EP0107689A1 - Procedure for manufacturing titanates - Google Patents
Procedure for manufacturing titanatesInfo
- Publication number
- EP0107689A1 EP0107689A1 EP83901347A EP83901347A EP0107689A1 EP 0107689 A1 EP0107689 A1 EP 0107689A1 EP 83901347 A EP83901347 A EP 83901347A EP 83901347 A EP83901347 A EP 83901347A EP 0107689 A1 EP0107689 A1 EP 0107689A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- procedure according
- procedure
- mixture
- titanium dioxide
- titanates
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/09—Inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the invention concerns a procedure for manufacturing titanates.
- radioactive waste solutions are produced in ample quantity.
- the aim is, by treatment of these wastes, both to reduce their volume and to solidify them for easier subsequent handling and storing.
- ion exchangers are one of the most important ways to bind radionuclides from waste solutions.
- Organic ion exchangers which are employed in cleaning the primary circuits of nuclear reactors, are however not suited for use in solidifying high-active waste because they cannot tolerate high radiation doses. Instead, organic ion exchangers are used in solidifying power plant waste, the ion exchangers loaded with waste being immobilized, most commonly, in cement or bitumen.
- Inorganic ion exchangers which group also includes titanates, are better appropriate for solidifying especially high-active waste. They tolerate radiation well as a rule. They may be used, for instance
- the ultimate object of nuclear waste treatment is to achieve a low-soluble, both mechanically durable and radiation and heat resistant final waste product.
- Inorganic ion exchangers are converted into final waste product either as they are at high pressure and temperature, or by admixing to them vitrifying or ceramizing substances before they are heated.
- Titanates are inorganic ion exchangers. They have the structure of hydrous oxides.
- sodium titanate is synthesized as follows:
- sodium titanate is synthesized from titanium tetrachloride and sodium hydroxide.
- the object of the invention is to achieve an improvement in procedures for the manufacturing of titanates known at present.
- the more detailed object of the invention is to provide a procedure which is substantially simpler and less expensive than any procedures of prior art.
- the other aims of the invention and the advantages gainable with its aid will become apparent from the disclosure of the invention.
- the procedure of the invention offers a single-step titanate synthesis based on an inexpensive and readily available raw material, titanium dioxide hydrate, which is obtained e.g. as an intermediate in the titanium dioxide pigment industry, and on a simple process technology.
- the product obtained by the procedure of the invention, titanate has high capacities for radionuclides; it tolerates radiation exceedingly well; and it can be ceramized to final waste product.
- the raw material of the titanate synthesis is titanium dioxide hydrate mass.
- the titanium dioxide hydrate mass is an intermediate from the manufacturing of titanium dioxide pigment, from the so-called sulphate process.
- ilmenite mineral mineral formula FeTiO 3
- the "extraction cake" obtained in this reaction is dissolved in water or in a weak acid, whereby a mixture of titanium sulphate and iron sulphates is produced.
- the ferrisulphate is reduced to ferrosulphate and removed by filtering.
- the solution is then concentrated and the concentrated titanium sulphate solution is converted by hydrolysis to titanium dioxide hydrate, which is the initial substance for the titanate synthesis. Its dry matter content is about 40 %. As a result of the process, it is exceedingly acidic.
- the titanium dioxide hydrate mass is suspended in water or in an organic solvent, e.g. ethanol, propanol or butanol, at weight proportions 1/10-1/5.
- the mixture is heated to the boiling point (water 100oC, water/ethanol 78oC, water/propanol 88oC, water/- 1-butanol 93oC) .
- a 20-40 % aqueous solution of an alkali or earth alkali metal hydroxide, such as NaOH, KOH or Ca(OH) 2 , NH 3 or of an organic amine, such as hydrazine, mono, di or trimethylamine, is slowly added at weight proportion 1/3-1/1 referred to the wet weight of the titanium hydrate.
