CN106574320A - Metal recovery method and metal recovery agent - Google Patents
Metal recovery method and metal recovery agent Download PDFInfo
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- CN106574320A CN106574320A CN201580042041.XA CN201580042041A CN106574320A CN 106574320 A CN106574320 A CN 106574320A CN 201580042041 A CN201580042041 A CN 201580042041A CN 106574320 A CN106574320 A CN 106574320A
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- 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
- C22B11/00—Obtaining noble metals
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- 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
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Abstract
The purpose of the present invention is to provide a novel technology for separating and recovering metal, namely, to provide a convenient, low-cost, and superiorly selective metal recovery method and metal recovery agent. This metal recovery method uses a metal recovery agent that has as an active component a photocurable resin that has a group that can bond to a metal ion. Specifically, the photocurable resin of this metal recovery method is represented be general formula (1) (X is a metal coordination site and represents a substituted or unsubstituted amino group or phosphino group. R is a linking group and represents a hydrogen atom, a C1-5 alkyl group, a phenyl group, or a biphenyl group. A is a polymerization site and represents a substituted or unsubstituted methacryloyl group, acryloyl group, vinyl group, cinnamoyl group, aryl group, vinylbiphenyl group, propargyl group, glycidyl group, or isocyanate group, and n indicates an integer from 2 to 3.).
Description
Technical field
The invention belongs to be used to reclaim the technical field of the noble metal contained in solution, it is directed to use with can be with gold
Belong to the metal recovery processes and the metal of the light-cured resin as the metal recovery agent of active ingredient of ionically bonded group
Recovery catalyst.
Background technology
In order to efficiently using having scarcity and noble metal also high in price, from using finishing containing your gold
The technology of separation/recovery noble metal is indispensable in the solution of category, it is proposed that various methods.For example have：Inhale noble metal
It is attached on ion exchange resin, then makes the aqueous solution and contacts ionic exchange resin of sodium chloride or ammonium chloride, so that your gold
Belong to the method (patent document 1) departed from from ion exchange resin；Make the Extraction solvent containing noble metal selective extraction agent and contain
The liquid for having noble metal carries out liquid-liquid contact, so as to optionally extract the method (patent document 2) of noble metal；Using amino
Compound or the method (patent document 3) of the selective precipitation agent for combining amino-compound and heteropoly acid；Your gold made
Category is adsorbed onto and introduces on polymeric matrix on the adsorbent for having chelate to form group, then makes inorganic acid, organic acid or has
Machine solvent is contacted with adsorbent, thus makes the method (patent document 4) that noble metal departs from from adsorbent；By coordination bonding by gold
The method (patent document 5) that category is reclaimed in the form of condensation product.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-192162 publications
Patent document 2：Japanese Unexamined Patent Publication 2001-115216 publications
Patent document 3：Japanese Unexamined Patent Publication 2005-194546 publications
Patent document 4：Japanese Unexamined Patent Publication 2006-026588 publications
Patent document 5：Japanese Unexamined Patent Publication 2011-132573 publications
The content of the invention
Invent problem to be solved
But, noble metal is absorbed ion-exchange group or chelation group described in patent document 1 or patent document 4
On method in, there is the operation of the noble metal wash-out that will be adsorbed in back segment, therefore, eluent is treated as problem；Specially
In the method for the use extractant described in sharp document 2, existing must use the organic solvents such as chloroform, toluene in Extraction solvent
Problem.In addition, in the method for the use selective precipitation agent described in patent document 3, the amino-compound for being used is low
Molecular compound, therefore there is a problem of stink, it is difficult to it is practical.Therefore, urgently expect easy, inexpensive and selective excellent
The separation/recovery technique of noble metal.
The present invention in view of situation as above and make, its object is to provide a kind of new metal separation and recovery skill
Art, that is, provide a kind of easy, inexpensive and selective excellent metal recovery processes and the metal recovery agent.
Means for solving the problem
Present inventor has performed further investigation, as a result finds, by using with the base that can be bonded with metal ion
Group light-cured resin as the metal recovery agent of active ingredient metal recovery processes, can easily realize noble metal from
Precipitation and separation/recovery in metal-containing solutions, so as to complete the present invention.
