CN1030710A - 用分散产品制成制品的方法 - Google Patents
用分散产品制成制品的方法 Download PDFInfo
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
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- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
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- Ceramic Engineering (AREA)
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- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Physical Or Chemical Processes And Apparatus (AREA)
- Seasonings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Fats And Perfumes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明涉及用分散产品如粉末成型后进行热处
理制成制品的方法，其中将细菌或真菌发酵所得产品
如呫吨胶加入分散产品后用各种已知方法成型并将
成型制品进行热处理。所得产品的机械性能特别是
耐碎性特别好。本发明特别适用于催化剂和陶瓷制
造业。
Description
本发明涉及用分散产品成型并进行热处理而制成制品的方法。
更具体地讲，本发明涉及机械性能提高了的催化剂载体，催化剂，吸附剂和陶瓷等制品的制造方法。
已知用分散产品如粉料制成制品的方法，其中将粉料成粒，预制成片或挤出等而使其结块，或将分散产品制成悬浮液或溶液后模制成型，然后将其干燥，再将其进行热处理以除去全部水后而得机械性能适于各种用途的固体制品。
热处理根据欲制成产品的要求可在高温或低温下进行。但在吸附剂，催化剂或催化剂载体情况下，按照制造大孔容制品的一般方式，热处理为于600℃左右进行焙烧以避免孔不均匀，相反的是在陶瓷制品情况下，热处理为高温下进行烧结而制成密实产品。
已知方法中还加入添加剂以优化成型。不过，所得产品热处理后的机械性能不高。
而且，氧化铝基催化剂或催化剂载体的耐碎性（ESH）或耐粒碎性（EGG）相当低，这可能导致催化剂生产或其应用过程中夹带粉尘。
此外，催化剂载体要用构成催化活性相的元素的母体溶液浸渍。按已知方法构成的载体可能在此浸渍过程中破裂。破裂百分比根据初始粉料不同而可能达到很高的值。
本发明目的是弥补这些缺陷，其中提出用分散产品制成制品并可在热处理（烧结或焙烧）后得到机械性能大大提高并且在多孔制品情况下易于浸渍而又不会破裂的方法。
因此，本发明用分散产品成型并随后进行热处理而制成制品的方法的特征是，向分散产品中加至少一种细菌发酵或真菌发酵所得多糖化合物。
这种化合物存在下进行热处理可得到机械性能特别好的制品。
本发明用细菌发酵所得多糖化合物可为呫吨胶，琥珀葡聚糖胶或杂多糖S194，这正如欧洲专利n°77680所述。
碳水化合物在微生物特别是黄单胞菌属细菌作用下可得到呫吨胶。
这些细菌在Bergey′s manual of determinative bacteriology（ e edition-1974-Williams N.Wilkins Co.，Baltimore）中有说明如
Xanthomonas begoniae，Xanthomonas campestris，Xanthomonas carotae，Xanthomonas hederae，Xanthomonas incanae，Xanthomonas malvacearum，Xanthomonas papavericola，Xanthomonas phaseoli，Xanthomonas pisi，Xanthomonas vasculorum，Xanthomonas vesicatoria，Xanthomonas vitians，Xanthomonas pelargonii.其它可产生类似性质多糖的微生物可举出Arthrobacter菌属，特别是Arthrobacter stabilis，Arthrobacter Viscosus;Erwinia菌属;Azotobacter菌属，特别是Azotobacter indicus;Agrobacteriun菌属，特别是Agrobacterium radiobacter，Agrobacterium rhizogenes，Agrobacterium tumefaciens。当然，上列细菌仅为举例，并不限制所用细菌。
本发明用真菌发酵所得多糖化合物可为硬葡聚糖胶，是用碳水化合物由Sclerotium菌属真菌特别是Sclerotium glucanicum和Sclerotium rolfsii发酵而合成的。
本发明多糖化合物分子量大，特别是大于106g，一般呈可分散到液体特别是水中并溶解的粉状，在溶液中具有假塑性。
本发明制品用分散产品制成，而分散产品意指粉末、团块等。
这些分散产品按已知的常见方法成型。
此外，为进行成型，可通过试剂的分散或混合而使分散产品成为干态，湿态，糊状，液态或悬浮态或胶状。
根据产品状态（干、湿、糊或液）而进行成型的方法可举例如压片、密实、成粒、包衣、挤出、喷雾干燥，“油滴”凝固以及模制。成型过程一般包括分散步骤如拌合。
为有利于成型，可采用本技术领域熟知的添加剂。
分散产品为化合物如金属氧化物，陶瓷或化合物混合物。
适于制造催化剂、催化剂载体、吸附剂的分散产品可举出金属氧化物如氧化铝，氧化钛，二氧化硅，氧化锆和金属硫化物以及用于制造这些制品的所有无机化合物。