- the bases it is possible by varying the bases, or when several different bases are used in one synthesis by varying their proportions, to influence the sorption properties of the product, in particular its ion selectivity.
- the mixture After adding the base, the mixture is allowed to react at the boiling point of the azeotrope, with powerful agitation, 2-4 hours. The mixture is left to stand over night and filtered and washed with water for 1-2 days. Drying at 105-110oC for 24 hours. The product is cake-like and can be ground and sieved to separate the desired grain sizes.
- One sodium titanate product has the chemical composition:
- This sodium titanate had specific surface area 12 m 2 /g.
- the product in completed form is cake-like. It can be ground and the different grain sizes can be separated by sieving. The greater part of the grains obtained are suitable for column use, and the grains are mechanically durable enough. The finest granular material may be used for batch equilibrations.
- the strontium sorption half-time is dependent on the grain size of the sodium titanate, the half-time with grain size 0.071-0.140 mm being
- the distribution coefficient is also higher than in the latter case by a factor over 4, i.e., 5.6 x 10 4 .
- the sorption capacities of sodium titanate are high.
- the capacities determined by column experiments are: for strontium 1.4 mmol/g, cesium 1.5 mmol/g and cobolt 1.8 mmol/g.
- the distribution coefficients increase powerfully with increasing pH, being at pH higher than 6: several ten thousand for strontium, several thousand for cobolt, but for cesium only from a few tens to hundreds.
- the sorption mechanism is not fully understood.
- the exchangeable ion in sodium titanate is sodium. Since Sr, Cs and Co exchange the stoichiometric quantity of sodium, this suggests chemical ion exchange. Sorption takes place in two steps. The greater part of the sorption is very rapid. At the second step the sorption is lower by one order of magnitude. The first step is believed to be exchange onto the surface of the grains and to the fine dust that is present. The second step would seem to be exchange into the grains.
- Sodium titanate tolerates radiation very well.
- a 10 Gy gamma dose has no effect on the sorption capacity, on structure, nor on the specific surface area.
- the finest granular material may be used in batch operation. This material is added to the waste solution and mixed during a couple of hours at the most. The material is then either separated e.g. by filtering, or red clay or other brick clay is admixed to it for baking. In the first instance, the filtered titanate is usually dried at a few hundred degrees and ceramized after grinding.
- Titanates may be used in columns either completely separated or to the purpose of binding the waste nuclides remaining in the residual solution from batch running. After the use, the material is removed from the column and it is usually dried, ground and ceramized.
- the evaporator waste concentrates of nuclear power stations have greatly variable origins. They present a high salt concentration as a rule. Titanates may best be applied to solidify them by equilibrating the waste and titanate in a batch, by thereafter adding brick clay and by preparing a brick. 4-M sodium concentration, which corresponds to the true situation in evaporator wastes, lowers the distribution coefficient of strontium in sodium titanate by one order of magnitude. A boric acid concentration of 1-M, also consistent with actual situations, lowers the distribution coefficient of strontium by one order of magnitude. The capacity is still high enough in spite of salt concentrations as mentioned above.
- the organic ion exchangers removed from the primary circuits of reactors are, on the side of the evaporator concentrates mentioned, the most important source of medium activity waste. At present they are usually embedded in concrete or bitumen.
- an alternative possibility is to elute the waste nuclides from the resins and to bind them e.g. to titanate in columns.
- complex-forming agents such as oxalates, citrates and EDTA.
- oxalates, citrates and EDTA One possible eluant , sodium citrate, causes no substantial weakening of the sorption of strontium in sodium titanate.