That is, the present invention is provided：
(1)
A kind of metal recovery processes, it is made using the light-cured resin with the group that can be bonded with metal ion
For the metal recovery agent of active ingredient；
(2)
Metal recovery processes described in (1) as described above, wherein, including the photo-curable tree for having metal ion to coordination bonding
Fat irradiates active energy beam and makes the operation of its solidification；
(3)
Metal recovery processes described in (1) or (2) as described above, wherein, the above-mentioned group that can be bonded with metal ion is
Selected from substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl constitute group in one or two with
On；
(4)
Metal recovery processes any one of (1)～(3) as described above, wherein, it is above-mentioned with can be with metal ion
The light-cured resin of the group of bonding contains selected from substituted or unsubstituted (methyl) acryloyl group, acryloyl group, ethene
One kind in the group that base, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl, glycidyl, NCO are constituted
Or it is two or more；
(5)
Metal recovery processes any one of (1)～(4) as described above, wherein, above-mentioned light-cured resin is by following
Formula (1) is represented；
(X is metal coordination sites, represents substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl.R
Linking group is represented, hydrogen atom, the alkyl that carbon number is 1～5, phenyl, xenyl is represented.A is polymerization position, represents and replaces
Or unsubstituted (methyl) acryloyl group, acryloyl group, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl,
Glycidyl, NCO.N represents 2～3 number.)
(6)
Metal recovery processes any one of (1)～(5) as described above, it has following operation：
Add in metal-containing solutions using with the light-cured resin of group that can be bonded with metal ion as having
The operation of the metal recovery agent of effect composition,
There is the light-cured resin irradiation active energy beam of metal ion to coordination bonding and make the operation of its solidification, and
Solidfied material to precipitating carries out burning disposal so as to reclaim the operation of metal；
(7)
A kind of metal recovery agent, it is using following light-cured resins represented by formula (1) as active ingredient.
(X is metal coordination sites, represents substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl.R
Linking group is represented, hydrogen atom, the alkyl that carbon number is 1～5, phenyl, xenyl is represented.A is polymerization position, represents and replaces
Or unsubstituted (methyl) acryloyl group, acryloyl group, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl,
Glycidyl, NCO.N represents 2～3 number.)
Invention effect
The metal recovery processes of use metal recovery agent of the invention, can provide a kind of making in metal-containing solutions
The separation/recovery technology of the noble metal that precipitation and separation/recovery is easy, inexpensive and selectivity is excellent of metal.
Description of the drawings
Fig. 1 is the photo of the sediment for illustrating embodiment 3,4.
Fig. 2 is the photo of the sediment for illustrating reference example.
Fig. 3 is the photo of the precipitation situation for illustrating comparative example 2.
Specific embodiment
Hereinafter, the principle of the metal recovery processes of the present invention is illustrated.
The metal recovery processes of the present invention are the gold for using the metal recovery agent using light-cured resin as active ingredient
The recovery method of category, wherein, there is the light-cured resin metal for metal is made from metallic solution carrying out coordination bonding to match somebody with somebody
Position position and polymerization position.Here, in the present invention, coordination bonding being carried out to metal and being referred to only by two atoms of bonding
Person provides the chemical bonding of bonding electron to molecular orbit.Therefore, the transition metal with the valence electron for coordination bonding becomes
Reclaim metal target.
First, add in the metal-containing solutions for be dissolved with transition metal with metal coordination sites and the position that is polymerized
Metal recovery agent of the light-cured resin as active ingredient.Then, metallic ion coordination is bonded on metal coordination sites.Need
It is noted that the so much metal ligand of ligancy is bonded with a metallic ion coordination.Thus, generate in metal-complexing portion
Position coordination bonding has the condensation product of metal ion.Thus, the metal ion in metal-containing solutions is captured to metal coordination sites.
If here, the quantity of the substituent that can carry out coordination bonding of light-cured resin is more than in metal-containing solutions
Metal ion number and ligancy product, then almost occur without in the water containing metal cannot carry out the metal of coordination bonding from
Son, therefore, metal recovery efficiency is further improved, so as to preferred.During the metal recovery agent of the addition present invention, moment formation passes through
The condensation product that the metal recovery processes of the present invention are formed.Therefore, it is possible to rapidly carry out metal recovery.In addition, the addition present invention
Metal recovery agent amount adding proportion relative to the amount of metal in solution be usually 0.01 weight %～50 weight % be close
Suitable, preferably 0.1 weight %～10 weight %.
