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WO1998026101A1 - Procede de preparation de zeolithes a partir de cendres volantes - Google Patents

Procede de preparation de zeolithes a partir de cendres volantes Download PDF

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Publication number
WO1998026101A1
WO1998026101A1 PCT/NL1997/000682 NL9700682W WO9826101A1 WO 1998026101 A1 WO1998026101 A1 WO 1998026101A1 NL 9700682 W NL9700682 W NL 9700682W WO 9826101 A1 WO9826101 A1 WO 9826101A1
Authority
WO
WIPO (PCT)
Prior art keywords
fly ash
zeolite
preparing
reaction mixture
hydroxide solution
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.)
Ceased
Application number
PCT/NL1997/000682
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English (en)
Inventor
Maria Janssen-Jurkovicova
Guido Gerard Hollman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kema NV
Original Assignee
Kema NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kema NV filed Critical Kema NV
Priority to AU53461/98A priority Critical patent/AU5346198A/en
Publication of WO1998026101A1 publication Critical patent/WO1998026101A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/22—Type X
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for preparing zeolites from fly ash. It is known that zeolites can be prepared from chemically pure materials such as aluminium hydroxide and silicon oxide, wherein chemically pure is understood to mean such a degree of purity as is usual commercially. This means that pure, i.e. expensive, raw materials are used for the preparation of zeolites.
  • Zeolites are being used increasingly in recent times, wherein for a number of applications it is not essential for the zeolite to be obtained with a high degree of purity.
  • the object of the present invention is to provide a method for preparing a zeolite product, wherein use can be made of cheaper raw materials, wherein a zeolite product is obtained with a degree of purity and definition which are possibly lower than those of traditional synthetic zeolites but which are better than those of natural zeolites, in combination with a zeolite product of much higher quality.
  • the present invention therefore provides a method for preparing zeolite of two different qualities, wherein a hydroxide solution is added to fly ash and the thus resulting mixture is separated into fly ash residue and silica extract, wherein the fly ash residue is then mixed with a hydroxide solution to form a reaction mixture, the reaction mixture is heated to a temperature between 80°C and 150°C for a period of 10 to 50 hours, wherein the fly ash is held continuously in suspension by stirring, and fly ash residues containing the zeolite product are subsequently separated from the process water.
  • the silica extract is zeolitized in the same manner after addition of the correct quantity of aluminium hydroxide suspension in order to synthesize pure zeolite (>99%) .
  • Another preferred embodiment of this process relates to the zeolitization of fly ash from the combustion of domestic refuse (WIP fly ash) and chemical waste (CWIP fly ash) , which produces a zeolite- immobilizer.
  • the zeolitization serves to immobilize the heavy metals present in excess in these fly ashes and proceeds similarly to the described basic process.
  • figure 1 shows a schematic view of the first method (basic process) according to the present invention
  • figure 2 shows a schematic view of a second method (first preferred embodiment) according to the present invention.
  • the present invention provides a method for providing zeolite products from diverse fly ashes .
  • fly ashes which have either a small positive value (coal fly ash) or a high negative value (WIP and CWIP fly ash)
  • WIP and CWIP fly ash can be sold as high-grade product on the environmental technology market (as absorbent) or, in the case of WIP and CWIP fly ash, can be sold more easily on the building market for bulk applications.
  • a pretreatment of the fly ash is carried out, wherein the fly ashes are washed with a water and specific organic extraction agents to remove a substantial part of the possibly present heavy metals which are usually to be found in fly ash, and also a part of the components which are inactive in the zeolite synthesis (particularly calcium, magnesium, sulphur and phosphor) . These substances are also usually present in fly ashes . A large part of the iron present in the fly ash is also removed via magnetic separating techniques. This situation is shown at 2 in figure 2. Pretreated fly ash 3 thus results.
  • the pretreated fly ash 3 is subjected to a zeolitization process, which is shown in figure 1 in the box 4.
  • hydroxide solution is fed to the pretreated fly ash.
  • the hydroxide solution is a so-called 2 -molar solution which is preferably formed by an NaOH or a KOH solution or a mixture thereof with a ratio of 2.5 liquid and solids. It is herein possible to optimize the ratio of silicon and aluminium or to increase the concentration of these two elements in the reaction mixture.
  • This will certainly be necessary for the zeolitization of WIP and CWIP fly ashes as referred to in preferred embodiment 2. In the case of coal fly ash, and certainly Dutch coal fly ash, this is generally not necessary.
  • a residual product from the aluminium-processing industry obtainable as residue at a low price from the said industry, can be used as additional aluminium source and amorphous silica or specific fly ashes with a high silicon content from an electricity power station can be used as additional silicon source.
  • Table 1 Overview of the required molar ratios of the components determining zeolite type for the synthesis of zeolite Na-Pl, ZK-19 and K-G in the basic process
  • the reaction mixture is then incubated at a temperature of between 80°C and 150 °C at autogenous pressure, preferably and subject to the reactors available as closely as possible to 100°C or 150°C, wherein the fly ash is held continuously in suspension by stirring.
  • the incubation time lies between 10 and 50 hours, and depends on the chosen temperature and stirring speed. In one example the incubation time amounted to 24 hours at 93 °C and 200 revolutions per minute, and in another example 12 hours at 150 °C and stirring at 5 revolutions per minute.
  • the zeolite product is separated from the process water, indicated at 5 in figure 1, whereafter the remaining zeolite product can be washed in step 6 and 8 and dried in step 9. After drying 9 the zeolite product 11 can be pelletized and be sold as absorbent on the environmental technology market . It is herein noted that about two-thirds of the glass fraction in the original coal fly ash is converted into zeolite.
  • the zeolite product contains roughly 60% zeolite, 15% mullite, 5% quartz and 20% residual glass, assuming a fly ash from a Dutch electricity power station .