- EDTA significally lowers the sorption at pH over 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
La matière première dans la production de titanates est l'hydrate de dioxide de titane, produit intermédiaire dans l'industrie des pigments à base de dioxide de titane. Le composé est mis en suspension dans de l'eau et de l'alcool et, après chauffage, une base est ajoutée au mélange en ébulliton. En faisant varier la base réactive, il est possible de modifier la sélectivité du produit à différents métaux. Les titanates possèdent des capacités élevées d'absorption de nucléides résiduels, et peuvent être avantageusement convertis en céramique et présentent une très bonne tolérance aux radiations.The raw material in the production of titanates is titanium dioxide hydrate, an intermediate product in the pigment industry based on titanium dioxide. The compound is suspended in water and alcohol and, after heating, a base is added to the boiling mixture. By varying the reactive base, it is possible to modify the selectivity of the product to different metals. Titanates have high capacities for absorbing residual nuclides, and can be advantageously converted to ceramic and have very good radiation tolerance.
Description
Procedure for manufacturing titanates
The invention concerns a procedure for manufacturing titanates.
In nuclear energy production, and also in the production and use of radionuclides, radioactive waste solutions are produced in ample quantity. The aim is, by treatment of these wastes, both to reduce their volume and to solidify them for easier subsequent handling and storing.
The use of ion exchangers is one of the most important ways to bind radionuclides from waste solutions. Organic ion exchangers, which are employed in cleaning the primary circuits of nuclear reactors, are however not suited for use in solidifying high-active waste because they cannot tolerate high radiation doses. Instead, organic ion exchangers are used in solidifying power plant waste, the ion exchangers loaded with waste being immobilized, most commonly, in cement or bitumen.
Inorganic ion exchangers, which group also includes titanates, are better appropriate for solidifying especially high-active waste. They tolerate radiation well as a rule. They may be used, for instance
- as ion exchangers for cleaning the primary circuit of the reactors
- for solidifying the waste nuclides eluted from organic ion exchange resins removed from the reactor's primary circuit
- for solidifying evaporator concentrates
- for solidifying waste solutions accruing at decommissioning or repairs of a nuclear power plant
- for solidifying high-active reprosessing waste.
The ultimate object of nuclear waste treatment is to achieve a low-soluble, both mechanically durable and radiation and heat resistant final waste product. Inorganic ion exchangers are
converted into final waste product either as they are at high pressure and temperature, or by admixing to them vitrifying or ceramizing substances before they are heated.
The state of the titanate manufacturing technology is illustrated by the British Patent No. 1.493.698 (Sandia Laboratories, U.S.A.) and by U.S. Patent No. 4.161.513 (PRAV Project, Sweden). However, the manufacturing procedures disclosed in these patents present the drawback of costliness and complexity of the titanate syntheses. In the syntheses expensive chemicals are required and they are in multiple steps. Moreover, the procedure of the first-mentioned patent is encumbered by the drawback that the synthetized sodium titanate loses half of its ion exchange capacity under a 107 Gy gamma radiation dose.
Titanates are inorganic ion exchangers. They have the structure of hydrous oxides. In the procedure of GB Patent No. 1.493.698, sodium titanate is synthesized as follows:
In the procedure of U.S. Patent No. 4.161.513, sodium titanate is synthesized from titanium tetrachloride and sodium hydroxide.
The object of the invention is to achieve an improvement in procedures for the manufacturing of titanates known at present. The more detailed object of the invention is to provide a procedure
which is substantially simpler and less expensive than any procedures of prior art. The other aims of the invention and the advantages gainable with its aid will become apparent from the disclosure of the invention.
The aims of the invention are achieved by a procedure which is mainly characterized in that the procedure comprises the following steps:
(a) titanium dioxide hydrate is dissolved in a solvent; (b) the mixture is heated; and
(c) a base giving off exchangeable cation to the titanium dioxide hydrate is added.
The remaining characteristic features of the procedure of the invention are stated in claims 2-9.
Numerous remarkable advantages are gained by the invention. First of all, the procedure of the invention offers a single-step titanate synthesis based on an inexpensive and readily available raw material, titanium dioxide hydrate, which is obtained e.g. as an intermediate in the titanium dioxide pigment industry, and on a simple process technology. The product obtained by the procedure of the invention, titanate, has high capacities for radionuclides; it tolerates radiation exceedingly well; and it can be ceramized to final waste product.
