CN1060162A - Method for recovering silver from waste color photosensitive material - Google Patents
Method for recovering silver from waste color photosensitive material Download PDFInfo
- Publication number
- CN1060162A CN1060162A CN 90108112 CN90108112A CN1060162A CN 1060162 A CN1060162 A CN 1060162A CN 90108112 CN90108112 CN 90108112 CN 90108112 A CN90108112 A CN 90108112A CN 1060162 A CN1060162 A CN 1060162A
- Authority
- CN
- China
- Prior art keywords
- silver
- temperature
- color sensitive
- silver halide
- sensitive material
- 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.)
- Granted
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 46
- 239000004332 silver Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 title abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- -1 silver halide Chemical class 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000010953 base metal Substances 0.000 claims abstract description 5
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims abstract 4
- 239000012670 alkaline solution Substances 0.000 claims abstract 2
- 239000003960 organic solvent Substances 0.000 claims abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- 125000000185 sucrose group Chemical group 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical group [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for recovering silver from waste colour photosensitive material includes immersing the waste colour photosensitive material in diluted sulfuric acid solution to elute silver-contained emulsion layer; adding chloride salt and heating to cause silver halide to aggregate and precipitate; chloridizing and roasting or washing with an organic solvent to remove organic matters; adding dilute hydrochloric acid and dilute sulfuric acid to leach out base metals; and (3) suspending and reducing the silver halide by using a saccharide solid in an alkaline solution to obtain pure silver. The purity of silver is more than or equal to 99.9 percent, and the direct yield is more than or equal to 98 percent. The method can also be used for recovering silver from waste black and white films, silver electrolysis waste liquid and silver halide materials.
Description
The invention relates to precious metals metallurgy.
The useless color sensitive material of photosensitive material factory is one of raw material that reclaims silver.Color sensitive material has film and emulsion two big classes.Color film ties up to coated color sensitive emulsion layer on the sheet base.Color sensitive emulsion is generally made by technical recipe by components such as carrier, emulsion, colorant, sensitizer, antistatic agent and water.Carrier is generally gelatin; The emulsion principal ingredient is a silver bromide, secondly is silver chloride, also has a small amount of silver iodide; Colorant is an oil-soluble combination dyestuff; Sensitizer and antistatic agent are the phenyl ring ester, organic compounds such as quinones.Useless color sensitive material silver content is lower, scrap rubber sheet argentiferous～1%, waste emulsion argentiferous 1.58～6.00%.Also do not have at present the more suitable method that from this type of material, reclaims silver, generally adopt hypo solution to leach silver, get slightly silver through electrolysis again.The shortcoming of this method is silver-colored direct yield low (≤80%), purity also low (silver-colored grade～95%), and raffinate and residue silver content are higher.
The objective of the invention is to propose a kind of effective ways from useless color sensitive material recovery silver, silver-colored direct yield height, the purity height, easy and simple to handle, equipment is simple, and flow process is short, and production cost is low.
Method provided by the present invention is:, be immersed in the industrial sulphuric acid of concentration 1～5% 40～80 ℃ of temperature 1, with described useless color sensitive material (film), be interrupted heating, soak time 20～180 minutes, treat that argentiferous emulsion layer solution-off is clean after, pull the sheet base out and clean, return the sheet based system and use; Perhaps in useless color sensitive material (emulsion), add 5～10% industrial sulphuric acid, change sulfuric acid medium emulsion into.2, to 1, add liquor capacity 0.5～10%(ml in the gained argentiferous emulsion: villaumite g) helps precipitation, sodium chloride preferably, and 50～100 ℃ of temperature, 1～3 hour time, silver halide is an aggregate and precipitate.3, with 2, the gained silver halide precipitation, or add villaumite solid mixing, preferably sodium chloride behind the oven dry moisture, its proportioning is material: sodium chloride (weight ratio)=2～4: 1,600～700 ℃ of roastings of temperature 1～5 hour, organic matter removal, silver halide fully were converted into silver chloride; Or repeatedly wash oil removing with ethanol; Not containing oil or oil less can be without this step.4, will, after 3 gained fired slags are levigate, leach except that impurity purification of chlorinated silver such as base metals liquid with 1～5% hydrochloric acid+1～5% sulfuric acid: Gu=6～10: 1,70～90 ℃ of temperature, 1 hour time, impurity less can be without this step.5, with 4, gained leached mud or 3, gained remove the dregs of fat and be added to alkaline medium, preferably in the sodium hydroxide solution, concentration 5～8N, liquid: Gu (ml: g)=5: 1, add the carbohydrate solid reduction, preferably sucrose, its addition is material: reductive agent (weight ratio)=3～5: the 1(film), or 1～3: 1(emulsion), 60～100 ℃ of temperature, 20～70 minutes time.Obtain the fine silver powder, purity 〉=99.9%, direct yield 〉=98%.Dilute sulfuric acid wash-out mother liquor can use repeatedly, goes back original nut liquid argentiferous 0.000Xg/l, can replenish alkali and use repeatedly.