适用于本发明的还有所有陶瓷、或者呈氧化物态如二氧化硅，硅酸盐（富铝红柱石，堇青石和锆石等），氧化铝，铝酸盐（尖晶石等），硅铝酸盐（粘土等），氧化钛TiO2，钛酸盐（BaTiO3和MgTiO3等），氧化镁，氧化锆，稀土氧化物（ThO2和CeO2等），或者呈非氧化物态如碳化硼，碳化硅，氮化硼或氮化硅;或者呈混合态如氧氮化硅和铝（Sialon）。
当然，上列化合物仅作为举例，并不限制所用化合物。还可采用这些化合物的混合物。
所得制品然后于100-150℃左右干燥。
最后将干燥制品热处理，或者是根据制品性质而于300-800℃焙烧，或者是于更高温度，优选是高于1000℃下焙烧。
本发明制品在热处理之前的多糖含量为分散产品的0.2-5%，特别是0.4-3%（重量）。
本发明其它细节，优点及目的可参见以下非限制性实施例。
实施例1
制造以氧化铝为基础的催化剂载体，其中在以氧化铝计为3%（重量）硝酸，60%（重量）水和1%（重量）Rhone-Poulenc公司以商标Rhodopol出售的呫吨胶存在下将比表面积230m2/g和孔容0.5Cm2/g的勃姆石拌合。
所得糊状物挤出后干燥并于600℃焙烧。用得到的本发明催化剂载体A进行浸渍试验以调节其“破碎率”。
该破碎率相当于200℃水中浸渍时制品破裂百分比。
在正好向水中挤出20个制品的情况下，将20个制品浸湿并确定破裂的颗粒数即可得知破裂比。更具体地讲，记下横向破裂的挤出体，因为得到的碎片不只是机械性能低并且根本就不能用。
还根据Shell方法测耐碎性（ESH）以及根据ASTM04179-82有关催化剂的标准方法测耐粒碎性。
结果列于表Ⅰ
比较例2
用相同产品并按相同方法进行实施例1，不过勃姆石中不加呫吨胶。得到催化剂载体B，其性能按实施例1确定。
表Ⅰ
实施例 制品 呫吨胶% ESH EGG 破碎%
MPa daN/mm
1 A 1 1.46 2.38 2
2 B 2 1.12 1.06 4
实施例3-4
操作与实施例1类似。分散产品为以商名gel Condea出售的含20%水的氧化铝凝胶。
向氧化铝凝胶中以氧化铝计加2%（重量）的粉状呫吨胶。
挤出、干燥并于600℃焙烧后得到可用作催化剂载体的制品（C）。
用相同的氧化铝凝胶并按相同的方法，但不加呫吨胶即可得到催化剂载体（D）。
所得制品性能列于表Ⅱ：
表Ⅱ
实施例 制品 呫吨胶% ESH EGG 破碎%
MPa daN/mm
3 C 2（粉状） 0.98 1.90 0
4 D 0 0.79 1.34 22
实施例5-8
在这些实施例中，呫吨胶以水溶液态并按不同比例加入氧化铝凝胶中。催化剂载体按施例1制得。
试验结果列于表Ⅲ：
表Ⅲ
实施例 制品 呫吨胶% ESH EGG 破碎%
MPa daN/mm
5 E 0 0.96 1.76 8
6 F 0.25（溶液） 1.10 1.87 2
7 G 0.5（溶液） 1.12 2.11 0
8 H 3（粉状） 1.33 2.15 0
实施例1-8清楚地表明了加呫吨胶并且通常是加本发明多糖化合物对以氧化铝为基础的制品的机械性能以及浸渍时的稳定性。
实施例9-12
制成重量组成如下的含陶瓷悬浮液或浇注泥浆：
30%未焙烧高岭土
62%焙烧高岭土
7.7%滑石
0.3%六偏磷酸钠
模制并干燥泥浆后于1400℃下烧结生片所得陶瓷为瓷料。
以陶瓷为基础向泥浆中加不同量的呫吨胶即可得到多种陶瓷。
用ZWICK测力计测定所得陶瓷的断裂强度。
结果列于表Ⅳ：
表Ⅳ
实施例 呫吨胶%（重量） 断裂强度（MPa）
9 0 64
10 0.4 84
11 0.7 128
12 1 92
实施例13-15
制成以氧化钛特别是锐钛矿为基础的催化剂，其中向锐钛矿粉中加水和硝酸制成钛凝胶。所得胶以氧化钛计的烧蚀量为40%，而酸量为6-10%（重量）。
拌合后挤出凝胶，所得制品于100-120℃干燥后于350℃焙烧。
测定以氧化钛计的不同呫吨胶比例下催化剂的耐粒碎性（EGG）。
结果列于表Ⅴ：
表Ⅴ
实施例 呫吨胶% 孔容 EGG
Cm3/g daN/mm
13 0 0.30 1.00
14 1.5 0.30 1.53
15 3 0.30 1.80
这些催化剂尤其适用于克劳斯（Claus）方法，其催化活性与不含呫吨胶或本发明多糖的催化剂类似。
Claims (15)
1、用分散产品成型后进行热处理制造固体制品的方法，其特征是向分散产品中加至少一种细菌或真菌发酵所得多糖化合物。
2、权利要求1的方法，其特征是多糖化合物为大分子量优选大于106g并且在溶液中具有假塑性的化合物。
3、权利要求1或2的方法，其特征是细菌发酵所得多糖化合物选自呫吨胶或琥珀葡聚糖胶。
4、权利要求1、2或3的方法，其特征是真菌发酵所得多糖化合物为硬葡聚糖胶。
5、权利要求1-4之一的方法，其特征是多糖化合物以固态优选以粉态加入。
6、权利要求1-4之一的方法，其特征是多糖化合物以溶液态加入。
7、前述权利要求之一的方法，其特征是呫吨胶为碳水化合物在黄单胞菌属细菌作用下发酵而得。
8、权利要求1、2、3、5、6或7之一的方法，其特征是细菌源多糖是碳水化合物在Arthrobacter，Erwina，Azotobacter和Agrobacterium菌属细菌作用下发酵而得。
9、前述权利要求之一的方法，其特征是以分散产品计的多糖加入量为0.2-5%（重量）。
10、权利要求9的方法，其特征是以分散产品计的多糖加入量为0.4-3%（重量）。
11、前述权利要求之一的方法，其特征是分散产品为选自金属氧化物的粉末。
12、权利要求11的方法，其特征是金属氧化物选自氧化铝，氧化钛，二氧化硅和氧化锆。
13、权利要求11或12的方法，其特征是制品为催化剂载体。
14、权利要求11或12的方法，其特征是制品为催化剂。
15、权利要求1-10之一的方法，其特征是分散产品为陶瓷。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8708606A FR2616693B1 (fr) | 1987-06-19 | 1987-06-19 | Procede de fabrication d'articles a partir de produit divise |
