NZ203890A - A process for recovery of ai and fe salts from acidic waste waters and the production of aluminosilicate crystalline zeolites from the recovered ai salts - Google Patents

A process for recovery of ai and fe salts from acidic waste waters and the production of aluminosilicate crystalline zeolites from the recovered ai salts

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Publication number
NZ203890A
NZ203890A NZ203890A NZ20389083A NZ203890A NZ 203890 A NZ203890 A NZ 203890A NZ 203890 A NZ203890 A NZ 203890A NZ 20389083 A NZ20389083 A NZ 20389083A NZ 203890 A NZ203890 A NZ 203890A
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NZ
New Zealand
Prior art keywords
hydroxide
waste waters
iron
sodium
aluminum hydroxide
Prior art date
Application number
NZ203890A
Inventor
R Fahn
H Buckl
Original Assignee
Sued Chemie Ag
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 Sued Chemie Ag filed Critical Sued Chemie Ag
Publication of NZ203890A publication Critical patent/NZ203890A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
    • C01B33/2823—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L) from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound

Abstract

1. A process for the treatment of acid waste water containing aluminum and iron, wherein (a) the acid waste containing small amounts of colloidal silicic acid is heated to just below boiling point so as to precipitate aluminum hydroxide and hydrated iron (III) oxide and is neutralized with calcium oxide and/or calcium hydroxide ; (b) the resultant aluminum hydroxide iron (III) hydroxide precipitate is trated with sodium hydroxide until dissolution of the aluminum hydroxide as aluminate ; (c) the remaining hydrated iron (III) oxide precipitate is separated from the sodium aluminate solution, washed dried and the hydrated iron (III) oxide is pelletised for use as a gas-purifying medium or is converted by thermal treatment into iron (III) oxide suitable for use as pigment ; (d) and the sodium aluminate solution is converted into a crystalline zeolite by reaction with a water glass solution.