Then, to the condensation product irradiation active energy beam for being formed, solidify condensation product.Condensation product after solidification is at this
Precipitate in metal-containing solutions.The sediment can by from lautertuns by and separated, as a result can reclaim metal.
As described above, the metal recovery processes of the present invention have following characteristics：Coordination is made by active energy beam irradiation
The condensation product for having metal further solidifies, so that its precipitation.Therefore, the metal of use metal recovery agent of the invention is returned
Receiving method, can make the precipitation and separation/recovery of the metal in metal-containing solutions becomes easy, inexpensive and selective excellent expensive
The separation/recovery of metal.
Hereinafter, the metal recovery agent used in the present invention is illustrated.
The metal recovery agent of the present invention using with the light-cured resin of group that can be bonded with metal ion as having
Effect composition.
In the present invention, the light-cured resin with the group that can be bonded with metal ion is by with the side of coordination bonding
Formula bond wire ion and be used to reclaim metal from metal-containing solutions.That is, the group that can be bonded with metal ion can be with
The slaine of supply metal ion carries out ion-exchange reactions, so as to metal ion is absorbed in light-cured resin.
As the group that can be bonded with metal ion, substituted or unsubstituted amino, phosphino-, carboxyl, mercapto can be enumerated
Base, phosphate, thioether group, sulfinyl, disulfide base etc..Can suitably be changed according to the metal of coordination bonding.For example,
Preferred amino in the case of tungsten, the preferred sulfydryl in the case of palladium, the preferred phosphino- in the case of indium.
As the position that is polymerized of the light-cured resin with the group that can be bonded with metal ion, replacement can be enumerated
Or unsubstituted (methyl) acryloyl group, acryloyl group, cinnamoyl, pi-allyl, vinyl, vinyl biphenyl base, propargyl,
Glycidyl, NCO etc., but it is not limited to these.Preferably substituted or unsubstituted (methyl) acryloyl group, propylene
Acyl group.
The light-cured resin with the group that can be bonded with metal ion used in the present invention is preferably by following
The light-cured resin that formula (1) is represented.
(X is metal coordination sites, represents substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl.R
Linking group is represented, hydrogen atom, the alkyl that carbon number is 1～5, phenyl, xenyl is represented.A is polymerization position, represents (first
Base) it is acryloyl group, acryloyl group, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl, glycidyl, different
Cyanic acid ester group.N represents 2～3 integer.)
But, the light-cured resin with the group that can be bonded with metal ion used in the present invention is not limited to
Above-mentioned preferred light-cured resin, it is as above-mentioned metal coordination sites X, such as substituted or unsubstituted in above-mentioned formula (1)
Amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl etc., its coordination atom can enumerate nitrogen, phosphorus, oxygen, sulphur.As concrete example,
Can enumerate phosphoric acid ester, pyridine, ammonia, triphenylphosphine, nitrate ion, bipyridyl, ethylenediamine, phenanthroline, acetylacetone,2,4-pentanedione, three
Bipyridyl, ethylenediamine tetra-acetic acid, porphyrin, crown ether-like etc., but it is not limited to these.Preferably phosphoric acid ester.
As above-mentioned polymerization position A, substituted or unsubstituted (methyl) acryloyl group, acryloyl group, Chinese cassia tree can be enumerated
Acyl group, pi-allyl, vinyl, vinyl biphenyl base, propargyl, glycidyl, NCO etc., but it is not limited to these.
Preferably substituted or unsubstituted (methyl) acryloyl group or acryloyl group.
