|---|
| JP11063389A JP2000256011A (en) | 1999-03-10 | 1999-03-10 | Boehmite and its production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11063389A JP2000256011A (en) | 1999-03-10 | 1999-03-10 | Boehmite and its production |
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| Publication Number | Publication Date |
|---|---|
| JP2000256011A true JP2000256011A (en) | 2000-09-19 |
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ID=13227910
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|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP2000256011A (en) |
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| JP2002522343A (en) * | 1998-08-14 | 2002-07-23 | エル・ヴェー・エー‐デー・エー・アー アクチエンゲゼルシャフト フィュール ミネラルオエル ウント ヒェミー | High temperature stable high porosity aluminum oxide composed of boehmite-type alumina and pure single phase obtained therefrom |
| WO2003014251A1 (en) * | 2001-08-09 | 2003-02-20 | Hitachi Maxell, Ltd. | Non-magnetic particles having a plate shape and method for production thereof, abrasive material, polishing article and abrasive fluid comprising such particles |
| JP2006507930A (en) * | 2002-12-02 | 2006-03-09 | アルベマーレ ネザーランズ ビー．ブイ． | Solid particle conversion and grinding methods |
| JP2007223836A (en) * | 2006-02-22 | 2007-09-06 | Taimei Chemicals Co Ltd | Method for producing boehmite, and boehmite |
| JP2012511496A (en) * | 2008-12-11 | 2012-05-24 | ユーオーピー エルエルシー | Method for producing reinforced alumina |
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| CN104907012A (en) * | 2014-03-13 | 2015-09-16 | 中国科学院过程工程研究所 | Reactor for deep decomposition of aluminum ammonium sulfate and application method thereof |
| CN111924865A (en) * | 2020-08-05 | 2020-11-13 | 北京化工大学 | Crystal face selective growth boehmite and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002522343A (en) * | 1998-08-14 | 2002-07-23 | エル・ヴェー・エー‐デー・エー・アー アクチエンゲゼルシャフト フィュール ミネラルオエル ウント ヒェミー | High temperature stable high porosity aluminum oxide composed of boehmite-type alumina and pure single phase obtained therefrom |
| JP2009001492A (en) * | 1998-08-14 | 2009-01-08 | Sasol Germany Gmbh | Method for producing boehmitic crystalline alumina and boehmitic crystalline alumina |
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| CN111924865A (en) * | 2020-08-05 | 2020-11-13 | 北京化工大学 | Crystal face selective growth boehmite and preparation method thereof |
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