Description

New Zealand Paient Spedficaiion for Paient Number £03890 Priority Date(s): ^ Complete Specification Filed: piete /-wc: a«r 19861"" Publication Date: P.O. Journal, No 2 03890 N .Z .No.
NEW ZEALAND Patents Act 3953 COMPLETE SPECIFICATION "PROCESS FOR THE RECOVERY OF ALUMINUM AND IRON SALTS FROM ACIDIC WASTE WATERS." * # We, SUD-CHEMIE AKTIENGESELLSCHAFT. Lenbachplatz 6, 8000 Munchen 2, Federal Republic of Germany, incorporated under the laws of the Federal Republic of Germany do hereby declare the invention, for which we pray that a Patent may be granted to us , and the method by which it is to be performed, to be particularly described in and by the following statement : - - 1 - (Followed by 1A.) 203890 The present invention concerns a process for the recovery of aluminum and iron salts from acidic waste waters.
It was previously usual practice either to neutralize such acidic waste waters and to direct them to the river, or to discharge them into the lake or sea.
These methods, however, are risky on the grounds of environmental protection. They have the further disadvantage that the materials contained in the acidic waste waters, especially aluminum and iron, can no longer be used.
Other possible methods, therefore, have been sought. For example, the acidic waste waters accumulating with the production of clay are used for the treatment of industrial and community waste waters, along with active bentonite as an inorganic precipitation-, floccula-tion-, separation-, and absorption means.
This utilizes only a comparatively small fraction of the accumulated acidic waste waters.
The invention is based on the problem of finding a process for the recovery of aluminum and iron salts from acidic waste waters, whereby not only can the previous environmentally harmful practices be eliminated, but the substances contained in the waste waters can also be transformed into industrially useful products.
The subject of the invention is thus a process for the recovery of aluminum and iron salts from acidic waste waters, characterized in that: A. the acidic waste waters are neutralized with calcium oxide and/or calcium hydroxide for the precipitation of aluminum hydroxide and iron (III) oxide hydrate; the aluminum hydroxide-iron (III) hydroxide precipitate obtained is treated with sodium hydroxide until the aluminum hydroxide dissolves as sodium aluminatej C. the remaining iron (III) oxide hydrate precipitate is separated from the sodium aluminate solution, washed, and dried; the iron (III) oxide hydrate is pelleted for use as a gas purification substance or converted by thermal treatment to an iron (III) oxide suitable for use a6 pigment; D. and the sodium aluminate solution is transformed into a crystalline zeolite by conversion with a water-glass solution.
With the recoverable acidic waste waters according to the invention, the first concern is with waste waters accumulating with the clay extraction. Such waste waters usually contain small quantities of colloidal silicic acid. These particles of colloidal silicic acid evidently act as crystallization nuclei in the zeolite formation (step D), since it is seen surprisingly, that the zeolite format! proceeds more slowly when the sodium aluminate solution is free of silicic acid.
The reasons for the improved crystal formation are, however, still not known exactly. The fact is that zeolite formation is improved to a surprising degree if silicic acid is present.
In general, the acidic waste waters used (from the clay production) have the following analytic composition: 19 AUG 1985 ' free HC1 A 6 g/liter lift*' 203890 The acidic waste waters in step A are neutralized to a pH value of 3-8, preferably 6.6-6.7.
In the case where the iron salt or a part of the iron salt in the waste water is present in the divalent condition, the precipitation in .step A occurs in a suitable manner when the waste water is brought into contact with a gas containing oxygen. In general, air is blown through the solution to achieve this; the iron (III) oxide hydrate thus obtained is especially well-suited as a gas purification substance.
The preferred waste waters used contain aluminum and iron (and sometimes other metals) in the form of the corresponding chlorides. They also contain some free HC1.
The starting materials can, however, be waste waters containing sulfuric acid, in which case a preneutralization is carried out before step A with calcium oxide and/or calcium hydroxide, by adjusting the pH to a value of about 3. Then the separated calcium sulfate is filtered off.
The scope of the invention includes additionally the use of the iron (III) oxide hydrate produced according to step C as a gas purification substance, or the use of the iron (III) oxide produced thereby as pigment. The scope of the invention includes also the use of the zeolite produced according to step D as a molecular sieve or as an absorption material.
Ptu«e>us(y The zeolite obtained is primarily a Y-zeolite, which, as Sb-oil|e4 oo-oal explained, evidently as formed because of the presence of the "nucleus formation substances" in a well-crystallized form. "With the same resulting materials, zeolites of the A- and Y-types^ai(eE duced. >iN 19 AUG 19851 f 203890 -A- The precipitation of aluminum hydroxide and of iron (III) oxide hydrate in step A is, in general, carried out as follows: The waste waters containing hydrochloric acid, aluminum chlor' ide, and iron chloride are first heated, by a blast of superheated steam, to just below the boiling po num hydroxide and iron (III) oxide hydrate precipitates.
The treatment of the aluminum hydroxide-iron (III) oxide hydrj precipitated with sodium hydroxide in step B is generally carried oui as follows: After filtering and washing the hydroxide precipitate, sodium hydroxide is added to the hydroxide mixture, and the aluminum hydroxide is converted into sodium aluminate.
The further treatment of the iron (III) oxide hydrate in step C is as follows: The iron (III) oxide hydrate is filtered from the dissolved aluminate and washed to be free of all aluminates. The drying of the materials for the gas purification takes place at 60-110"C. In industrial use, the iron (III) oxide hydrate is formed into pellets with the addition of a pressing aid for removal of hydrogen sulfide from gas mixtures.