In (methyl) acrylate compounds with the group that can be bonded with metal ion, as with carboxyl
(methyl) acrylate compounds, can enumerate (methyl) acrylic acid, lactone-modified (methyl) acrylic acid, phthalic acid 2-
(methyl) acryloyloxyethyl ester (for example, Kyoeisha Chemical Co., Ltd.'s manufacture, HOA-MPL), phthalic acid 2- (methyl)
Acryloxy propyl ester (for example, Osaka organic chemistry Co., Ltd. manufacture, Biscoat (trade name) #2100), hexahydro neighbour's benzene two
Formic acid 2- (methyl) acryloyloxyethyl ester (for example, Kyoeisha Chemical Co., Ltd.'s manufacture, HOA-HH), ethylene-oxide-modified amber
Amber acid esters acrylate (for example, Kyoeisha Chemical Co., Ltd.'s manufacture, HOA-MS), P-carboxy ethyl acrylates (for example, contest
Fine jade UCB. S.A. (BE) Bruxelles Belgium manufacture, β-CEA), ω-carboxy-polycaprolactone mono acrylic ester (for example, Toagosei Co., Ltd manufacture,
ARONIX (trade name) M-5300) etc..As (methyl) acrylate compounds with phosphate, oxirane can be enumerated
Modified phenoxylation (methyl) acrylate phosphate, ethylene-oxide-modified butoxylated (methyl) acrylate phosphate, ring
Oxidative ethane is modified octyloxy (methyl) acrylate phosphate, ethylene-oxide-modified (methyl) acrylate phosphate, epoxy
Oxide-modified two ((methyl) acrylate) phosphate, ethylene-oxide-modified three ((methyl) acrylate) phosphate etc., can be with
With Nippon Kayaku K. K manufacture PM-2 (ethylene-oxide-modified two (methacrylate) phosphate with it is ethylene-oxide-modified
The mixture of methacrylate phosphate) etc. form obtain.As with sulfonic (methyl) acrylate compounds, can
To enumerate tert-butyl acrylamide sulfonate (for example, MRC Unitec Co., Ltd. manufacture, TBAS).
In addition, as (methyl) the acrylate phosphate compound with the group that can be bonded with metal ion,
If (methyl) acrylate with phosphate backbone, then be not particularly limited to monoesters, diester or three esters etc., can enumerate
For example：Ethylene-oxide-modified phenoxylation (methyl) acrylate phosphate, ethylene-oxide-modified butoxylated (methyl) propylene
Acid esters phosphate, ethylene-oxide-modified octyloxy (methyl) acrylate phosphate, ethylene-oxide-modified two ((methyl) propylene
Acid esters) phosphate, ethylene-oxide-modified three ((methyl) acrylate) phosphate etc., can be manufactured with Nippon Kayaku K. K
The form such as PM-2 (ethylene-oxide-modified two (methacrylate) phosphate) obtain.(methyl) acrylate phosphate can be with
It is used in mixed way using one kind or with arbitrary proportion two or more.
As the linking group of above-mentioned R, alkyl, phenyl, xenyl that hydrogen atom, carbon number are 1～5 can be enumerated
Deng, but it is not limited to these.
Hereinafter, the concrete example of the light-cured resin represented by formula (1) is illustrated.But, can use in the present invention
The light-cured resin represented by formula (1) should restrictively not explained by these concrete examples.
(in formula, R1Represent hydrogen atom or methyl；R2Represent the straight or branched alkylidene that carbon number is 1～4.N be 0～
3 integer.A is 1 or 2 integer)
As the example of phosphate ester acid, 2- ethylhexyl phosphate ester acids, isodecyl phosphate ester acid, different can be enumerated
Dodecyl phosphate ester acid, isotridecyl phosphate ester acid, oleyl phosphate ester acid, 2- hydroxy ethyl methyl acrylic acid
Ester phosphate ester acid, double (2- ethylhexyls) phosphates etc..
In the metal recovery agent of the present invention, as by the metallic atom of the metal ion of coordination bonding, can enumerate and be selected from
Metal class in alkali metal, alkaline-earth metal, transition metal, late transition metal, lanthanide series metal and actinide metals.Specifically, it is excellent
Select manganese, iron, cobalt, nickel, copper, zinc, neodymium, sodium, potassium, calcium, magnesium.
In addition, as heretofore described metal, as long as transition metal, can illustrate platinum group metal (palladium,
Ruthenium, rhodium, osmium, iridium, platinum) and gold, silver, iron group metal (iron, nickel, cobalt), chromium race metal (chromium, molybdenum, tungsten,), rare earth metal (neodymium,
Dysprosium, praseodymium).