The use of the invention is illustrated in detail in the attached drawing, but to the used depicted in which the invention is not meant to be exclusively confined. The drawing shows the procedure of the invention in the form of a synthesis scheme.
In the procedure of the invention, the raw material of the titanate synthesis is titanium dioxide hydrate mass. The titanium dioxide hydrate mass is an intermediate from the manufacturing of titanium dioxide pigment, from the so-called sulphate process. Herein, ilmenite mineral (mineral formula FeTiO3) is allowed to react with hot concentrated sulphuric acid. The "extraction cake"
obtained in this reaction is dissolved in water or in a weak acid, whereby a mixture of titanium sulphate and iron sulphates is produced. The ferrisulphate is reduced to ferrosulphate and removed by filtering. The solution is then concentrated and the concentrated titanium sulphate solution is converted by hydrolysis to titanium dioxide hydrate, which is the initial substance for the titanate synthesis. Its dry matter content is about 40 %. As a result of the process, it is exceedingly acidic.
The titanium dioxide hydrate mass is suspended in water or in an organic solvent, e.g. ethanol, propanol or butanol, at weight proportions 1/10-1/5. The mixture is heated to the boiling point (water 100ºC, water/ethanol 78ºC, water/propanol 88ºC, water/- 1-butanol 93ºC) . A 20-40 % aqueous solution of an alkali or earth alkali metal hydroxide, such as NaOH, KOH or Ca(OH)2, NH3 or of an organic amine, such as hydrazine, mono, di or trimethylamine, is slowly added at weight proportion 1/3-1/1 referred to the wet weight of the titanium hydrate. It is possible by varying the bases, or when several different bases are used in one synthesis by varying their proportions, to influence the sorption properties of the product, in particular its ion selectivity. After adding the base, the mixture is allowed to react at the boiling point of the azeotrope, with powerful agitation, 2-4 hours. The mixture is left to stand over night and filtered and washed with water for 1-2 days. Drying at 105-110ºC for 24 hours. The product is cake-like and can be ground and sieved to separate the desired grain sizes.
In the following is presented an example of sodium titanate synthesis in 1-butanol. 2.025 kg of titanium hydrate mass were suspended in 5 litres of 1-butanol. Heating to 93ºC. Addition during 15 min. of 4.313 kg of 30 % aqueous NaOH solution. Allowed to react at the boiling point of the azeotrope with powerful agitation, 3 hours. Allowed to stand over night, filtrated and washed with water in a Soxhlet extraction apparatus for two days. Drying for one day at 110ºC. The cake was ground and the different grain sizes were separated by sieving.
The filtered, wet product had the weight 3890 g The product dried at 110°C had the weight 920 g Of grain fraction 0.315-0.850 mm was obtained 480 g
In the following are presented some properties of the sodium titanate typically obtained by this procedure.
One sodium titanate product has the chemical composition:
Ti 37 % by weight
Na 16 % by weight
H2O 12 % by weight
CO3= 5 % by weight
SO4 1 % by weight The rest hydrogen and oxygen.
This sodium titanate had specific surface area 12 m2/g.
The product in completed form is cake-like. It can be ground and the different grain sizes can be separated by sieving. The greater part of the grains obtained are suitable for column use, and the grains are mechanically durable enough. The finest granular material may be used for batch equilibrations. The strontium sorption half-time is dependent on the grain size of the sodium titanate, the half-time with grain size 0.071-0.140 mm being
< 20 s, and with 0.350-0.850 mm grain size 95 s. With the first-mentioned grain size the distribution coefficient is also higher than in the latter case by a factor over 4, i.e., 5.6 x 104.