Advantage of the present invention is: 1, the single dilute sulfuric acid of eluent can elute the argentiferous emulsion layer on the scrap rubber sheet effectively; 2, make of sodium chloride and help precipitation agent effective, silver halide precipitation is rapid fully; 3, chloridising roasting remove base metal and organism effective, it is complete that silver halide is converted into silver chloride; 4, sucrose is that silver is selective at alkaline medium reduction silver halide; 5, technological process is brief, and is easy to operate, with short production cycle; 6, agents useful for same is cheap, does not need specific installation again, and production cost is low; 7, product silver purity height, direct yield is also high; 8, operating conditions is good, and is nontoxic, free from environmental pollution; 9, method applicability is wide.
Embodiment
Example 1.Argentiferous is 1.191% the total silver content 8.337g of useless color film 700g(), process: 1, be immersed in the 4% industrial sulphuric acid solution, temperature～70 ℃, about 60 minutes of time, the argentiferous emulsion layer promptly is eluted in the solution, picks up the sheet base.2, adding～3%(volume in argentiferous emulsion: weight, ml: sodium chloride g) helps precipitation, 80～100 ℃ of temperature, time seventy points clock, silver chloride aggregate and precipitate.3, add solid sodium chloride behind the silver halide precipitation oven dry moisture and mix material: sodium chloride=2.5: 1,600～700 ℃ of roastings of temperature 4 hours, silver halide was converted into silver chloride, and organism burnouts.4, fired slags levigate after, leach base metal with 5% hydrochloric acid+5% sulfuric acid, purification of chlorinated silver, liquid: Gu=10: 1, leached 1 hour temperature～90 ℃.5, with 4, the gained leached mud is added in the 5N sodium hydroxide solution liquid: Gu (ml: g)=5: 1, add the sucrose reduction, addition is material: reductive agent (weight ratio)=4: 1,70～100 ℃ of temperature, 30 minutes time, silver chloride reduction is silvery white sponge silver.Silver powder filters, washing, and oven dry, founding gets product 8.2g, purity 99.95%, direct yield 98.36%.
Example 2.Argentiferous is 3.61% the total silver content 97.271g of useless color sensitive emulsion 2.6945kg(), process: 1, add the dilute sulfuric acid of～7% concentration, material: liquid=1: the 1(volume ratio), mixing becomes sulfuric acid medium emulsion.2, the sodium chloride that adds liquor capacity～2%, mechanical raking, 80～100 ℃ of temperature, 80 minutes time, silver halide precipitation is complete, Lu liquid argentiferous 0.0001g/l.3, silver halide is added in 7～8N sodium hydroxide solution, liquid: Gu (ml: g)=5: 1, add the sucrose reduction, addition is material: reductive agent (weight ratio)=2: 1,70～100 ℃ of temperature 1.1 hours, mechanical raking, sponge silver powder gets silver ingot 96.00g through founding, purity 99.95%, direct yield 98.69%.
Example 3. is mainly silver bromide, argentiferous 5.751g by color sensitive emulsion through the silver halide slag 10.0g(of dilute sulfuric acid breakdown of emulsion precipitation gained) in the alkali lye after being added to use once (adding alkali to 5.1625N, 50 milliliters), add the sucrose reduction, addition 5g, 70～100 ℃ of temperature, 1 hour time.Get sponge silver powder 5.750g, silver-colored purity 99.98% direct yield 99.98%.
The invention is not restricted to the foregoing description, also can be used for the recovery of silver in the useless black and white film, or reclaim silver in waste silver electrolyte and the silver halide class material.