The iron (III) oxide to be used as pigment is obtained by cal cining the oxide hydrate at 600#C.
The iron (III) oxide hydrate obtained according to the invention is especially well-suited for gas purification, i.e., for the removal of hydrogen sulfide from diverse gas mixtures.
For the gas purification, the gases containing are led over the pelleted iron (III) oxide hydr&te substances he steam, the pH is adjusted to about .5- 203890 reactors. The more or less strongly hydrated iron oxide reacts with the hydrogen sulfide according to the following equation: Fe203 + 3H2S Fe2S3 + 3H20 +14.9 kcal The conversion of the sodium aluminate solution obtained in step D into a crystalline Y-zeolite is carried out, in general, as follows: Following known procedures., ^ crystallized Y—zeolite is obtained by producing a suspension Gf nuclei for crystal formation is produced by the reaction of sodium aluminate with sodium silicate with an excess of caustic soda; the suspension is then converted with sodium silicate to a zeolite having a Si02/Al203 mole ratio of about 5:1.
The zeolite so produced may be used as a molecular sieve or as an absorption material.
Through the "Si0o-contamination" in the aluminate obtained fron r water * the acid waste | the crystal nucleus formation seems to be improved, so that the time necessary for the crystallization of the zeolite can be greatly shortened.
The same is true for the production of zeolites of the A- and X-types.
The invention is in no way limited by the following examples: EXAMPLE 1 1500 liters of clay decompensation solution, containing hydro- chloric acid, (17.7 g/iiter A1203, 8.6 g/lbifcer Fe203) are stirred strongly with 66 kg CaO to a pH of 6.7. Then 50 g of flocculating agent, dissolved in 5 lit ere of water, is added to improve the fil- trability of the resulting hydroxide [A1(0H)3 or FE(0H)31.
After a reaction time of 4 hours, the hydroxide mixtjuxfewis filtered off in a filter press. un r 18 MAR 1986^ 203890 A The filter cake (512 kg hydroxide mixture with 90% H20) is added to 30 kg NaOH flakes, which are contained in a container of corrosion-resistant steel. The liquefying mixture is then heated and held for one hour at 90-95°C.
After cooling to 80#C, the sodium aluminate solution is separated from the iron oxide hydrate in the filter press. 631 kg of sodium aluminate solution (3.3% Al203, 3.55% Na20) is mixed with 169 kg NaOH (50% solution) and 29 kg NaOH flakes, so that 830 kg of a solution with 2.5% A1203 and 14.5% NaOH results.
The aluminate solution (830 kg), cooled to 20-25°C, is then added to 265.6 kg of sodium water glass (41° Be, 28.6% Si02) with intensive stirring. From the clear solution, the suspension of nuclei for the crystal formation is formed after a short time. After 20 minutes of stirring and warming to 40°C, the substance is filtered and washed. rsubstance 301 kg of this filtered substance (any'26%) is stirred with 421 kg sodium water glass (41® Be), 145 kg NaOH (7.5% solution), and 90 kg of water, heated to 98®C and held at this temperature for 4 hours.
After this reaction time, a crystallized Y-zeolite with a crystallinity of 100% is formed.
EXAMPLE 2 Ubo* 1500 lit ere of clay- decompensation solution containing sulfuric litre Jitfe. acid (17.7 g/liter A1203, 8.6 g/litcg Fe203) is adjusted by the addition of calcium oxide under strong stirring to a pH value of 3. The precipitated calcium sulfate is then separated over a fil£er~^ress, and the filtrate is brought up to a pH of 6.6 by the finphier addition of CaO. r 18 MAR 1986 ir ^ / f 203890 The hydroxides of aluminum and iron are filtered after the addition of 50 g of flocculating agents dissolved in 5 liters of water, and processed further as in Example 1, with a reaction time of A hours.
The accumulated iron (III) oxide hydrate still contains some calcium sulfate, which, however, does not impair the effectivity fo: the H2S-removal.
The Y-zeolite obtained by this process has, in any case, a crystallinity of 100% after a reaction time of A hours.
EXAMPLE 3 litoe. ufa. 1 liter of a sodium aluminate solution with 33 g/litcr A1«0~ , ,, , r>fc titfc and 47 g/idtcr Na^O is stirred strongly into 1 liter of an 80°C sod- U'tfe title, ium silicate solution with 81 g/liter SiC^ and 2A g/litcr Na90. Thf sodium aluminate solution is produced as described in Example 1 and increased to the desired Na20-content with sodium hydroxide.
After 8 hours of reaction^ time at 80#C, while it is stirred slowly, the resulting A-zeolite is filtered, washed, and dried (to about 20% water of hydration). A crystallized A-zeolite with a calcium bonding capacity of 130 g Ca/g of water-free product is obtaine EXAMPLE A For the synthesis of a zeolite of the Y-type, a sodium silicic l.*t?c cate solution with 83.5 g Na20/H£«r and 62 g SiC^/Wrfce-r is heated to 95*C and mixed intensively with a sodium aluminate solution con- irtle/ litis taining 71 g Na20/liter, or 66gg AljO^/Htfce*-, and also heated to 95° The sodium aluminate solution obtained according to Example 3. (3 l.'tfc, fitfe, ^ g A^O^/lrtfeer or 35.5 g Na20/iite*) must be evaporated by half in order to obtain the necessary Na20/Al203 ratio. The of 203890 SiC^/Al^O^ of the component mixture amounts to 2.5. Also, the mole ratio of l^O/SiC^ is 2, and the mole ratio of Na20/Al202 is 5.
After a reaction time of 2 hours (without stirring), the crystallized zeolite is filtered, washed, and dried.
EXAMPLE OF APPLICATION To the effectivity of the iron (III) oxide hydrate, obtained according to the invention, as a gas purification substance, a gas composed of 4 vol.% hydrogen sulfide, 42 vol.Z 52 vol.Z methane, and 2 vol.Z water, at room temperature, with a spac qoa yo/ft by u<ju«*e. of pev rie- by uolu*e aj. subvWco, cm hoiw is velocity of aboutl900/hr,l passed over 500 ml of the iron (III) oxide hydrate, obtained according to Example 1, which is in a stationary reactorj after 5 hours the sulfur content of the substance is analyti cally determined.
The sulfur content amounts to 35%. In comparison thereto, about 30Z is measured with known gas purification substances. 203890