| FR8708606 | 1987-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1030710A true CN1030710A (zh) | 1989-02-01 |
Family
ID=9352254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88103680.3A Pending CN1030710A (zh) | 1987-06-19 | 1988-06-18 | 用分散产品制成制品的方法 |
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| Country | Link |
|---|---|
| US (1) | US4983563A (zh) |
| EP (1) | EP0297942B1 (zh) |
| JP (1) | JPS6465066A (zh) |
| CN (1) | CN1030710A (zh) |
| AT (1) | ATE161247T1 (zh) |
| BR (1) | BR8802969A (zh) |
| CA (1) | CA1325002C (zh) |
| DE (1) | DE3856087T2 (zh) |
| DK (1) | DK333488A (zh) |
| ES (1) | ES2112825T3 (zh) |
| FR (1) | FR2616693B1 (zh) |
| IE (1) | IE80680B1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109622014A (zh) * | 2018-12-12 | 2019-04-16 | 安徽大学 | 一种电催化氧气产生过氧化氢的催化剂的制备方法 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912069A (en) * | 1986-10-14 | 1990-03-27 | Ruben George C | Use of pectin or pectin-like material in water-based ceramics |
| EP0325425B1 (en) * | 1988-01-20 | 1993-08-11 | Takeda Chemical Industries, Ltd. | Plastic compositions of inorganic powders and sintered bodies of the same |
| US5154771A (en) * | 1989-07-19 | 1992-10-13 | Takeda Chemical Industries, Ltd. | Hydraulic inorganic composition and molded articles thereof |
| JPH03215343A (ja) * | 1990-01-16 | 1991-09-20 | Agency Of Ind Science & Technol | ファインセラミックスの成形方法及び成形装置 |
| FR2665168B1 (fr) * | 1990-07-30 | 1994-03-25 | Rhone Poulenc Chimie | Composition comportant un succinoglycane. |
| FR2665167B1 (fr) * | 1990-07-30 | 1994-03-25 | Rhone Poulenc Chimie | Composition comportant un polysaccharide obtenu par fermation microbiemnne. pa |
| ATE130831T1 (de) * | 1991-01-07 | 1995-12-15 | Takeda Chemical Industries Ltd | Verfahren zur formgebung und zum brennen von zeolith-pulver. |
| US7192464B2 (en) * | 2003-09-03 | 2007-03-20 | Apex Advanced Technologies, Llc | Composition for powder metallurgy |
| US7111731B2 (en) * | 2004-01-15 | 2006-09-26 | Ogio International, Inc. | Pocket closure device |
| US8641815B2 (en) * | 2011-02-28 | 2014-02-04 | Corning Incorporated | Ceramic compositions for improved extrusion |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1273547A (en) * | 1918-02-02 | 1918-07-23 | White Heat Products Company | Process of making artificial stone. |
| US1610182A (en) * | 1923-12-28 | 1926-12-07 | Gen Electric | Fused quartz product and process of producing same |
| US2603610A (en) * | 1949-06-11 | 1952-07-15 | Dow Chemical Co | Preparation of a dehydrogenation catalyst |
| US2776897A (en) * | 1953-05-06 | 1957-01-08 | Mcgraw Electric Co | Method and composition for making ceramic articles |
