CN102311198A - Method for treating wastewater of copper-based methanol synthesis catalysts - Google Patents
Method for treating wastewater of copper-based methanol synthesis catalysts Download PDFInfo
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- CN102311198A CN102311198A CN 201010212322 CN201010212322A CN102311198A CN 102311198 A CN102311198 A CN 102311198A CN 201010212322 CN201010212322 CN 201010212322 CN 201010212322 A CN201010212322 A CN 201010212322A CN 102311198 A CN102311198 A CN 102311198A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title abstract 4
- 238000003786 synthesis reaction Methods 0.000 title abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000004065 wastewater treatment Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001021 polysulfide Polymers 0.000 claims description 9
- 239000005077 polysulfide Substances 0.000 claims description 9
- 150000008117 polysulfides Polymers 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000050 nutritive effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000247 postprecipitation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- 101001137074 Homo sapiens Long-wave-sensitive opsin 1 Proteins 0.000 description 1
- 101000598987 Homo sapiens Medium-wave-sensitive opsin 1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100035576 Long-wave-sensitive opsin 1 Human genes 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention provides a method for treating wastewater of copper-based methanol synthesis catalysts according to the water quality characteristics of the wastewater of the copper-based methanol synthesis catalysts. The method comprises the steps of: directly adding a CaSX precipitant into the wastewater on the premise that no pretreatment is carried out on the wastewater of the copper-based methanol synthesis catalysts; removing Cu2+and Zn2+ in the wastewater in the meantime to ensure that the content of metal ions in the treated wastewater is up to the country first-grade discharge standard, wherein the copper and zinc ions are recovered and treated along with the precipitates; and discharging the treated wastewater up to the standard after subjecting the treated wastewater to biochemical treatment again. The method provided by the invention has the advantages that the process flow is short; the treatment cost is low; the secondary pollution is nonexistent; and the better economic and environmental benefits are provided.
Description
Technical field
The present invention relates to a kind of cupric, zinc catalyst wastewater treatment method, more particularly, relate to a kind of Cu-series catalyst for synthesizing methanol wastewater treatment method, concrete application industry is mainly the catalyzer Industrial Wastewater Treatment.
Background technology
Such wastewater source adds the prepared process of the required catalyzer of carbonic acid gas system methyl alcohol in hydrogen; Because this catalyzer is to be carrier with the aluminium sesquioxide; Metal objects such as cupric oxide, zinc oxide in the load by a certain percentage; Such waste water is after micropore fine filtration reclaims most copper, zinc solid particulate, and copper, zine ion Pollutant levels still are far longer than discharging standards in the waste water.
Present domestic cupric, zinc catalyst wastewater treatment method are a lot, mainly contain biological process, physico-chemical processes and chemical method.
Biological process is mainly bio-flocculation process and biosorption process: bio-flocculation process is the metabolite that utilizes mikrobe or microorganisms; Thereby method with heavy metal ion flocculation sediment in the water; This method is higher to water quality requirement, needs the necessary nutritional condition of biological growth, and specific aim is stronger.Biosorption process is to utilize microbial cells, plant living body or residual body to make the treatment process of sorbent material; The subject matter that this method exists is; How microbe body is in time separated from the treatment solution of continued running; Though this problem can solve through immobilization technology, cost increases, and heavy metal ion is resolved and reclaimed and also is difficult to solve; Utilize the adsorption technology of plant living body or residual body then to be subject to the geographical environment of being administered.
Physico-chemical processes mainly is a kind of ion exchange method and membrane separation technique or both bonded technology.Ion exchange method receives the restriction of exchanger kind, output and cost.Membrane separation technique is to utilize a kind of special semi-permeable membranes, adopts the separation or the concentrating means of electrodialysis or diaphragm electrolysis principle, and the problem of existence is the problems such as corrosion that fouling appears in operational process.The domestic gore film technology that starts in how tame metal company is to be principle with the press filtration, and effect is better, but cost of investment is too high.