In the metal recovery processes of the present invention, it is also possible to be properly added Photoepolymerizationinitiater initiater, curing accelerator.It is poly- as light
The concrete example of initiator is closed, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, diethyl can be enumerated
Epoxide acetophenone, dibenzoyl dimethyl ketal, 2- hydroxy-2-methyl propiophenones, 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyls-
1- { 4- [4- (2- hydroxy-2-methyl propionos) benzyl] phenyl } -2- methylpropane -1- ketone, benzophenone, 2,4,6- trimethyls
Benzoyl diphenyl phosphine oxide, 2- methyl-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 2- benzyl -2- dimethyl
Amino -1- (4- morphlinophenyls)-butane -1- ketone, Michler's keton, N, N- dimethylaminobenzoic acid isopentyl ester, CTX,
2,4- diethyl thioxanthones, oligomeric { 2- hydroxy-2-methyl -1- [4- (1- methyl ethylenes) phenyl] acetone } etc., these light gather
Closing initiator can also be suitably and with two or more.
As the concrete example of curing accelerator, the phosphines such as triphenylphosphine, double (methoxyphenyl) Phenylphosphines can be illustrated；2-
The imidazoles such as methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole；2- (dimethylaminomethyl) phenol, three (diformazans
Base amino methyl) tertiary amines such as phenol, diazabicyclo endecatylene；4-butyl ammonium, triisopropyl methyl ammonium salt, dodecane
The quaternary ammonium salts such as base leptodactyline, cetyltrimethylammonium ammonium salt；TriphenylbenzylphosphoniumSalt, triphenyl ethylSalt, the tetrabutylThe seasons such as salt(counter ion counterionsl gegenions of quaternary salt are halide ion, organic acid anions, hydroxide ion etc. to salt, are not referred in particular to
It is fixed, particularly preferred organic acid anions, hydroxide ion)；Metallic compounds such as tin octoate etc..
Hereinafter, the metal recovery processes of the use metal recovery agent of the present invention are illustrated.
In the method for the present invention, refer to as the liquid containing metal (hereinafter referred to as metal-containing solutions) of process object
The solution containing metal or its compound (the particularly material of colloidal state) obtained in various industrial process.It typically is water
Property solution, but it is not precluded from Organic solution.As the example of such metal-containing solutions, can illustrate containing carrying out chemistry
So-called catalyst chemical industry sequence during plating, the work for sowing on plating object the active nucleus of catalyst such as platinum family system metal
The catalyst liquid of (or will use) metal colloid particles crossed used in sequence；In order to from the raw material containing metal, material
Middle recovery metal and use sour or leaching/lysate obtained from alkali process solid content containing metal；Above-mentioned leaching/lysate is passed through
Containing after being processed using the absorption of ion exchange resin or activated carbon, electroextraction, precipitation crystallization, solvent extraction method etc.
Raffinate of trace meter etc..
With regard to the concentration of the metal in the metal-containing solutions of the process object as the present invention, as long as at least containing in the solution
There is metal, can be arbitrary concentration, usually 100mg/L～1000mg/L.It should be noted that such containing metal
Solution can in advance concentrate or dilute as needed after for the method for the present invention.
Metal in metal-containing solutions forms reaction with the absorption/agglomerate of recovery catalyst can be entered rapidly at normal temperatures and pressures
OK, therefore special reaction unit need not be prepared, by the way that the metal recovery agent of metal-containing solutions and the present invention is sufficiently mixed,
Adsorption reaction can be carried out and form agglomerate, but preferably carry out pH regulations as needed.In order to adjust pH, as acid, Ke Yilie
Organic acid, the sulfamic acids such as inorganic acid, formic acid, the acetic acid such as sulfuric acid, hydrochloric acid etc. are lifted, as alkali, NaOH, hydrogen-oxygen can be enumerated
Change potassium, ammonia etc..Then can be arbitrary pH as long as pH is less than 9, preferably less than 8, more preferably less than 7.Containing metal
It is sufficient that solution is usually 1 minute～30 minutes with the time of contact of selective metal recovery catalyst, the agglomerate within the time
Form reaction to terminate.
Light-cured resin used in the metal recovery processes of the present invention can be using a kind of or mixed with arbitrary ratio
Close using two or more.It is usually 0.1 weight %～6.0 weight %, is preferably 0.5 weight relative to the addition of metal-containing solutions
Amount %～5.0 weight %.When addition is very few compared with 0.1 weight %, it is possible to cannot effectively reclaim metal.In addition, with
When 6.0 weight % compare excessive, the light-cured resin for having neither part nor lot in recovery increases, light-cured resin residual, it is possible to cause
Waste.
Metal-containing solutions are mixed with the metal recovery agent, agglomerate is formed, then to mixing the metal recovery agent and shape
Into agglomerate irradiation active energy beam, solidify condensation product.Condensation product after solidification is precipitated in the metal-containing solutions.Should
Sediment can by from lautertuns by and separated, as a result, metal can be reclaimed.
In the irradiation of active energy beam, from unilateral or two sides ultraviolet～near ultraviolet (wavelength about 200nm～about is irradiated
Light 400nm) and solidified.Exposure is preferably from about 50mJ/cm2～about 1500mJ/cm2, particularly preferably for about 100mJ/
cm2～about 1000mJ/cm2.When being solidified using ultraviolet～near ultraviolet light irradiation, as long as irradiate ultraviolet～near ultraviolet
Light lamp, then do not limit light source.Such as low pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, (pulse) can be enumerated
Xenon lamp or electrodeless lamp etc..
The metal precipitates for being generated easily carry out separation of solid and liquid, therefore can efficiently be carried out by separating and filtering operation
Separation of solid and liquid in solution, it is possible to use general dewaterer is dehydrated.As dewaterer, such as vacuum dehydration can be enumerated
Machine, belt filter press, fly press, centrifugal dehydrator etc., but it is not particularly limited.
Metal precipitates after separation can reclaim noble metal by carrying out burning disposal, can be in various applications
In recycled.
Embodiment
Specific embodiment described below, so as to illustrate the content of the present application in further detail.Shown below
Material, process content, process step can changed suitably without departing from the spirit of the invention.Therefore, it is of the invention
Scope should not be explained by being defined property of concrete example shown below.
Embodiment 1
Solution (hereinafter referred to as metal-containing solutions) 100ml of the molybdenum containing concentration 700mg/L (Mo) is prepared, has added thereto
The phosphate (" KAYAMER (trade name) PR-2 " (Nippon Kayaku K. K's manufacture)) for having added 0.1 weight % is returned as metal
Receive agent.Then its reaction 30 minutes is made, is then filtered each treatment fluid with filter paper (ADVANTEC manufactures), in having obtained filtrate
The concentration of molybdenum.Show the result in table 1.
Embodiment 2
In addition to the addition for making PM-2 is 0.5 weight %, obtained in filtrate using method similarly to Example 1
Molybdenum concentration.Show the result in table 1.
Embodiment 3
Except used the FRM-1000 (Nippon Kayaku K. K's manufacture) of 0.1 weight % as metal recovery agent with
Outward, the concentration of the molybdenum in filtrate has been obtained using method similarly to Example 1.Show the result in table 1.FRM- is shown in Fig. 1
1000 is (left：0.1 weight %, the right side：0.5 weight %) coagulative precipitation thing.As a reference example, FRM-1000 (1.0 is shown in Fig. 2
Weight %) state of aggregation.
Embodiment 4
In addition to the addition for making FRM-1000 is 0.5 weight %, using method similarly to Example 3 filter is obtained
The concentration of the molybdenum in liquid.Show the result in table 1.Illustrate that FRM-1000 is (left in Fig. 1：0.1 weight %, the right side：0.5 weight %) it is solidifying
Coagulation starch.
Compare synthesis example 1
The synthesis of double (3- acryloxypropyls) phosphine oxides of normal-butyl
Input is made in the reactor for possessing reflux condenser, agitator, thermometer, temperature-adjusting device and separator
For double (3- hydroxypropyls) phosphine oxide 222.3g of normal-butyl of alcoholic compound (a), as having ethylenically unsaturated group in molecule
Monocarboxylic acid compound (b) acrylic acid 172.9g (2.4mol), as the p-methyl benzenesulfonic acid monohydrate of acid catalyst
3.46g, the quinhydrones 1.31g as hot polymerization inhibitor, the toluene 138.3g as reaction dissolvent, hexamethylene 59.3g, 95 DEG C～
Product water and solvent azeotropic distillation are removed under 105 DEG C of reaction temperature, while being reacted, in product water 31.7ml is reached
When, as the terminal of reaction.Add toluene 507.2g and hexamethylene 217.4g in the reactive mixture, with 25 weight % caustic soda
The aqueous solution is neutralized, and has then cleaned 3 times with 15 weight % saline solution 100g.Vacuum distillation removes solvent, so as to be compared
Reactive compounds (BPPA) 294.2g (yield 87.7%).After synthesis, utilize1H-NMR confirms structure.
1H-NMR(CDCL3、δ)
0.92 (t, J=13.5,3H), 1.43-1.54 (m, 4H), 1.71-2.06 (m, 10H), 4.21 (t, J=5.7,
4H), 5.84 (dd, J=10.5Hz, J=1.52Hz, 2H), 6.11 (dd, J=10.3Hz, J=17.5Hz, 2H), 6.40 (dd, J
=17.5Hz, J=1.52Hz, 2H)
Comparative example 1
In addition to using the compound obtained in synthesis example 1 (BPPA) is compared as metal recovery agent, by with enforcement
The same method of example 1 has obtained the concentration of the molybdenum in filtrate.Show the result in table 1.
Comparative example 2
In addition to the addition for making BPPA is 0.5 weight %, obtained in filtrate by the method same with comparative example 1
Molybdenum concentration.Show the result in table 1.Illustrate that BPPA is (left in Fig. 3：0.1 weight %, the right side：0.5 weight %) coagulative precipitation
Thing.
[table 1]
As shown in Table 1, compared with comparative example 1,2, in the metal recovery processes of the use metal recovery agent of the present invention, containing gold
Mo major parts in category liquid are precipitated in the form of agglomerate, can be reclaimed the Mo in liquid.
The present invention is described in detail by with reference to specific mode, it will be obvious to those skilled in the art that can
To make various changes and modifications without departing from the spirit and scope of the present invention.
It should be noted that Japanese patent application (Japanese Patent Application 2014- of the application based on the proposition on the 4th of August in 2014
158458) entire contents, are quoted by reference.In addition, cited herein all referring to as being generally introduced this specification
In.
Industrial applicability
The metal recovery agent of the present invention and metal recovery processes optionally and inexpensively, can be reclaimed easily containing metal
Metal in solution.Further, since can remove metal adsorption from metal-containing solutions, therefore can be used for Wastewater Treatment Technology
Art.
Claims (7)
1. a kind of metal recovery processes, its use using the light-cured resin with the group that can be bonded with metal ion as
The metal recovery agent of active ingredient.
2. metal recovery processes as claimed in claim 1, wherein, the metal recovery processes include there is metal ion to coordination bonding
Light-cured resin irradiation active energy beam and make its solidify operation.
3. metal recovery processes as described in claim 1 or claim 2, wherein, it is described to be bonded with metal ion
Group is the one kind or two in the group constituted selected from substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl
More than kind.
4. metal recovery processes as any one of claim 1 to claim 3, wherein, it is described with can be with gold
The light-cured resin for belonging to ionically bonded group contains selected from substituted or unsubstituted (methyl) acryloyl group, acryloyl
In the group that base, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl, glycidyl, NCO are constituted
One or more.
5. metal recovery processes as any one of claim 1 to claim 4, wherein, the light-cured resin
Represented by following formulas (1),
X is metal coordination sites, represents substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl；R represents company
Group is connect, hydrogen atom, the alkyl that carbon number is 1～5, phenyl, xenyl is represented；A is polymerization position, represents and replaces or do not take
(methyl) acryloyl group in generation, acryloyl group, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl, shrink are sweet
Oil base, NCO；N represents 2～3 integer.
6. metal recovery processes as any one of claim 1 to claim 5, wherein, the metal recovery processes
With following operation：
Add in metal-containing solutions using with the light-cured resin of group that can be bonded with metal ion as effectively into
The operation of the metal recovery agent for dividing；
There is the light-cured resin irradiation active energy beam of metal ion to coordination bonding and make the operation of its solidification；With
Burning disposal is carried out to the solidfied material after precipitation so as to reclaim the operation of metal.
7. a kind of metal recovery agent, its using the light-cured resin that represented by following formulas (1) as active ingredient,
X is metal coordination sites, represents substituted or unsubstituted amino, phosphino-, carboxyl, phosphate, sulfo group, sulfydryl；R represents company
Group is connect, hydrogen atom, the alkyl that carbon number is 1～5, phenyl, xenyl is represented；A is polymerization position, represents and replaces or do not take
(methyl) acryloyl group in generation, acryloyl group, vinyl, cinnamoyl, pi-allyl, vinyl biphenyl base, propargyl, shrink are sweet
Oil base, NCO；N represents 2～3 integer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-158458 | 2014-08-04 | ||
| JP2014158458A JP6351427B2 (en) | 2014-08-04 | 2014-08-04 | Metal recovery method and metal recovery agent |
| PCT/JP2015/071989 WO2016021559A1 (en) | 2014-08-04 | 2015-08-03 | Metal recovery method and metal recovery agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106574320A true CN106574320A (en) | 2017-04-19 |
Family
ID=55263824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580042041.XA Pending CN106574320A (en) | 2014-08-04 | 2015-08-03 | Metal recovery method and metal recovery agent |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6351427B2 (en) |
| CN (1) | CN106574320A (en) |
| WO (1) | WO2016021559A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502706A (en) * | 2018-12-30 | 2019-03-22 | 太原理工大学 | A kind of method that automatically controlled ion exchange material recycles metal ion in waste water |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6829805B2 (en) * | 2017-03-30 | 2021-02-17 | 国立研究開発法人産業技術総合研究所 | High-precision mutual separation method for rare earth ions |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040826A (en) * | 1988-08-25 | 1990-03-28 | 联合碳化化学品及塑料有限公司 | The recovery of transition metal |
| CN1392107A (en) * | 2001-06-15 | 2003-01-22 | 住友金属矿山株式会社 | Process for recovering noble metal from noble metal microparticle dispersive liquid |
| JP2005182971A (en) * | 2003-12-24 | 2005-07-07 | Bridgestone Corp | Photocuring resin composition for optical information recording medium, photocuring transfer sheet, and optical information recording medium |
| CN1871260A (en) * | 2003-10-31 | 2006-11-29 | 兴和株式会社 | Cellulose II phosphate ester and metal-adsorbing material using the same |
| CN1890303A (en) * | 2003-10-07 | 2007-01-03 | 普利司通股份有限公司 | Photocuring transfer sheet, method for manufacturing optical information recording medium using the sheet, and optical information recording medium |
-
2014
- 2014-08-04 JP JP2014158458A patent/JP6351427B2/en not_active Expired - Fee Related
-
2015
- 2015-08-03 WO PCT/JP2015/071989 patent/WO2016021559A1/en active Application Filing
- 2015-08-03 CN CN201580042041.XA patent/CN106574320A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040826A (en) * | 1988-08-25 | 1990-03-28 | 联合碳化化学品及塑料有限公司 | The recovery of transition metal |
| CN1392107A (en) * | 2001-06-15 | 2003-01-22 | 住友金属矿山株式会社 | Process for recovering noble metal from noble metal microparticle dispersive liquid |
| CN1890303A (en) * | 2003-10-07 | 2007-01-03 | 普利司通股份有限公司 | Photocuring transfer sheet, method for manufacturing optical information recording medium using the sheet, and optical information recording medium |
| CN1871260A (en) * | 2003-10-31 | 2006-11-29 | 兴和株式会社 | Cellulose II phosphate ester and metal-adsorbing material using the same |
| JP2005182971A (en) * | 2003-12-24 | 2005-07-07 | Bridgestone Corp | Photocuring resin composition for optical information recording medium, photocuring transfer sheet, and optical information recording medium |
Non-Patent Citations (1)
| Title |
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| MELIKE FIRLAK ET AL: "Adsorption of Ag (I) Ions from Aqueous Solutions Using Photocured Thiol-Ene Hydrogel", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502706A (en) * | 2018-12-30 | 2019-03-22 | 太原理工大学 | A kind of method that automatically controlled ion exchange material recycles metal ion in waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016035090A (en) | 2016-03-17 |
| JP6351427B2 (en) | 2018-07-04 |
| WO2016021559A1 (en) | 2016-02-11 |
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