| US2887394A (en) * | 1956-04-04 | 1959-05-19 | Corning Glass Works | Method of making a nonporous, semicrystalline ceramic body |
| US3379543A (en) * | 1964-03-27 | 1968-04-23 | Corning Glass Works | Composition and method for making ceramic articles |
| JPS55167048A (en) * | 1979-06-15 | 1980-12-26 | Kureha Chem Ind Co Ltd | Manufacture of spherical chitin molding |
| FR2516527B1 (fr) * | 1981-11-16 | 1986-05-23 | Rhone Poulenc Spec Chim | Compositions a base de gommes hydrosolubles, leur preparation et leur utilisation |
| US4477579A (en) * | 1983-04-14 | 1984-10-16 | Nalco Chemical Company | Electrode coating and coated electrodes |
| US4774211A (en) * | 1983-08-08 | 1988-09-27 | International Business Machines Corporation | Methods for predicting and controlling the shrinkage of ceramic oxides during sintering |
| GB8323501D0 (en) * | 1983-09-01 | 1983-10-05 | Ici Plc | Making refractory units |
-
1987
- 1987-06-19 FR FR8708606A patent/FR2616693B1/fr not_active Expired - Lifetime
-
1988
- 1988-06-15 EP EP88401477A patent/EP0297942B1/fr not_active Expired - Lifetime
- 1988-06-15 ES ES88401477T patent/ES2112825T3/es not_active Expired - Lifetime
- 1988-06-15 AT AT88401477T patent/ATE161247T1/de not_active IP Right Cessation
- 1988-06-15 DE DE3856087T patent/DE3856087T2/de not_active Expired - Fee Related
- 1988-06-17 JP JP63148443A patent/JPS6465066A/ja active Pending
- 1988-06-17 CA CA000569765A patent/CA1325002C/fr not_active Expired - Fee Related
- 1988-06-17 IE IE185088A patent/IE80680B1/en not_active IP Right Cessation
- 1988-06-17 BR BR8802969A patent/BR8802969A/pt not_active IP Right Cessation
- 1988-06-17 DK DK333488A patent/DK333488A/da not_active Application Discontinuation
- 1988-06-18 CN CN88103680.3A patent/CN1030710A/zh active Pending
- 1988-06-20 US US07/208,501 patent/US4983563A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109622014A (zh) * | 2018-12-12 | 2019-04-16 | 安徽大学 | 一种电催化氧气产生过氧化氢的催化剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DK333488A (da) | 1989-02-01 |
| BR8802969A (pt) | 1989-01-10 |
| DK333488D0 (da) | 1988-06-17 |
| DE3856087T2 (de) | 1998-07-16 |
| ES2112825T3 (es) | 1998-04-16 |
| IE881850L (en) | 1988-12-19 |
| EP0297942A1 (fr) | 1989-01-04 |
| FR2616693A1 (fr) | 1988-12-23 |
| JPS6465066A (en) | 1989-03-10 |
| EP0297942B1 (fr) | 1997-12-17 |
| US4983563A (en) | 1991-01-08 |
| CA1325002C (fr) | 1993-12-07 |
| FR2616693B1 (fr) | 1991-04-26 |
| DE3856087D1 (de) | 1998-01-29 |
| IE80680B1 (en) | 1998-12-02 |
| ATE161247T1 (de) | 1998-01-15 |
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