Claims (14)

WHAT WE CLAIM IS:-
1. A process for the recovery of aluminum and iron salts from acidic waste waters and the production of alumino-silicate crystalline zeolites from the removed aluminum salts which comprises the steps of: (a) adding an alkaline-precipitating agent compris-ing the oxides or hydroxides of calcium to said waste waters to adjust the pH of said waste waters; (b) precipitating aluminum hydroxide and trivalent ferric oxide hydrate from said waste waters and separating said aluminum hydroxide and ferric oxide hydrate from the treated waste water; (c) treating the aluminum hydroxide-ferric oxide precipitate with sodium hydroxide to leach out the aluminum hydroxide by converting it to sodium aluminate; (d) separating the ferric oxide hydrate precipitate from the sodium aluminate solution; and (e) reacting said sodium aluminate solution with sodium silicate to form a crystalline alumino-silicate zeolite. ^ including
2. A process, as defined in Claim 1, the further steps of: (a) washing and drying the precipitated ferric oxide hydrate; "A "A -2MAYI986Sj 203800 - 10 - (b) pelleting the dried ferric oxide hydrate precipitate for use as an absorbant for hydrogen sulfide. including
3. A process, as defined in Claim 1,[the further steps of: (a) washing and drying the ferric oxide hydrate precipitate; (b) calcining the dry material to convert it to the oxide.
4. A process, as defined in Claim 1, in which the step of reacting said sodium aluminate solution with sodium silicate includes: (a) mixing the separated sodium aluminate solution with sodium silicate with an excess of caustic soda until a suspension of crystal-forming nuclei forms; (b) filtering this supension; (c) mixing said filtered material with additional sodium silicate and sodium hydroxide; and (d) maintaining this mixture under crystalline growth conditions for sufficient time to form crystalline zeolites, having a SiC^/A^O-^ mole ratio of substantially 5:1. ^ including
5. A process, as defined in Claim l,jthe further step of: (a) bubbling an oxygen-containing gas through said waste water to convert any divalent iron salt to the trivalent state. P including
6. A process, as defined in Claim 4, the improvement wherein the sodium aluminate solution contains small quantities of colloidal silicic acid to accelerate zeolite forma^vpin^A/ P / ^ z -2 MAY 1986 o m -11- 203890
7. A process, as defined in Claim 1, in which the acidic waste waters have the following average analysis: Al3+ 12-16 g/litre Fe3+ 4-6 g/litre Ca2+ 2-4 g/litre Mg2+ 2-4 g/litre sio2 0.2-0.4 g/litre CI" 65-90 g/litre Free HC1 4-6 g/litre .—including
8. A process, as defined in Claim 1, the improvement of adjusting the pH of the acidic waste waters in step(a) by the addition of an alkaline precipitating agent to the range of 3-8.
9. A process, as defined in Claim 1, in which the pH value is adjusted by the addition of an alkaline precipitating agent to a range of 6.6-6.7.
10. A process, as defined in Claim 1, in which the waste r including the initial waters contain sulfuric acid, step of adding the oxide or hydroxide of calcium to said waste waters so as to react said sulfuric acid to form insoluble calcium sulfate and thereafter filtering off the insoluble precipitate.
11. A gas purification substance comprising trivalent ferric according to claim 1 oxide hydrate producedfby the simultaneous precipitation of said ferric oxide hydrate and aluminum hydroxide by the addition of an alkaline precipitating agent to the waste waters and the subsequent leaching out of said aluminum hydroxide with sodium hydroxide. , v -••••. il - 2 MAY 1986Sj) i / - 12 - 203890 j- according to claim
12. A trivalent iron oxide pigment produced]by the precipitation of trivalent iron oxide hydrate and aluminum hydroxide from acidic waste waters, the subsequent leaching out of the aluminum hydroxide by treatment with sodium hydroxide solution, followed by washing, drying, and calcining to convert the hydrate over to the trivalent ferric oxide.
13. A zeolite molecular sieve or absorptive material produced according to the steps of Claim 4.
14. The use of the zeolite produced according to claim 1 as a molecular sieve or as an absorption material. SUD-CHEMIE AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By:^
NZ203890A 1982-04-15 1983-04-14 A process for recovery of ai and fe salts from acidic waste waters and the production of aluminosilicate crystalline zeolites from the recovered ai salts NZ203890A (en)