Claims (4)
1, a kind of useless color sensitive material reclaims the method for silver, it is characterized in that:
A, the color sensitive material that will give up are immersed in 1～10% sulfuric acid solution, 40～80 ℃ of temperature, and 20～180 minutes time, argentiferous emulsion layer wash-out is in solution.
B, the villaumite that goes the emulsion of sheet base to add liquor capacity 0.5～10% A, institute's score help precipitation, and 50～100 ℃ of temperature heated the silver halide precipitation that obtains assembling 1～3 hour.
C, with B, gained silver halide precipitation, or add the villaumite solid behind the oven dry moisture and mix, 600～700 ℃ of roastings of temperature 1～5 hour, organic matter removal, silver halide is converted into silver chloride; Or repeatedly wash oil removing with organic solvent.
D, C, gained sizing is thin, leach liquid with 1～5% hydrochloric acid+1～5% sulfuric acid: Gu=6～10: 1,70～90 ℃ of temperature, are removed base metal at 1 hour time.
E, C or D, gained slag are added in the alkaline solution, are reduced to silver with the carbohydrate solid reductant, 60～100 ℃ of temperature, 20～70 minutes time.
2, a kind of useless color sensitive material as claimed in claim 1 reclaims the method for silver, and it is characterized in that: it is sodium chloride that the villaumite that adds when carrying out 1B, process helps precipitation agent.
3, a kind of useless color sensitive material as claimed in claim 1 reclaims the method for silver, and it is characterized in that: the chlorating agent that adds when carrying out 1C, process is a sodium chloride, and its proportioning is material: sodium chloride (weight ratio)=2～4: 1; Or repeatedly wash oil removing with ethanol.
4, a kind of useless color sensitive material as claimed in claim 1 reclaims the method for silver, when it is characterized in that carrying out 1E, process, medium is a sodium hydroxide solution, concentration 5～8N, liquid: Gu (ml: g)=5: 1, reductive agent is a sucrose, and its addition is material: reductive agent (weight ratio)=3～5: the 1(film), or=1～3: 1(emulsion).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108112 CN1028567C (en) | 1990-09-29 | 1990-09-29 | Method for recovering silver from waste color photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108112 CN1028567C (en) | 1990-09-29 | 1990-09-29 | Method for recovering silver from waste color photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1060162A true CN1060162A (en) | 1992-04-08 |
| CN1028567C CN1028567C (en) | 1995-05-24 |
Family
ID=4880858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108112 Expired - Fee Related CN1028567C (en) | 1990-09-29 | 1990-09-29 | Method for recovering silver from waste color photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028567C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393898C (en) * | 2003-09-24 | 2008-06-11 | 苏州大学 | Method of recovering silver for silver-containing waste liquid |
| CN102747234A (en) * | 2011-04-22 | 2012-10-24 | 苏州市奥普斯等离子体科技有限公司 | Method for recovering silver from silver-containing waste liquid |
| CN104212973A (en) * | 2014-09-09 | 2014-12-17 | 崔理博 | Method for extracting silver from silver chloride recovered from silver-contained waste water |
| CN110466090A (en) * | 2019-09-10 | 2019-11-19 | 珠海市安能环保科技有限公司 | A method of recycling silver and PET film from HW16 waste photographic film |
-
1990
- 1990-09-29 CN CN 90108112 patent/CN1028567C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393898C (en) * | 2003-09-24 | 2008-06-11 | 苏州大学 | Method of recovering silver for silver-containing waste liquid |
| CN102747234A (en) * | 2011-04-22 | 2012-10-24 | 苏州市奥普斯等离子体科技有限公司 | Method for recovering silver from silver-containing waste liquid |
| CN104212973A (en) * | 2014-09-09 | 2014-12-17 | 崔理博 | Method for extracting silver from silver chloride recovered from silver-contained waste water |
| CN110466090A (en) * | 2019-09-10 | 2019-11-19 | 珠海市安能环保科技有限公司 | A method of recycling silver and PET film from HW16 waste photographic film |
| CN110466090B (en) * | 2019-09-10 | 2021-03-30 | 珠海市安能环保科技有限公司 | Method for recovering silver and PET (polyethylene terephthalate) film from HW16 waste photosensitive film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1028567C (en) | 1995-05-24 |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |