CA1052021A - Fixing agent of heavy metal - Google Patents
Fixing agent of heavy metalInfo
- Publication number
- CA1052021A CA1052021A CA191,195A CA191195A CA1052021A CA 1052021 A CA1052021 A CA 1052021A CA 191195 A CA191195 A CA 191195A CA 1052021 A CA1052021 A CA 1052021A
- Authority
- CA
- Canada
- Prior art keywords
- heavy metal
- compound
- water
- heavy
- compounds
- 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.)
- Expired
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Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Sludge (AREA)
Abstract
Abstract of the Disclosure This invention relates to fixing agents for heavy metals and heavy metal compounds and in particular to fixing agents which react with heavy metal ions or heavy metal compound precipitates of heavy metal ions and heavy metal compounds, and render heavy metal compounds insoluble.
According to the invention, aliphatic dithiocarbamate compound means a compound having an aliphatic chain which may contain a nitrogen atom in place of a carbon atom and at least two dithiocarbamate groups (>N-?-S-) and which is contained in the compound in the form of acid (R-NHCSSH or
According to the invention, aliphatic dithiocarbamate compound means a compound having an aliphatic chain which may contain a nitrogen atom in place of a carbon atom and at least two dithiocarbamate groups (>N-?-S-) and which is contained in the compound in the form of acid (R-NHCSSH or
Description
~05ZO:~
This invention re]ates to fl~ing agent~s for heavy ~eta's and heavy metal ccmlpounds and in particular to fixing agerlts which react with - heavy metal ions or heavy metal compound precipitates of heavy metal ions and heavy metal compounds, and render heavy metal compounds insoluble.
Large areas of the environment have already become polluted with heavy metals and heavy metal compounds which are discharged from mines, factories, cars, hospitals, laboratories or are scattered by-products containing heavy metals such as electric batteries and luminescent lamps.
The heavy metals and heavy metal compounds dissolve in river water or subterranean waters and are ingested by plants and animals, and then by humans when they consume the plants and animals.
It is an object of this invention to provide a fixing agent which selectively fixes heavy metals and heavy metal compounds and renders them insoluble in water.
It is another object of this invention to provide fixing agents that prevent or interfere with ingestion of heavy metals by plants.
~; It is another object to provide a fixing agent which prevents i release of heavy metals from drainage or sewage which contains heavy metal and which comes from a factory, laboratory or hospital.
It is another object to provide a method of rendering slurry or solid waste which contains heavy metal or heavy metal compounds harmless and insoluble and to prevent leaching out of heavy metal or heavy metal compounds.
Other objects of this invention will become apparent from the following specification and claims.
According to the invention, aliphatic dithiocarbamate compounds are used as fixing age~ts for heavy metals and may be mixed with soil, water or solid or slurry waste which contains heavy metal or heavy metal compounds. The fixing agents react with heavy metal or heavy metal compounds and form compounds insoluble in water.
The compounds of the invention have certain novel uses in addition - 1 - ~
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1 to being precipitants. ~or example, when slurry or granular waste contain-ing heavy metals or heavy metallic compounds, such as mud containing mercuric compounds produced as a result of electrolysis of alkali-chloride in a n~7e~r~rcell waste is packed in concrete containers which are dumped into the sea or buried in the ground. In many instances, the heavy metals or heavy metal compounds are exude through the walls of the concrete containers and pollute thelr surroundings. In such cases mixing a fixing agent such as an aliphatic or aromatic dithiocarbamate with the waste at a rate of 0.1 to 50% of the agent per volume of waste completely prevents the exudation of harmful heavy metal and heavy metal compounds and further when the agent is homogeneously mixed in concrete or mortar - in an amount of 0.001~ to 10% preferably 0.001 to 1% by volume of cement in the concrete or mortar, heavy metals and heavy metal compounds are prevented from passing through the cement or mortar walls. Moreover materials which solidify for example cement e.g. Portland cement, or resinous materials containing 0.001% to 10% preferably 0.001% to 1% of the agent can be used for packing harmful heavy metallic compounds and further, walls or containers made from such solidifying material will prevent passage there-through of heavy metals and heavy metal compounds. Such structures for example could be drainage pipes.
The agents may be used in agriculture when soils contain heavy metal or heavy metal compounds so that crops planted in the soil take up the metals or metal compounds. In such cases the passing of heavy metal or heavy metallic compound into the plants can be prevented by adding the agents to the soil. Ordinarily 0.001% to 10%, preferably 0.01% to 2~, of ; the agent is added and homogeneously mixed in the soil. The agents are most effective, when the soil has weak acidity to weak alkalinity, from pH 11 to pH 5, against mercury, copper and cadmium. Heavy metal or heavy metallic compound in irrigation water is precipitated by adding the fixing agent to the water in order to protect crops from pollution.
According to the invention, aliphatic dithiocarbamate compound means 105ZOZl a compound having an al-iphatic chain whicll may contain a nitrogen atom in place of a carbon atom and at least two dithiocarbamate groups (> N-C-S-) S
and which is contained in the compound in the form of acid (R-NHCSSH or R' > NCSSH), or salt or esters of alkali metals, alkaline earth metals and ammonium hydroxide, of the dithiocarbamic acid group.
Examples of aliphatic dithiocarbamate compounds are the following:
ethylene-di-dithiocarbamic acid (H52CNHCH2CH2NHCS2H) N,N,N-tris(dithiocarboxyl)ethylenediamine N,N,N',N'-tetra(dithiocarboxyl)ethylenediamine 1,3- or 1,2-propylenebisdithiocarbamic acid N,N,N'-tris(dithiocarboxyl)propylenediamine N,N,N',N'-tetra(dithiocarboxyl)propylenediamine tetramethylenebisdithiocarbamic acid tris or tetra-(dithiocarboxyl)propylenediamine hexamethylenebisdithiocarbamic acid octamethylenebisdithiocarbamic acid N,N -bis~dithiocarboxyl)diethylenetriamine (HS2CHNCH2CH2NHCH2CH2NHCS2H) N ,N ,N -tris(dithiocarboxyl)diethylenetriamine N ,N ,N ,N3-tetra(dithiocarboxyl)diethylenetriamine N ,N ,N ,N ,N -penta(dithiocarboxyl?diethylenetriamine Nl,N -bis(dithiocarboxyl)triethylenetetramine (HS2CNHC2H4NHC2H4NHC2H4NHCS2H) N ,N ,N -tris(dithiocarboxyl)triethylenetetramine ; 25 N ,N ,N ,N -tetra(dithiocarboxyl)triethylenetetramine N ,Nl,N2,N ,N -penta(dithiocarboxyl)triethylenetetramine N ,N ,N ,N ,N ,N -hexa(dithiocarboxyl)triethylenetetramine '-~ - 3 -~0520Zl N ,N -bis(dithioc<lrl-oxyl)tctraetb~lellepentamine N ,N3,N5-tris(dithiocarboxyl)tetraethylenepentamine (HS2CNHC2HLNHC2H4NCS211C2H4NHC2H4NHCS2H) N ,N ,N ,N -tetra(dithiocarboxyl)tetraethylenepentamine N ,N ,N3,N4,N5-penta(dithiocarboxyl)tetraethylenepentamine N ,N ,N ,N ,N ,N ,N -hepta(dithiocarboxyl)tetraethylenetenpamine - 3a -Nl,Nl,N2,1;3,N4,Ns-he,xa(dithiocarhoxylltctr3etllylenepcntflmine Nl ,N6-bis(di~h-ocarl)oxyl)pentaeLllylenehexamine N~ ,N3,N6-tri(dithiocarboxyl)pentaetllylenellexamine Nl ,N3,N4 ,N6-tetra(dithiocarboxyl)pcntaetllylcnehexamine Nl,N2,N3,N~,Ns,N6-hcxa(di~llioc~rboxyl)pent2ethylellellexamine bis(dithiocarboxyl)propylcnedi~mine trisdithiocarboxyldipropylenc~riamine Nl, N4 - bis(ditl-iocarbox.yl)tripropylenetetramine Nl,N2,N4-tris(di.thiocarboxyl)tripropylcnetetraminc N~,N2,N3,N4-tetra(dithiocarboxyl)tripropylellete~ramine Nl,NI,N2,N3,N4-renta(ditlliocarboxyl)tripropylctletetramille Nl,NI,N2,N3,N4,N4-hc,xa(d$thiocarboxyl)trirropyleltetetramine Nl ,Ns-his(dithiocarboxyl)tetrapropylenepentamine Nl,N3,Ns-tris(ditlliocarbox~l)tetrapro~ylencpent~mine Nl,N2,N3,Ns-tetra(dithiocarboxyl)tetrapropylenepentamine Nl,N2,N3,N4,Ns-penta(diLhiocarboxyl)totrapropylenol)entaminc Nl,NI,N2,N3,N~,Ns-hexa(clithiocarboxyl)tetrapropy~ellepelltamine .NI,N3-bi.s(dithi.ocarboxyl?dibutylenetriamille Nl,N2,N3-trls(dithiocarboxyl)dibutylcnecriamille . , Nl,N3-bls(dithioc~rboxyl)tributylcnctriamine Nl,N2,N3--tris(dithiocarboxyl)~rib~tylenetriamine : N~ -bis(dithi.vcarboxyl?tetrahu~ylenepentamine Nl,N2,N~-tris(ditllioc~rhoxy~)tctri~butylenepentam;ne Nl,N2,N3,N'-tetra(dithiocarhoY:yl)tetrabuLylenepetltamine poly(N-dithiocarboxyl)polyetliyleneimine .. .
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~052021 Allphatic dithiocarbaulate ~ompvunds h~lving ~ess ~han 4 carbon atoms show phytotoxicity, and aromatic dithlocarban)ate compounds are le&~
stable than aliphatic dithiocarbamate compounds, 50 that aliphatic dithio-carbamate compounds having 5 or more carbon atoms are preferred according to the invention.
These dithiocarbamate compounds can be easily prepared from corres-ponding amine compounds such as ethylenediamine, diethylenetriamir.e, triethyl-enetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetri-amine,tripropylenetetramine, tetrapropylenepe~tamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine by reacting carbon bisulfide in thepresenceof solvent such as acetone, methylethyl ketonc dnd water, and alkaline catalysts such as sodium hydroxide, potassium hydroxide and ammonium hydrox~eat a temperature from -10C. to 60C., preferably at 20C. to 45C.
The reaction mixtures contain dithiocarbamate compound which has a red-orange or brown colour, in the form of a salt. The reflction between the hydrogen atom which combines with the nitrogen atom of an amino or imino group and carbon bisulfide proceedsquantitatively. Accordingly the same number of gram molecules of carbon disulfide as the proposed number of dithlocarbamate groups of the proposed compound iB employed in its preparation.
For example, when two dithiocarbamate groups are intended to be introduced in amine compound, two gram moles of carbon bisulfide are reacted with one gram mole of amine compound. Ordinarily aliphatic dithio-carbamate compounds can be used in the form of an aqueous solution as a fixing agent. If desired an aqueous solution of an aliphatic dithiocarba-mate compound may be impregnated into a carrier and a granular or paste fixing agent can be obtained. In this case 1 to 30% of aliphatic or aromatic dithiocarbamate compound is preferably used.
Many kinds of materials having a porous structurc and large specific surfaces can be emyloyed as the carrier and preferably porous lOSZOZl materlal having large 6pecific surface~ mo~e than 1 m /g (BET's method using argon gas), for example, diatomaceous earth, pumice stone, zeolite, kaolin, vermiculite, alumina (aluminum oxide), silicagel, co~e, activa~ed charcoal, graphlte, bentonite, foamed urethane res~n having open cells.
The fixing agents can s¢lectlvely react with heavy metal and heavy metallic compounds such as: nickel, chromium, zinc, lead, copper, cadmium, silver, arsenic, manganese, bismuth, vsnadium, and particularly, mercury, even if the heavy metals or compounds exist as nonionlc or ionic compounds. So far as concerns mercuric and silver compounds, various types of compound can be fixed, for example, metallic oxides such as HgO andAg2O, metallic chlorides such as HgC12 and AgCl, metalllc sulphates such as HgS04, Hg2S04 and AgS04, metallic nitrates such as Hg(N03)2 and Hg2(N03)2, metallic sulphides such as HgS and Hg2S, and organometallic cDmpounds such as methylmercuric chloride, ethylmercuric chloride, phenylmercuric acetate, ethylmercuric iodide, methylmercuric iodide, methylmercuric bromide, phenylmercuric chloride, diphenylmercury and phenylmercuric benzoate are fixed.