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DE19823213932 DE3213932A1 (en) 1982-04-15 1982-04-15 METHOD FOR THE TREATMENT OF ALUMINUM AND IRONIC ACIDS

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DE4306663A1 (en) * 1993-03-03 1994-09-08 Sued Chemie Ag Process for the environmentally friendly utilization of acid wastewater
DE10324561A1 (en) * 2003-05-30 2004-12-16 Süd-Chemie AG Semi-synthetic bleaching earth
EP1730324B1 (en) * 2004-03-31 2008-11-05 G. R. Trattamenti Termici - GRTT S.R.L. Process for recovering caustic soda solutions from pickling of aluminium extrusion dies
DE102004027619B4 (en) * 2004-06-05 2008-04-03 Hottinger Baldwin Messtechnik Gmbh Overload protection for a force measuring element
CN101830477B (en) * 2010-06-10 2012-12-05 济宁医学院 Technology for preparing PSAF (Polymer Silica Aluminum Ferrum) by waste rock base raw material
RU2013157943A (en) * 2011-06-03 2015-07-20 Орбит Элюминэ Инк. HEMATITIS METHOD
DE102012108298B4 (en) * 2012-05-23 2015-05-21 Envirochemie Gmbh Removal of aluminum from wash liquor
CN102718267B (en) * 2012-07-18 2013-11-20 广西大学 Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag
CN103253797B (en) * 2013-06-04 2015-06-03 苏州南风优联环保工程有限公司 Online treatment and recycling technique for waste water on anode oxidization production line
CN103788708A (en) * 2014-02-12 2014-05-14 铜陵瑞莱科技有限公司 Chitosan-containing iron oxide green pigment
US20210198768A1 (en) 2018-05-30 2021-07-01 Lixivia, Inc. Selective Extraction of Metals From Complex Inorganic Sources
CN109455748A (en) * 2018-12-17 2019-03-12 北京建工金源环保发展股份有限公司 A method of recycling aluminum nitrate from waste acid liquor
CN112551535A (en) * 2020-12-30 2021-03-26 泉州市利芝新材料科技有限公司 Spodumene iron-removing and whitening process

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DE1517727A1 (en) * 1963-03-31 1969-04-24 Baer Dr Erhardt Process for cleaning up industrial waste water
US3425800A (en) * 1967-10-05 1969-02-04 Aluminum Co Of America Production of crystalline zeolites
GB1218601A (en) * 1968-01-01 1971-01-06 Unifloc Ltd Disposal of waste liquors from pickling processes
US3494864A (en) * 1969-06-16 1970-02-10 Robert A Willihnganz Water purification process
US3798160A (en) * 1971-03-29 1974-03-19 American Metal Climax Inc Treatment of aluminum waste liquors
GB1454933A (en) * 1974-10-12 1976-11-10 Tioxide Group Ltd Process for the treatment of acidic waste liquid containing dissolved salts
JPS5221197A (en) * 1975-08-07 1977-02-17 Nitto Electric Ind Co Method of collecting laver spores

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JPS58181722A (en) 1983-10-24
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ZA832667B (en) 1983-12-28
DK166883D0 (en) 1983-04-15
ATE29869T1 (en) 1987-10-15
DE3213932A1 (en) 1983-10-27
EP0092108B1 (en) 1987-09-23
EP0092108A2 (en) 1983-10-26
DE3373806D1 (en) 1987-10-29
NO831323L (en) 1983-10-17
DK166883A (en) 1983-10-16

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