Chemical method mainly comprises electrolytic process and chemical precipitation method.Electrolytic process is mainly used in the processing of electroplating wastewater, and applicable surface is narrower.Chemical precipitation method mainly is to make the heavy metal that is dissolved state in the waste water change water-fast heavy metal compound into through chemical reaction; With separating throw out is removed through filtering from the aqueous solution then, comprising neutralization precipitation method, sulphide precipitation, ferrite coprecipitation method etc.
In the prior art, Chinese patent information at present with waste water in the relevant patented technology of heavy metal removal have: a, utilize the treatment process (200510046816) of chestnut peel for a kind of acid heavy metal polluted waste water of sorbent material; B, copper, zinc complex ion waste water and dregs purifying treatment method (CN 1066257); C, new technology for treating electroplating waste water with micro-organism (CN 1096769); D, utilize shell to remove the method (CN 101538073) of heavy metallic salt in the trade effluent; E, contain the wastewater treatment method (CN1332701) of heavy metal.These methods all are not suitable for the processing of such containing wastewater from catalyst, as: patent a, d are absorption method, are applicable to the high density heavy metal wastewater thereby, but the parsing of post precipitation heavy metal ion and recovery are difficult to solution, have the secondary pollution problem; Patent b mainly uses the milk of lime contact break precipitator method and handles a plating type copper, zinc waste water; Patent c, e mainly utilize micro-reduction to produce processing waste water such as sulfide precipitation, are not suitable for the processing of Cu-series catalyst for synthesizing methanol waste water.
Summary of the invention
The technical problem that the present invention will solve:
The object of the invention is to overcome the defective that exists in the prior art, according to the water quality characteristics of Cu-series catalyst for synthesizing methanol waste water, a kind of Cu-series catalyst for synthesizing methanol wastewater treatment method is provided.This method is Cu-series catalyst for synthesizing methanol waste water not to be done under any pretreated prerequisite, directly in waste water, added calcium polysulfide (CaS
X) precipitation agent, remove Cu in the waste water simultaneously
2+, Zn
2+, make the metal ion content of processed waste water reach national grade one discharge standard, copper, zine ion are with the deposition recycling; Processed waste water is qualified discharge after biochemical treatment again.Technical process of the present invention is short, and processing cost is low, does not have secondary pollution, has good energy economy & environment benefit.
Concrete technical scheme of the present invention:
The treatment process of copper, zinc in a kind of Cu-series catalyst for synthesizing methanol waste water, the water quality situation of such waste water is seen table 1, such wastewater treatment method may further comprise the steps:
Table 1 waste water quality situation
A, in waste water, add the calcium polysulfide precipitation agent
B, reaction and separation
C, biochemical treatment
In the specific implementation, in step a, precipitation agent calcium polysulfide (CaS
x) through the ordinary method preparation, wherein x is 2～4; At former water according to S: (Cu+Zn)=(0.5～2): 1 (mol ratio), in waste water, add calcium polysulfide solution, temperature is a normal temperature, adopts machinery or aeration type to stir, adding the precipitation agent afterreaction time is 0.5～2h.
In the specific implementation, in step b, staticly settle 0.5～2h behind the waste water reaction, the throw out Separation and Recovery, supernatant liquid overflow to biochemistry pool is handled.
In the specific implementation, in step c, get into biochemistry pool waste water quality pH 6～9, COD5～60mg/L; NH
4 +-N 2.5～390mg/L, NO
3 --N 1000～3000mg/L; Cu
2+0～0.3mg/L; Zn
2+0～0.8mg/L; Al
3+0～0.5mg/L; Through biochemical treatment the time, the waste water hydraulic detention time is that 6～24h, pH 6.5～8.0, dissolved oxygen 0.5～5.5mg/L, water temperature are normal temperature; The nutritive salt dosage is in the waste water: Ca
2+10～25mg/L, Mg
2+10～25mg/L, Fe
3+30～60mg/L, KH
2PO
4500～800mg/L; Waste water is qualified discharge after biochemical treatment.