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10520Zl 1 lurtl~orm(!r(~ (lmillm ;~ (lnli~lm compollnd~ (~.ln l-(~ fixed by the agent even lf the cadmium compounds are nonionic or ionic, for example CdSO4.
CdC12, CdS, CdO, Cd(OH)2.
The advantages of the present invention will be shown in the following Examples. All quantities described in this specification and the appended claims as "parts" or "percent" refer to "parts by weight" or 'percent by weight" unless expressly stated otherwise.
Example 1 Preparation of fixing agents.
80 parts of NaOH, 500 parts of water and 60 parts of ethylene diamine were mixed together, and 152 parts of carbon bisulfide were added dropwise at 30C. to 40C. under vigorous stirring. After 1 hour of digestion nitrogen gas was blown through the reaction mixture in order to remove unreacted carbon bisulfide, and a brown-orange transparent aqueous solution containing 31.0% of sodium ethylenebisdithiocarbamate (NaS2CNH-CH2CH2NHCS2Na) was obtained. The reaction solution was used as a fixing agent without further treatment.
. ., Example 2~ 25 Various amines, basic compounds and carbon bisulfide, as shown in Table 1, were reacted according to Example 1 and various kinds of fixing agents were obtained, as listed in Table 1.
` Example 26 An aliphatic dithiocarboxyl compound identified in Table 1, ;". ' .
``~` Portland cement, water, and mud containing mercuric compounds by-produced in a sodium chloride electroylsis plant were mixed according to Table 2 and solidified as blocks 16 cm high x 4 cm wide x 4 cm long. The blocks were allowed to stand for 14 days and were then soaked in a quantity of sea water 4 times the volume of the block.
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105ZOZl Concentrat on of mercury of the sea water or water was determined after 1 hour, 1 day, 14 days, 1 month and 1 year, the results belng listed in Table 2.
Mud contained NaCl, Mg(OH)2, CaS04 2H20, CaC03, C, about 120 ppm of Mercury, and about 45% of water.
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~ ~ ~ __ _~ _ ~ __ __ ---pl~ 27 1~5ZOZl 500 parts of dry slutge contalning copper and copper compounds s by-products of a factory electro plating copper, aDd 0.5 part of tetra (dlthlocarboxyl sodi~m) triethylenetetramine tNo. 5 in Table 1) were mixed ell and 25 parts of cxfpoxidc resin and 25 parts of curing agent ~amines) vere lncorporated.
The mixture was cured in a mould and a test block 4 cm x 4 cm x 4 cm was produced.
Tbe test block was soaked ln sea water or water 4 times the 10 ~olume of the block. After 1 day, 1 month and 3 months copper concentration of the sea water or water was determined, the results belng llsted in Table 3. j Table 3 comp osition (parts)~oppel test copper concentration (ppm) resin fixing agent sludge water 1 day 1 month ¦ 3 monthS
._ l not not not . tetra(dlthiocarboxyl- waterdetected* detected detected sodium) eriethylene 500 _ tetramine (0.5) water ~. n ., ., . _ water n 0.23 l.S
non 500 (control) __ ~ter 0.46 2.4 * less than 0.1 ppm ~-ample 28 100 parts of mud contalning 28 ppm of mercury and 38X of water, by-products of an electrolysis plant for sodium chloride, ant fixing agent, ~Identified by number in Table 1) were mixed well for 10 minutes and a slurry obtained.
After 1 hour, 1 week, 1 month, 3 months, 6 months and 1 year, 8 grs 30 of the mi~cture and 200 ml of pure water or 200 ml of diluted aqueous solution of hydrochloric acid of pH 8 were mixed for 5~15 minutes ant the concentra-- tion of mercury in the water was determlned.
; The results are listed ln Table 4.
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lOSZ021 Example 29 100 parts of copper sludge, by-product of a factory of electro plating copper, was ad~usted to pH 7 and 1.0~ 0.5 part of fixing agent (converted to net content of effective compound) was added to the sludge and mixed for lO minutes. Then the treated sludge was tested by the method of Example 28 and the concentratlon of copper in the extracting water was determined.
The results are listed in Table 5.
In Table 5, fixing agents are identified by number according to Table 1.
Table 5 fixing agent concentration of copper (ppm) copper mixing number sludge time time , of (parts) (parts) (min.) l 3 : Table 1 1 hour 1 week 1 month months S 1.0 100 10 detected* detected detected ted __ _ __ 3 0.5 100 15 ~ .- .. ..
13 0.5 100 10 .. .. ll .-17 1.0 100 10 .. .- ll ., 20 - 20 1.0 100 15 ll .. .. ..
_ _ 0 _ 100 0 12 19 17 14 ~control) _ * less than 0.1 ppm Example 30 100 parts of cadmium sludge (containing 13 ppm of cadmium and 73.5% of water) was ad~usted to pH 8 and 0.1~ 0.5 parts of fixing agent ,~ (converted to net content of effective compound) was added to the sludge and mixed for 10 minutes. Then the treated sludge was tested by the method of Example 28 and the concentration of cadmium in the extracting water were determined.
t The results are listed in Table 6.
lOS202~
1 Table 6 fixing ~gent concentration of cadmium (ppm) _ _ cadmium mixing _ number sludge time test time of (part) (parts) (min.) water _ Table 1 1 hours 1 week 1 month 3 nths water ~0.01 <0.01 <0.01 cO.01 1 0.1 100 10 . _ .. _ _ 3 0.1 100 10 sea water l water ..
; 4 0.2 100 10 .. wetewater _ , . .
8 O S 100 15 sea water _ _ water 14 0.1 100 10 Saetewater - __ - 16 0.3 100 10 _ _ . waetaera t er ~ " n 17 0.5 100 15 sea water - l ~ _ water _ j _ !~ 20 0.5 100 10 sea water i "
water 0.6 O.S 0.4 0.5 O _ 100 O . .
sea water 0.8 1.1 1.0 0.8 . .
~ *< 0.01 means less than 0.01 r 20 Example 31 270 parts of soil (containing 20.3 ppm of cadmium and 63X of water) from a paddy field and 1.0~ 0.3 parts of fixing agent were mixed well.
After 3 days, 14 days, 1 month, 3 months and 6 months, 100 grs of the soil was treated to the extent that the water content was 5~, and 10.0 grs of soil were mixed with 50 m~ of an aqueous solution of citric acid of pH 3. Then the mixture was shaken for 1 hour and the concentration of extracted cadmium ln the aqueous solution was determined.
The results, and the fixing agents are listed in Table 7. Fixing agents were shown by number according to Table 1.
:
lOSZ02~
1 Table 7 fixing agent ConccntraLion of cad~ium (ppm) . . . . _ numbcr tlme of (parts) Table 1 3 days 14 days 1 month 3 months 6 months . ... ._. __ .
0.5 0.31 0.28 0.27 0.27 0.25 6 0.3 0.56 0.53 0.52 0.51 0.49 8 0.5 0.49 0.48 0.46 0.46 0.45 7 0.3 0.63 0.61 0.59 0.57 0.57 3 0.5 0.23 0.20 0.18 0.19 0.16 1 0.5 0.35 0.31 0.30 0.30 0.28 - 1010 0.5 0.65 0.63 0.63 0.61 0.61 11 1.0 0.74 0.73 0.73 0.71 0.72 12 O. 0.31 0.28 0.27 0.27 0.26 13 0.3 0.39 0.35 0.32 0.32 0.30 14 0.5 0.32 0.31 0.30 0.28 0.28 0.5 0.41 0.40 0.38 0.37 0.37 ; 16 0.5 0.52 0.50 0.49 0.47 0.48 ; ~ 17 0.5 0.65 0.65 0.63 0.62 0.61 18 1.0 0.58 0.57 0.54 0.53 0.53 .~ 19 0.3 0.73 0.71 0.68 0.66 0.65 - 20 0.5 0.63 0.~2 0.60 0.59 0.59 (control) 0 1.2 1.3 1.1 1.2 1.2 . . .
ample 32-, .
Soil (Ohiso-machi Naka-gun Kanagawa-ken Japan) was dried for 11 days at room temperature and for 5 hours at 110C. 900 grs of the æoil were placed in each of several pots, 11.5 cm inside diameter snd 11 cm high and an aqueous solution of CdSO4-4H2O was added in order to give a total cadmium content of 20 ppm in the soil of each pot and 4 m~ of fertilizer containing 120 mg of KH2P04, 40 mg of KC~ and 320 mg of tNH4)2S04 and 250 mL of water were then added to each pot. After 1 day, 0.003X, 0.03%
or 0.3X of fixing agents were added in each pot and mixed well. After 4 days, 100rV200 m~ of water was added and 15 grains of rice were planted in each pot.
The water was kept at a depth of 2 cm over the surface of 80il in the 30 pots, and for 50 days the pots were placed in a greenhouse ant lighted at night.
After 50 days rice plants were pulled out and washed well and the concentration of cadmium in rootsJ or stalks and leaves was determined.
The results and the fixlng agents used in ~:he exampleare~edin 10520Zl ~ 1,~
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.
This invention re]ates to fl~ing agent~s for heavy ~eta's and heavy metal ccmlpounds and in particular to fixing agerlts which react with - heavy metal ions or heavy metal compound precipitates of heavy metal ions and heavy metal compounds, and render heavy metal compounds insoluble.
Large areas of the environment have already become polluted with heavy metals and heavy metal compounds which are discharged from mines, factories, cars, hospitals, laboratories or are scattered by-products containing heavy metals such as electric batteries and luminescent lamps.
The heavy metals and heavy metal compounds dissolve in river water or subterranean waters and are ingested by plants and animals, and then by humans when they consume the plants and animals.
It is an object of this invention to provide a fixing agent which selectively fixes heavy metals and heavy metal compounds and renders them insoluble in water.
It is another object of this invention to provide fixing agents that prevent or interfere with ingestion of heavy metals by plants.
~; It is another object to provide a fixing agent which prevents i release of heavy metals from drainage or sewage which contains heavy metal and which comes from a factory, laboratory or hospital.
It is another object to provide a method of rendering slurry or solid waste which contains heavy metal or heavy metal compounds harmless and insoluble and to prevent leaching out of heavy metal or heavy metal compounds.
Other objects of this invention will become apparent from the following specification and claims.
According to the invention, aliphatic dithiocarbamate compounds are used as fixing age~ts for heavy metals and may be mixed with soil, water or solid or slurry waste which contains heavy metal or heavy metal compounds. The fixing agents react with heavy metal or heavy metal compounds and form compounds insoluble in water.
The compounds of the invention have certain novel uses in addition - 1 - ~
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lOSZOZ~
1 to being precipitants. ~or example, when slurry or granular waste contain-ing heavy metals or heavy metallic compounds, such as mud containing mercuric compounds produced as a result of electrolysis of alkali-chloride in a n~7e~r~rcell waste is packed in concrete containers which are dumped into the sea or buried in the ground. In many instances, the heavy metals or heavy metal compounds are exude through the walls of the concrete containers and pollute thelr surroundings. In such cases mixing a fixing agent such as an aliphatic or aromatic dithiocarbamate with the waste at a rate of 0.1 to 50% of the agent per volume of waste completely prevents the exudation of harmful heavy metal and heavy metal compounds and further when the agent is homogeneously mixed in concrete or mortar - in an amount of 0.001~ to 10% preferably 0.001 to 1% by volume of cement in the concrete or mortar, heavy metals and heavy metal compounds are prevented from passing through the cement or mortar walls. Moreover materials which solidify for example cement e.g. Portland cement, or resinous materials containing 0.001% to 10% preferably 0.001% to 1% of the agent can be used for packing harmful heavy metallic compounds and further, walls or containers made from such solidifying material will prevent passage there-through of heavy metals and heavy metal compounds. Such structures for example could be drainage pipes.
The agents may be used in agriculture when soils contain heavy metal or heavy metal compounds so that crops planted in the soil take up the metals or metal compounds. In such cases the passing of heavy metal or heavy metallic compound into the plants can be prevented by adding the agents to the soil. Ordinarily 0.001% to 10%, preferably 0.01% to 2~, of ; the agent is added and homogeneously mixed in the soil. The agents are most effective, when the soil has weak acidity to weak alkalinity, from pH 11 to pH 5, against mercury, copper and cadmium. Heavy metal or heavy metallic compound in irrigation water is precipitated by adding the fixing agent to the water in order to protect crops from pollution.
According to the invention, aliphatic dithiocarbamate compound means 105ZOZl a compound having an al-iphatic chain whicll may contain a nitrogen atom in place of a carbon atom and at least two dithiocarbamate groups (> N-C-S-) S
and which is contained in the compound in the form of acid (R-NHCSSH or R' > NCSSH), or salt or esters of alkali metals, alkaline earth metals and ammonium hydroxide, of the dithiocarbamic acid group.
Examples of aliphatic dithiocarbamate compounds are the following:
ethylene-di-dithiocarbamic acid (H52CNHCH2CH2NHCS2H) N,N,N-tris(dithiocarboxyl)ethylenediamine N,N,N',N'-tetra(dithiocarboxyl)ethylenediamine 1,3- or 1,2-propylenebisdithiocarbamic acid N,N,N'-tris(dithiocarboxyl)propylenediamine N,N,N',N'-tetra(dithiocarboxyl)propylenediamine tetramethylenebisdithiocarbamic acid tris or tetra-(dithiocarboxyl)propylenediamine hexamethylenebisdithiocarbamic acid octamethylenebisdithiocarbamic acid N,N -bis~dithiocarboxyl)diethylenetriamine (HS2CHNCH2CH2NHCH2CH2NHCS2H) N ,N ,N -tris(dithiocarboxyl)diethylenetriamine N ,N ,N ,N3-tetra(dithiocarboxyl)diethylenetriamine N ,N ,N ,N ,N -penta(dithiocarboxyl?diethylenetriamine Nl,N -bis(dithiocarboxyl)triethylenetetramine (HS2CNHC2H4NHC2H4NHC2H4NHCS2H) N ,N ,N -tris(dithiocarboxyl)triethylenetetramine ; 25 N ,N ,N ,N -tetra(dithiocarboxyl)triethylenetetramine N ,Nl,N2,N ,N -penta(dithiocarboxyl)triethylenetetramine N ,N ,N ,N ,N ,N -hexa(dithiocarboxyl)triethylenetetramine '-~ - 3 -~0520Zl N ,N -bis(dithioc<lrl-oxyl)tctraetb~lellepentamine N ,N3,N5-tris(dithiocarboxyl)tetraethylenepentamine (HS2CNHC2HLNHC2H4NCS211C2H4NHC2H4NHCS2H) N ,N ,N ,N -tetra(dithiocarboxyl)tetraethylenepentamine N ,N ,N3,N4,N5-penta(dithiocarboxyl)tetraethylenepentamine N ,N ,N ,N ,N ,N ,N -hepta(dithiocarboxyl)tetraethylenetenpamine - 3a -Nl,Nl,N2,1;3,N4,Ns-he,xa(dithiocarhoxylltctr3etllylenepcntflmine Nl ,N6-bis(di~h-ocarl)oxyl)pentaeLllylenehexamine N~ ,N3,N6-tri(dithiocarboxyl)pentaetllylenellexamine Nl ,N3,N4 ,N6-tetra(dithiocarboxyl)pcntaetllylcnehexamine Nl,N2,N3,N~,Ns,N6-hcxa(di~llioc~rboxyl)pent2ethylellellexamine bis(dithiocarboxyl)propylcnedi~mine trisdithiocarboxyldipropylenc~riamine Nl, N4 - bis(ditl-iocarbox.yl)tripropylenetetramine Nl,N2,N4-tris(di.thiocarboxyl)tripropylcnetetraminc N~,N2,N3,N4-tetra(dithiocarboxyl)tripropylellete~ramine Nl,NI,N2,N3,N4-renta(ditlliocarboxyl)tripropylctletetramille Nl,NI,N2,N3,N4,N4-hc,xa(d$thiocarboxyl)trirropyleltetetramine Nl ,Ns-his(dithiocarboxyl)tetrapropylenepentamine Nl,N3,Ns-tris(ditlliocarbox~l)tetrapro~ylencpent~mine Nl,N2,N3,Ns-tetra(dithiocarboxyl)tetrapropylenepentamine Nl,N2,N3,N4,Ns-penta(diLhiocarboxyl)totrapropylenol)entaminc Nl,NI,N2,N3,N~,Ns-hexa(clithiocarboxyl)tetrapropy~ellepelltamine .NI,N3-bi.s(dithi.ocarboxyl?dibutylenetriamille Nl,N2,N3-trls(dithiocarboxyl)dibutylcnecriamille . , Nl,N3-bls(dithioc~rboxyl)tributylcnctriamine Nl,N2,N3--tris(dithiocarboxyl)~rib~tylenetriamine : N~ -bis(dithi.vcarboxyl?tetrahu~ylenepentamine Nl,N2,N~-tris(ditllioc~rhoxy~)tctri~butylenepentam;ne Nl,N2,N3,N'-tetra(dithiocarhoY:yl)tetrabuLylenepetltamine poly(N-dithiocarboxyl)polyetliyleneimine .. .
,~ I
~052021 Allphatic dithiocarbaulate ~ompvunds h~lving ~ess ~han 4 carbon atoms show phytotoxicity, and aromatic dithlocarban)ate compounds are le&~
stable than aliphatic dithiocarbamate compounds, 50 that aliphatic dithio-carbamate compounds having 5 or more carbon atoms are preferred according to the invention.
These dithiocarbamate compounds can be easily prepared from corres-ponding amine compounds such as ethylenediamine, diethylenetriamir.e, triethyl-enetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetri-amine,tripropylenetetramine, tetrapropylenepe~tamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine by reacting carbon bisulfide in thepresenceof solvent such as acetone, methylethyl ketonc dnd water, and alkaline catalysts such as sodium hydroxide, potassium hydroxide and ammonium hydrox~eat a temperature from -10C. to 60C., preferably at 20C. to 45C.
The reaction mixtures contain dithiocarbamate compound which has a red-orange or brown colour, in the form of a salt. The reflction between the hydrogen atom which combines with the nitrogen atom of an amino or imino group and carbon bisulfide proceedsquantitatively. Accordingly the same number of gram molecules of carbon disulfide as the proposed number of dithlocarbamate groups of the proposed compound iB employed in its preparation.
For example, when two dithiocarbamate groups are intended to be introduced in amine compound, two gram moles of carbon bisulfide are reacted with one gram mole of amine compound. Ordinarily aliphatic dithio-carbamate compounds can be used in the form of an aqueous solution as a fixing agent. If desired an aqueous solution of an aliphatic dithiocarba-mate compound may be impregnated into a carrier and a granular or paste fixing agent can be obtained. In this case 1 to 30% of aliphatic or aromatic dithiocarbamate compound is preferably used.
Many kinds of materials having a porous structurc and large specific surfaces can be emyloyed as the carrier and preferably porous lOSZOZl materlal having large 6pecific surface~ mo~e than 1 m /g (BET's method using argon gas), for example, diatomaceous earth, pumice stone, zeolite, kaolin, vermiculite, alumina (aluminum oxide), silicagel, co~e, activa~ed charcoal, graphlte, bentonite, foamed urethane res~n having open cells.
The fixing agents can s¢lectlvely react with heavy metal and heavy metallic compounds such as: nickel, chromium, zinc, lead, copper, cadmium, silver, arsenic, manganese, bismuth, vsnadium, and particularly, mercury, even if the heavy metals or compounds exist as nonionlc or ionic compounds. So far as concerns mercuric and silver compounds, various types of compound can be fixed, for example, metallic oxides such as HgO andAg2O, metallic chlorides such as HgC12 and AgCl, metalllc sulphates such as HgS04, Hg2S04 and AgS04, metallic nitrates such as Hg(N03)2 and Hg2(N03)2, metallic sulphides such as HgS and Hg2S, and organometallic cDmpounds such as methylmercuric chloride, ethylmercuric chloride, phenylmercuric acetate, ethylmercuric iodide, methylmercuric iodide, methylmercuric bromide, phenylmercuric chloride, diphenylmercury and phenylmercuric benzoate are fixed.
~i ~
10520Zl 1 lurtl~orm(!r(~ (lmillm ;~ (lnli~lm compollnd~ (~.ln l-(~ fixed by the agent even lf the cadmium compounds are nonionic or ionic, for example CdSO4.
CdC12, CdS, CdO, Cd(OH)2.
The advantages of the present invention will be shown in the following Examples. All quantities described in this specification and the appended claims as "parts" or "percent" refer to "parts by weight" or 'percent by weight" unless expressly stated otherwise.
Example 1 Preparation of fixing agents.
80 parts of NaOH, 500 parts of water and 60 parts of ethylene diamine were mixed together, and 152 parts of carbon bisulfide were added dropwise at 30C. to 40C. under vigorous stirring. After 1 hour of digestion nitrogen gas was blown through the reaction mixture in order to remove unreacted carbon bisulfide, and a brown-orange transparent aqueous solution containing 31.0% of sodium ethylenebisdithiocarbamate (NaS2CNH-CH2CH2NHCS2Na) was obtained. The reaction solution was used as a fixing agent without further treatment.
. ., Example 2~ 25 Various amines, basic compounds and carbon bisulfide, as shown in Table 1, were reacted according to Example 1 and various kinds of fixing agents were obtained, as listed in Table 1.
` Example 26 An aliphatic dithiocarboxyl compound identified in Table 1, ;". ' .
``~` Portland cement, water, and mud containing mercuric compounds by-produced in a sodium chloride electroylsis plant were mixed according to Table 2 and solidified as blocks 16 cm high x 4 cm wide x 4 cm long. The blocks were allowed to stand for 14 days and were then soaked in a quantity of sea water 4 times the volume of the block.
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105ZOZl Concentrat on of mercury of the sea water or water was determined after 1 hour, 1 day, 14 days, 1 month and 1 year, the results belng listed in Table 2.
Mud contained NaCl, Mg(OH)2, CaS04 2H20, CaC03, C, about 120 ppm of Mercury, and about 45% of water.
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~ ~ ~ __ _~ _ ~ __ __ ---pl~ 27 1~5ZOZl 500 parts of dry slutge contalning copper and copper compounds s by-products of a factory electro plating copper, aDd 0.5 part of tetra (dlthlocarboxyl sodi~m) triethylenetetramine tNo. 5 in Table 1) were mixed ell and 25 parts of cxfpoxidc resin and 25 parts of curing agent ~amines) vere lncorporated.
The mixture was cured in a mould and a test block 4 cm x 4 cm x 4 cm was produced.
Tbe test block was soaked ln sea water or water 4 times the 10 ~olume of the block. After 1 day, 1 month and 3 months copper concentration of the sea water or water was determined, the results belng llsted in Table 3. j Table 3 comp osition (parts)~oppel test copper concentration (ppm) resin fixing agent sludge water 1 day 1 month ¦ 3 monthS
._ l not not not . tetra(dlthiocarboxyl- waterdetected* detected detected sodium) eriethylene 500 _ tetramine (0.5) water ~. n ., ., . _ water n 0.23 l.S
non 500 (control) __ ~ter 0.46 2.4 * less than 0.1 ppm ~-ample 28 100 parts of mud contalning 28 ppm of mercury and 38X of water, by-products of an electrolysis plant for sodium chloride, ant fixing agent, ~Identified by number in Table 1) were mixed well for 10 minutes and a slurry obtained.
After 1 hour, 1 week, 1 month, 3 months, 6 months and 1 year, 8 grs 30 of the mi~cture and 200 ml of pure water or 200 ml of diluted aqueous solution of hydrochloric acid of pH 8 were mixed for 5~15 minutes ant the concentra-- tion of mercury in the water was determlned.
; The results are listed ln Table 4.
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-- 12 ~
lOSZ021 Example 29 100 parts of copper sludge, by-product of a factory of electro plating copper, was ad~usted to pH 7 and 1.0~ 0.5 part of fixing agent (converted to net content of effective compound) was added to the sludge and mixed for lO minutes. Then the treated sludge was tested by the method of Example 28 and the concentratlon of copper in the extracting water was determined.
The results are listed in Table 5.
In Table 5, fixing agents are identified by number according to Table 1.
Table 5 fixing agent concentration of copper (ppm) copper mixing number sludge time time , of (parts) (parts) (min.) l 3 : Table 1 1 hour 1 week 1 month months S 1.0 100 10 detected* detected detected ted __ _ __ 3 0.5 100 15 ~ .- .. ..
13 0.5 100 10 .. .. ll .-17 1.0 100 10 .. .- ll ., 20 - 20 1.0 100 15 ll .. .. ..
_ _ 0 _ 100 0 12 19 17 14 ~control) _ * less than 0.1 ppm Example 30 100 parts of cadmium sludge (containing 13 ppm of cadmium and 73.5% of water) was ad~usted to pH 8 and 0.1~ 0.5 parts of fixing agent ,~ (converted to net content of effective compound) was added to the sludge and mixed for 10 minutes. Then the treated sludge was tested by the method of Example 28 and the concentration of cadmium in the extracting water were determined.
t The results are listed in Table 6.
lOS202~
1 Table 6 fixing ~gent concentration of cadmium (ppm) _ _ cadmium mixing _ number sludge time test time of (part) (parts) (min.) water _ Table 1 1 hours 1 week 1 month 3 nths water ~0.01 <0.01 <0.01 cO.01 1 0.1 100 10 . _ .. _ _ 3 0.1 100 10 sea water l water ..
; 4 0.2 100 10 .. wetewater _ , . .
8 O S 100 15 sea water _ _ water 14 0.1 100 10 Saetewater - __ - 16 0.3 100 10 _ _ . waetaera t er ~ " n 17 0.5 100 15 sea water - l ~ _ water _ j _ !~ 20 0.5 100 10 sea water i "
water 0.6 O.S 0.4 0.5 O _ 100 O . .
sea water 0.8 1.1 1.0 0.8 . .
~ *< 0.01 means less than 0.01 r 20 Example 31 270 parts of soil (containing 20.3 ppm of cadmium and 63X of water) from a paddy field and 1.0~ 0.3 parts of fixing agent were mixed well.
After 3 days, 14 days, 1 month, 3 months and 6 months, 100 grs of the soil was treated to the extent that the water content was 5~, and 10.0 grs of soil were mixed with 50 m~ of an aqueous solution of citric acid of pH 3. Then the mixture was shaken for 1 hour and the concentration of extracted cadmium ln the aqueous solution was determined.
The results, and the fixing agents are listed in Table 7. Fixing agents were shown by number according to Table 1.
:
lOSZ02~
1 Table 7 fixing agent ConccntraLion of cad~ium (ppm) . . . . _ numbcr tlme of (parts) Table 1 3 days 14 days 1 month 3 months 6 months . ... ._. __ .
0.5 0.31 0.28 0.27 0.27 0.25 6 0.3 0.56 0.53 0.52 0.51 0.49 8 0.5 0.49 0.48 0.46 0.46 0.45 7 0.3 0.63 0.61 0.59 0.57 0.57 3 0.5 0.23 0.20 0.18 0.19 0.16 1 0.5 0.35 0.31 0.30 0.30 0.28 - 1010 0.5 0.65 0.63 0.63 0.61 0.61 11 1.0 0.74 0.73 0.73 0.71 0.72 12 O. 0.31 0.28 0.27 0.27 0.26 13 0.3 0.39 0.35 0.32 0.32 0.30 14 0.5 0.32 0.31 0.30 0.28 0.28 0.5 0.41 0.40 0.38 0.37 0.37 ; 16 0.5 0.52 0.50 0.49 0.47 0.48 ; ~ 17 0.5 0.65 0.65 0.63 0.62 0.61 18 1.0 0.58 0.57 0.54 0.53 0.53 .~ 19 0.3 0.73 0.71 0.68 0.66 0.65 - 20 0.5 0.63 0.~2 0.60 0.59 0.59 (control) 0 1.2 1.3 1.1 1.2 1.2 . . .
ample 32-, .
Soil (Ohiso-machi Naka-gun Kanagawa-ken Japan) was dried for 11 days at room temperature and for 5 hours at 110C. 900 grs of the æoil were placed in each of several pots, 11.5 cm inside diameter snd 11 cm high and an aqueous solution of CdSO4-4H2O was added in order to give a total cadmium content of 20 ppm in the soil of each pot and 4 m~ of fertilizer containing 120 mg of KH2P04, 40 mg of KC~ and 320 mg of tNH4)2S04 and 250 mL of water were then added to each pot. After 1 day, 0.003X, 0.03%
or 0.3X of fixing agents were added in each pot and mixed well. After 4 days, 100rV200 m~ of water was added and 15 grains of rice were planted in each pot.
The water was kept at a depth of 2 cm over the surface of 80il in the 30 pots, and for 50 days the pots were placed in a greenhouse ant lighted at night.
After 50 days rice plants were pulled out and washed well and the concentration of cadmium in rootsJ or stalks and leaves was determined.
The results and the fixlng agents used in ~:he exampleare~edin 10520Zl ~ 1,~
K . a O. ~__ ~C= U~ OD ~ O 00 _ ~ ~ o~ c~ co a~ co o~ oD
~ _ :~ 'CO ~D. _ _ ,., `O, ~ - O _ . l _ _ _ X ~ 00 ~ ~ CO O O
1 o ~ o =~ ~ u~ ~ u~ ~ _ ~ ~
,~ ~ ~ ~ ~ a~ ~ ~ ~
~ c~ ~1 ~ o~ ~ ~ a~ oo ~ _ ,.; O ~ = I~ ~D v~ O~ ~ _ ~ ~1 O
a C ~o O ~ ~ c~ o~ ~ . ,~ ~;r u a~
~; ~ _ _ __ __ ~ _ ~i _1 ~ , ,. ~ . C~P. ~ ~D OD ~O ~O I~ ~:r ~o ~O
'' ' ~ __ ~C= o _l ~ _ ~ _ o -~tl .
,' E~ 0 Co=~ ~ _~ _1 ~ ~1 O _ 0 0 ~a P o u~ ~ o~ c~l I~ O
1: . ~. c~a. c~ ~1 ,~ ~1 C`J ~ C`~ Z
o .- ~= U~ ~ o o ~ __ ~: ~ ~ ~ ~o ~ _~ ~ _ _l _ ~ o " to ~ I~ CO o ~ o ~ CO ~ S;
C~ a~ ~ ~ ~1 ~ ~ ~O 3 ' ~ . __ _ ~: ~ Z
c ~ C ~<~ ~ ~ ~u~ a~ u~a u ~a ' ~ , ~C~ :~ s~ Z :Z Z I ss Z C C
.
Claims (5)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of fixing heavy metals or heavy metallic compounds contained in sewage, solid or slurried wastes or soil, which comprises the addition to said sewage, solid or slurried wastes or soil of an aliphatic dithiocarbamate compound which is the reaction product of 1 mole of ethy-lenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylene-tetramine, tetrapropylenepentamine or pentapropylenehexamine with 2 to 5 moles of carbon bisulfide.
2. The method of Claim 1, wherein said dithiocarbamate compound is added in an amount of from about 0.1% to about 50% by weight of the sewage, solid or slurried wastes or soil.
3. The method of Claim 1, wherein said method is applied to fixing heavy metals or heavy metallic compounds in a cement composition and said dithiocarbamate compound is added in an amount of from about 0.001 to about 10% by weight of said composition.
4. The method of Claim 1, wherein said method is applied to fixing heavy metals or heavy metallic compounds in sewage or slurried wastes and said dithiocarbamate compound is added in an amount if from about 20% to about 80% by weight of said sewage or slurried wastes.
5. The method of Claim 1, wherein said method is applied to fixing heavy metals or heavy metallic compounds in soil and said dithio-carbamate compound is added in an amount of from about 0.001% by weight to about 10% by weight of said soil.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1231173A JPS5639358B2 (en) | 1973-01-30 | 1973-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1052021A true CA1052021A (en) | 1979-04-03 |
Family
ID=11801759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA191,195A Expired CA1052021A (en) | 1973-01-30 | 1974-01-29 | Fixing agent of heavy metal |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5639358B2 (en) |
| BE (1) | BE810369A (en) |
| CA (1) | CA1052021A (en) |
| DE (1) | DE2404403B2 (en) |
| FR (1) | FR2215393B1 (en) |
| GB (1) | GB1454342A (en) |
| IT (1) | IT1048990B (en) |
| NL (1) | NL7401301A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6057920B2 (en) * | 1976-06-15 | 1985-12-17 | ミヨシ油脂株式会社 | Heavy metal collection method |
| JPS52152657A (en) * | 1976-06-15 | 1977-12-19 | Miyoshi Yushi Kk | Heavy metal collecting method |
| JPS55159835A (en) * | 1979-05-30 | 1980-12-12 | Unitika Ltd | High selective heavy metal ion adsorbing agent, and method of preparation and adsorption thereof |
| DE2950462A1 (en) * | 1979-12-14 | 1981-06-19 | VFI Verwertungsgesellschaft für Industrierückstände mbH, 3161 Dollbergen | METHOD FOR THE DISPOSAL AND FINAL STORAGE OF WASTE MATERIALS |
| NL8300447A (en) * | 1983-02-05 | 1984-09-03 | Unie Van Kunstmestfab Bv | METHOD FOR REMOVING HEAVY METALS FROM AQUEOUS MEDIA |
| NL8300446A (en) * | 1983-02-05 | 1984-09-03 | Unie Van Kunstmestfab Bv | METHOD FOR REMOVING HEAVY METALS FROM AQUEOUS MEDIA |
| US4670180A (en) * | 1985-04-26 | 1987-06-02 | Miyoshi Yushi Kabushiki Kaisha | Metal scavenger and metal scavenging process |
| DE3685861T2 (en) * | 1985-08-05 | 1992-12-17 | Miyoshi Yushi Kk | METHOD FOR DEPOSITING METALS. |
| GB2204861A (en) * | 1987-04-24 | 1988-11-23 | Central Glass Co Ltd | Preparation of inorganic metal compounds of ultrahigh purity |
| EP0433580B1 (en) * | 1989-12-20 | 1993-12-22 | Miyoshi Yushi Kabushiki Kaisha | Metal scavengers and wastewater treatment processes |
| JP3912812B2 (en) * | 1995-12-28 | 2007-05-09 | 日本曹達株式会社 | A chelating agent comprising an aqueous metal salt of dithiocarbamate and a method for producing the same |
| JP2001115136A (en) * | 1999-10-20 | 2001-04-24 | Miyoshi Oil & Fat Co Ltd | Production of metal scavenger |
| GB0406532D0 (en) * | 2004-03-24 | 2004-04-28 | British Nuclear Fuels Plc | Treatment of elemental mercury |
| JP4832921B2 (en) * | 2006-03-01 | 2011-12-07 | 東亜ディーケーケー株式会社 | Electrode body |
| RU2579131C1 (en) * | 2014-11-28 | 2016-03-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Юго - Западный государственный университет" (ЮЗГУ) | Method of purifying waste water from ions of chromium (iii) and copper (ii) |
| CN105906103A (en) * | 2016-06-13 | 2016-08-31 | 台州市神州电热电器厂 | Recovery process for electroplating wastewater |
| CN112794692A (en) * | 2021-01-13 | 2021-05-14 | 广东碧通百年科技有限公司 | Mortar capable of consolidating polluted soil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA955035A (en) * | 1970-02-05 | 1974-09-24 | Osaka Soda Co. | Treatment process for removal of metals and treating agent therefor |
-
1973
- 1973-01-30 JP JP1231173A patent/JPS5639358B2/ja not_active Expired
-
1974
- 1974-01-29 GB GB408474A patent/GB1454342A/en not_active Expired
- 1974-01-29 FR FR7402895A patent/FR2215393B1/fr not_active Expired
- 1974-01-29 CA CA191,195A patent/CA1052021A/en not_active Expired
- 1974-01-30 NL NL7401301A patent/NL7401301A/xx not_active Application Discontinuation
- 1974-01-30 DE DE19742404403 patent/DE2404403B2/en not_active Withdrawn
- 1974-01-30 IT IT4803174A patent/IT1048990B/en active
- 1974-01-30 BE BE140349A patent/BE810369A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2404403B2 (en) | 1977-10-20 |
| GB1454342A (en) | 1976-11-03 |
| NL7401301A (en) | 1974-08-01 |
| IT1048990B (en) | 1980-12-20 |
| FR2215393B1 (en) | 1977-09-23 |
| JPS4999978A (en) | 1974-09-20 |
| JPS5639358B2 (en) | 1981-09-12 |
| FR2215393A1 (en) | 1974-08-23 |
| BE810369A (en) | 1974-05-16 |
| DE2404403A1 (en) | 1974-08-22 |
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