  • The. cation-exchanging capacity of the zeolite product obtained in the basic process amounts to about 3 meq/g, assuming a sodium-ammonia exchange.
  • the process water contains per litre about 0.5 mol hydroxide, 5,000 to 15,000 mg silicon and less than 50 mg aluminium and can hereby be circulated and thus used for: 1. the production of the zeolites of the types
  • the above described process is designated as the l-stage zeolite preparation process. It is however possible to apply a 2-stage process as referred to in the first preferred embodiment. Such a 2-stage process is shown in figure 2. This process corresponds with the process steps of the l-stage process as shown in figure 1, with the proviso that the pretreated fly ash 3 is subjected to silica extraction by adding hydroxide solution 7, as designated at 14.
  • the silicon concentration in the process water reaches a maximum value of 10,000 to 20,000 mg silicon per litre, depending on the type of hydroxide solution used and the stirring speed.
  • a silica extract and a fly ash residue are obtained. Both parts, fly ash residue and silica extract, are then converted separately and simultaneously into zeolites in the second stage.
  • 10% to 20% of the Si0 2 present in the fly ash is dissolved by the silica extraction.
  • step 15 A separation of solid and liquid thereafter takes place in step 15.
  • the remaining solid, the fly ash residue 16, is subsequently subjected to the same steps 4,5,6,8 and 10 as in the l-stage process.
  • the silica extract 17 obtained in step 15 is used for the synthesis of pure zeolites of the types A, X, Y, ZK-19 or K-G.
  • the Na 2 0;K 2 0; Al 2 0 3 ,-Si0 2 ratio of the silica extract is optimized by adding aluminium hydroxide or an aluminate solution thereto in a quantity which depends on the silicon concentration of the silica extract.
  • components determining the zeolite types must be present in the ratios shown in table 2.
  • Table 2 Overview of the required molar ratios of the components determining zeolite type for the production of zeolite A, X , Y, ZK- 19 and K--G from the silica extract
  • the molar ratios differ slightly because the residual product includes much sodium and moreover contains a complexing substance which holds aluminium in solution. Applicable here are the molar ratios as shown in table 3.
  • Table 3 Overview of the required molar ratios of the components determining zeolite type for the production of zeolite A, X, Y, ZK-19 and K-G from the silica extract when aluminium- containing residual product is used
  • zeolites takes place by incubating the optimized silica extract for 24 to 48 hours at 90°C, which is shown in step 18. Stirring is herein only necessary at the start to homogenize the mixture.
  • the zeolite product which consists almost entirely of zeolite, is separated from the process water in step 20.
  • the yield amounts to about 100 g zeolite per kg fly ash.
  • the remaining process water (with 1000-2000 mg silicon and 50-200 mg aluminium per litre) can be used as hydroxide source for:
  • step 4 1. the production of zeolite from power station fly ash as according to the described l-stage zeolitization process (step 4) ;
  • step 21 the remaining solid is then washed in step 21, separated again into liquid and solid in step 22 and subsequently dried in step 24.
  • a variant of the part of this preferred embodiment relating to the silica extraction is a continuous process wherein (washed) coal fly ash is mixed with the desired hydroxide solution in a continuous flow reactor.
  • the .average residence time of the process water is the same as said induction period (4 to 8 hours, depending on the chosen temperature) .
  • Aluminium hydroxide suspension is added to the process water from the reactor, being a silica extract, in order to precipitate silicon as amorphous aluminium silicate. This precipitate is separated off and the process water is returned to the reactor again.
  • the average residence time of the fly ash amounts to 10 to 40 hours and is modified such that silicon concentrations in the silica extract remain high enough for a cost-effective process.
  • a proportion of the process water is periodically replaced. Left over are a fly ash residue, a silicon aluminium precipitate and process water. In this variant these latter two together form the silica extract.
  • Further zeolite formation from the fly ash residue and the silica extract proceeds in a manner analogous to that from the fly ash residue and silica extract from the batch-wise silica extraction described above.
  • the zeolitization as performed with the silica extract can also be carried out with the process water from the l-stage zeolitization process. The only difference is that due to the lower silica concentrations in the process water the yield of pure zeolites will also be lower, i.e. about 50 g zeolite per kg fly ash, than when the silica extract is used.
  • the fly ash residue obtained in the separation of the silica extract can be used for:
  • zeolitization process can be linked a process for the production of a zeolite-immobilizer from WIP and CWIP fly ashes, which produces a variant of preferred embodiment 2.
  • the process water obtained from the zeolitization power station fly ash in the 1- and 2-stage process is herein used as additional silicon and hydroxide source in addition to other forms of (reactive) alumina and silica and a hydroxide solution.
  • a reaction mixture is required in which the components determining zeolite type occur in the molar ratios as stated in table 4.
  • Table 4 Overview of the required molar ratios of the components determining zeolite type for the production of a zeolite-immobilizer from WIP and CWIP fly ash
  • the obtained reaction mixture is incubated at a temperature of 80 to 150°C and autogenous pressure, wherein the solid phase is held in suspension by stirring.
  • the incubation time amounts to 10 to 50 hours and depends on the chosen temperature and the stirring speed (for instance 24 hours at 95 °C and 200 revolutions per minute, 12 hours at 150 °C and 5 revolutions per minute) .
  • the zeolite product is separated from the process water, washed and dried.
  • the zeolite product contains about 60% to 80% zeolite and 20% to 40% residual fly ash and other new compounds (including salts and amorphous phases) .
  • the quality of the product in terms of environmental " protection is such that the product complies at the very least with the requirements laid down in the waste disposal regulations for classification in category 4. For some fly ashes, depending on the concentrations of heavy metals present, it is possible that the zeolite-immobilizer fulfills the requirements laid down in the building materials regulations for category 2 bulk products .

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  • Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé de préparation de zéolithe de deux qualités différentes, consistant à ajouter une solution d'hydroxyde à des cendres volantes, et à séparer le mélange résultant en résidu de cendres volantes et en extrait de silice, puis à mélanger le résidu de cendres volantes avec une solution d'hydroxyde, afin de former un mélange de réaction, à chauffer ce mélange de réaction pour le porter à une température comprise entre 80 et 150 °C, pendant une durée de 10 à 50 heures, en agitant continuellement les cendres volantes afin de les maintenir en suspension, puis à séparer à partir de l'eau de traitement les résidus de cendres volantes contenant le produit à base de zéolithe. Selon un mode de réalisation préféré de l'invention, on ajoute de l'(hydr)oxyde d'aluminium à l'extrait de silice résultant, et on fait incuber le mélange ainsi résultant à une température augmentée selon le procédé ci-dessus, de façon à synthétiser de la zéolithe pure. Selon un autre mode de réalisation préféré, on convertit des cendres volantes, provenant d'installations d'incinération de déchets, en un agent d'immobilisation des zéolithes, comme dans le procédé ci-dessus décrit, et on ajoute éventuellement de l'(hydr)oxyde d'aluminium et de la silice supplémentaires, selon les besoins.
PCT/NL1997/000682 1996-12-09 1997-12-09 Procede de preparation de zeolithes a partir de cendres volantes Ceased WO1998026101A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53461/98A AU5346198A (en) 1996-12-09 1997-12-09 Method for preparing zeolites from fly ash

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1004729A NL1004729C2 (nl) 1996-12-09 1996-12-09 Werkwijze voor het vervaardigen van zeoliet uit vliegassen.
NL1004729 1996-12-09

Publications (1)

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WO1998026101A1 true WO1998026101A1 (fr) 1998-06-18

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NL (1) NL1004729C2 (fr)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6027708A (en) * 1998-09-08 2000-02-22 Council Of Scientific & Industrial Research Process for the synthesis of flyash based zeolite-Y
GB2345056A (en) * 1998-03-13 2000-06-28 Council Scient Ind Res Process for the synthesis of flyash based zeolite-a
KR100274118B1 (ko) * 1998-07-08 2001-01-15 이동훈 석탄비산재로부터 에이형 제올라이트를 제조하는 방법
EP1078882A1 (fr) * 1999-08-24 2001-02-28 K.E.M. Corporation Procédé de préparation d'une zéolite artificielle par une méthode de réaction en barbotine
US6599494B2 (en) 1999-08-19 2003-07-29 K.E.M. Corporation Process for preparing artificial zeolite by a slurry reaction method
CN111533135A (zh) * 2020-05-13 2020-08-14 华能国际电力股份有限公司 一种动态自调节水热法制备a型粉煤灰基分子筛的方法
EP3978436A4 (fr) * 2019-07-19 2023-03-08 Nakanishi Industry Co., Ltd. Procédé de production se rapportant à la production en masse industrielle de zéolite artificielle de haute pureté

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310496A (en) * 1976-11-11 1982-01-12 Degussa Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type A
US4798709A (en) * 1986-09-08 1989-01-17 Carbovan Inc. Process for treatment of flyash
JPH02229709A (ja) * 1989-03-01 1990-09-12 Nippon Steel Corp フライアッシュからのゼオライト合成方法
JPH0345512A (ja) * 1989-07-13 1991-02-27 Nippon Steel Corp フライアッシュからのゼオライト製造方法
JPH03232716A (ja) * 1990-02-06 1991-10-16 Nippon Steel Corp フライアッシュより高品質ゼオライトを製造する方法
JPH07109117A (ja) * 1993-10-04 1995-04-25 Agency Of Ind Science & Technol Ａ型ゼオライトの製造方法
JPH07165418A (ja) * 1993-12-13 1995-06-27 Minako Ishikawa ゼオライトの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310496A (en) * 1976-11-11 1982-01-12 Degussa Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type A
US4798709A (en) * 1986-09-08 1989-01-17 Carbovan Inc. Process for treatment of flyash
JPH02229709A (ja) * 1989-03-01 1990-09-12 Nippon Steel Corp フライアッシュからのゼオライト合成方法
JPH0345512A (ja) * 1989-07-13 1991-02-27 Nippon Steel Corp フライアッシュからのゼオライト製造方法
JPH03232716A (ja) * 1990-02-06 1991-10-16 Nippon Steel Corp フライアッシュより高品質ゼオライトを製造する方法
JPH07109117A (ja) * 1993-10-04 1995-04-25 Agency Of Ind Science & Technol Ａ型ゼオライトの製造方法
JPH07165418A (ja) * 1993-12-13 1995-06-27 Minako Ishikawa ゼオライトの製造方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 543 (C - 0783) 30 November 1990 (1990-11-30) *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 181 (C - 0830) 9 May 1991 (1991-05-09) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 006 (C - 0900) 9 January 1992 (1992-01-09) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 007 31 August 1995 (1995-08-31) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 009 31 October 1995 (1995-10-31) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2345056A (en) * 1998-03-13 2000-06-28 Council Scient Ind Res Process for the synthesis of flyash based zeolite-a
GB2345056B (en) * 1998-03-13 2000-11-01 Council Scient Ind Res Process for the synthesis of fly ash based zeolite-a
KR100274118B1 (ko) * 1998-07-08 2001-01-15 이동훈 석탄비산재로부터 에이형 제올라이트를 제조하는 방법
US6027708A (en) * 1998-09-08 2000-02-22 Council Of Scientific & Industrial Research Process for the synthesis of flyash based zeolite-Y
US6599494B2 (en) 1999-08-19 2003-07-29 K.E.M. Corporation Process for preparing artificial zeolite by a slurry reaction method
EP1078882A1 (fr) * 1999-08-24 2001-02-28 K.E.M. Corporation Procédé de préparation d'une zéolite artificielle par une méthode de réaction en barbotine
EP3978436A4 (fr) * 2019-07-19 2023-03-08 Nakanishi Industry Co., Ltd. Procédé de production se rapportant à la production en masse industrielle de zéolite artificielle de haute pureté
CN111533135A (zh) * 2020-05-13 2020-08-14 华能国际电力股份有限公司 一种动态自调节水热法制备a型粉煤灰基分子筛的方法

Also Published As

Publication number Publication date
AU5346198A (en) 1998-07-03
NL1004729C2 (nl) 1998-06-18

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