The sorption capacities of sodium titanate are high. The capacities determined by column experiments are: for strontium 1.4 mmol/g, cesium 1.5 mmol/g and cobolt 1.8 mmol/g. The distribution coefficients increase powerfully with increasing pH, being at pH higher than 6: several ten thousand for strontium, several thousand for cobolt, but for cesium only from a few tens to hundreds.
The sorption mechanism is not fully understood. The exchangeable ion in sodium titanate is sodium. Since Sr, Cs and Co exchange the stoichiometric quantity of sodium, this suggests chemical ion exchange. Sorption takes place in two steps. The greater part of the sorption is very rapid. At the second step the sorption is lower by one order of magnitude. The first step is believed to be exchange onto the surface of the grains and to the fine dust that is present. The second step would seem to be exchange into the grains.
Sodium titanate tolerates radiation very well. A 10 Gy gamma dose has no effect on the sorption capacity, on structure, nor on the specific surface area.
The finest granular material may be used in batch operation. This material is added to the waste solution and mixed during a couple of hours at the most. The material is then either separated e.g. by filtering, or red clay or other brick clay is admixed to it for baking. In the first instance, the filtered titanate is usually dried at a few hundred degrees and ceramized after grinding.
Titanates may be used in columns either completely separated or to the purpose of binding the waste nuclides remaining in the residual solution from batch running. After the use, the material is removed from the column and it is usually dried, ground and ceramized.
The evaporator waste concentrates of nuclear power stations have greatly variable origins. They present a high salt concentration as a rule. Titanates may best be applied to solidify them by equilibrating the waste and titanate in a batch, by thereafter adding brick clay and by preparing a brick. 4-M sodium concentration, which corresponds to the true situation in evaporator wastes, lowers the distribution coefficient of strontium in sodium titanate by one order of magnitude. A boric acid concentration of 1-M, also consistent with actual situations, lowers the distribution coefficient of strontium by one order of magnitude. The capacity is still high enough in spite of salt concentrations as mentioned
above.
The organic ion exchangers removed from the primary circuits of reactors are, on the side of the evaporator concentrates mentioned, the most important source of medium activity waste. At present they are usually embedded in concrete or bitumen. However, an alternative possibility is to elute the waste nuclides from the resins and to bind them e.g. to titanate in columns. In the elution may be used complex-forming agents such as oxalates, citrates and EDTA. One possible eluant , sodium citrate, causes no substantial weakening of the sorption of strontium in sodium titanate. In contrast, EDTA significally lowers the sorption at pH over 6.
Claims
1. Procedure for manufacturing titanates, characterized in that the procedure comprises the following steps:
(a) titanium dioxide hydrate is suspended in a solvent,
(b) the mixture is heated, and
(c) a base giving off exchangeable cation to the titanium dioxide hydrate is added.
2. Procedure according to claim 1, characterized in that water is used for solvent.
3. Procedure according to claim 1, characterized in that an organic solvent is used for solvent.
4. Procedure according to claim 3, characterized in that as organic solvent is used ethanol, propanol or butanol or a mixture of these.
5. Procedure according to any one of claims 1-4, characterized in that for cation-releasing base is used an aqueous solution of an alkali or alkaling earth metal hydroxide, such as NaOH, KOH or Ca(OH)2.
6. Procedure according to any one of claims 1-4, characterized in that for cation-releasing base is used ammonia or an aqueous solution of an organic amine, such as hydrazine, mono, di or trimethylamine.
7. Procedure according to any one claims 1-6, characterized in that after adding base giving off exchangeable cation to the titanium dioxide hydrate the mixture is mixed and the mixture is allowed to react during a few hours.
8. Procedure according to claim 7, characterized in that after reacting the mixture is left to stand over night.
9. Procedure according to claim 8, characterized in that the mixture is filtered, washed and dried.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI821535 | 1982-04-30 | ||
| FI821535A FI821535L (en) | 1982-04-30 | 1982-04-30 | FRAME STEERING FRAME STEERING |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0107689A1 true EP0107689A1 (en) | 1984-05-09 |
Family
ID=8515448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83901347A Withdrawn EP0107689A1 (en) | 1982-04-30 | 1983-04-26 | Procedure for manufacturing titanates |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0107689A1 (en) |
| FI (1) | FI821535L (en) |
| WO (1) | WO1983003819A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3725740A1 (en) * | 1987-08-04 | 1989-02-16 | Kernforschungsz Karlsruhe | METHOD FOR THE PRODUCTION OF SINTERABLE POWDER FOR BINARY AND MULTINERAL, CERAMIC OXIDE MATERIALS |
| US5082648A (en) * | 1989-01-26 | 1992-01-21 | Pfizer Inc. | Process for the preparation of high purity calcium titanate hydrates and product produced thereby |
| US6106799A (en) * | 1995-12-22 | 2000-08-22 | Ivo International Ltd. | Preparation of granular titanate ion exchangers |
| FI956222A0 (en) * | 1995-12-22 | 1995-12-22 | Ivo International Oy | Framstaellning av granulaera titanatjonbytare |
| CN1126717C (en) * | 1998-07-01 | 2003-11-05 | 卡伯特公司 | Hydrothermal process for making barium titanate powders |
| RU2564339C2 (en) * | 2010-03-25 | 2015-09-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный университет" (СПбГУ) | Layered titanates, methods for production and use thereof |
| JP6106952B2 (en) * | 2012-05-29 | 2017-04-05 | 栗田工業株式会社 | Radioactive material adsorbent, and adsorption vessel, adsorption tower, and water treatment apparatus using the same |
| CN115155540B (en) * | 2022-07-11 | 2023-06-16 | 沈阳理工大学 | Method for preparing porous nano titanate microsphere by resin adsorption template and gas thermal catalysis |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1697929A (en) * | 1925-06-02 | 1929-01-08 | Titanium Pigment Co Inc | Alkali-metal titanate and method of making same |
| DE497626C (en) * | 1926-11-17 | 1930-05-15 | Titan Co As | Manufacture of titanium compounds |
| US2218655A (en) * | 1938-06-15 | 1940-10-22 | Du Pont | Process for producing insoluble titanates |
| US2757069A (en) * | 1954-09-30 | 1956-07-31 | Du Pont | Silver titanates and their preparation |
| US3331658A (en) * | 1963-11-14 | 1967-07-18 | Du Pont | Process for producing fibrous alkali metal titanates |
| US3701828A (en) * | 1971-02-03 | 1972-10-31 | Johns Manville | Hydrothermal synthesis of perovskite composed of cao tio2 |
| JPS5611668B1 (en) * | 1971-03-26 | 1981-03-16 | ||
| JPS516200A (en) * | 1974-07-05 | 1976-01-19 | Central Glass Co Ltd | Kaatsukadatsusuihonyoru chitansankarisenino seizohoho |
| SE404353B (en) * | 1976-12-15 | 1978-10-02 | Forberg Sevald | METHOD OF PREPARING AS ION EXCHANGE MATERIAL RELEASED TITANATES |
| DE2707229C2 (en) * | 1977-02-19 | 1983-08-25 | Bayer Ag, 5090 Leverkusen | Production of zinc and alkaline earth titanates |
| SU812721A1 (en) * | 1979-02-28 | 1981-03-15 | Предприятие П/Я А-3481 | Method of froducing cas103-t102 ceramic material |
-
1982
- 1982-04-30 FI FI821535A patent/FI821535L/en not_active Application Discontinuation
-
1983
- 1983-04-26 EP EP83901347A patent/EP0107689A1/en not_active Withdrawn
- 1983-04-26 WO PCT/FI1983/000036 patent/WO1983003819A1/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8303819A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FI821535A0 (en) | 1982-04-30 |
| WO1983003819A1 (en) | 1983-11-10 |
| FI821535L (en) | 1983-10-31 |
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