Characteristics of the present invention:
1, Cu-series catalyst for synthesizing methanol waste water does not need any pre-treatment, has reduced processing cost;
2, copper, zine ion recyclable utilization after precipitate and separate in the waste water has reached the purpose of handling and reclaiming;
3, this treating processes need not regulated pH, has saved a large amount of medicaments;
4, post precipitation waste water is through the direct qualified discharge of biochemical treatment.
Description of drawings
Fig. 1 is the schematic flow sheet of Cu-series catalyst for synthesizing methanol wastewater treatment method of the present invention.
Embodiment
Below in conjunction with description of drawings of the present invention concrete steps of the present invention.
Treatment scheme:
The preparation of calcium polysulfide: according to S: Ca=(2～4): 1, get calcium hydroxide earlier and be dissolved in zero(ppm) water, will stick with paste with the sulphur of warm water furnishing in advance again and pour in the water slowly.With water big fire heating, constantly stir and make it even.In the process of boiling, supply the moisture content that evaporates with hot water at any time.Approximately endured 40～60 minutes, soup becomes sorrel by yellow-white, and is clear by turbid change, endures when bits become yellow-green colour.The stoste of enduring can be filtered with fine screen mesh, removes residue.Stoste is once tood many or too much for use, and preferably is contained in the vial of osculum sealing and preserves, and prevents long-term the contact with air of medicament and reduces drug effect.
Wastewater treatment: with the Cu-series catalyst for synthesizing methanol factory effluent is example; From copper is the waste water that is produced in catalyst for methanol parent and the preparing carriers process; Such waste water flows into the precipitin reaction pond behind the homogeneous of homogeneous pond, in the precipitin reaction pond according to waste water in copper, zinc content stream add a certain proportion of calcium polysulfide solution, control certain stirring velocity; Waste water hydraulic detention time in reaction tank is controlled at 0.5～2h; Reaction back overflow to settling tank deposition 0.5～2h, the supernatant overflow is discharged after biochemical treatment is up to standard to biochemical reaction tank.
Use the present invention and handle containing wastewater from catalyst, western without any pretreatment condition, copper, the recyclable utilization again of zine ion in the waste water after the precipitate and separate; But waste water is qualified discharge after biochemical treatment again; Can reduce investment outlay greatly, reduce cost for wastewater treatment, be widely used and promotional value.
Embodiment 1
Certain Cu-series catalyst for synthesizing methanol factory effluent water quality: pH 6.8～7.5, COD 20～35mg/L; NH
4 +-N 350～380mg/L; NO
3 --N 2300～2700mg/L; Cu
2+150～190mg/L; Zn
2+175～210mg/L; Al
3+450～485mg/L; 20 ℃ of water temperatures;
A, waste water introduce the homogeneous pond by pump, behind the homogeneous overflow to reaction tank, in reaction tank according to S: (Cu+Zn)=(1.5～2): 1 (mol ratio) adds precipitation agent, and hydraulic detention time is 1.5～2h in the reaction tank, and reaction back overflow is to settling tank.
Through 1.5～2h post precipitation, the supernatant overflow gets into biochemistry pool, recycles after the precipitate and separate at settling tank for b, processing rear catalyst waste water.
Waste water quality after precipitate and separate: pH 7.8～8.5, COD 20～30mg/L; NH
4 +-N350～380mg/L; NO
3 --N 2300～2700mg/L; Cu
2+0～0.3mg/L; Zn
2+0～0.8mg/L; Al
3+0～0.5mg/L; 20 ℃ of water temperatures;
C, supernatant overflow get into the biochemistry pool aeration, after biochemical treatment reaches national grade one discharge standard, discharge.
Add biological respinse nutrition: Ca in the biochemistry pool
2+: 20mg/L, Mg
2+: 15mg/L, Fe
2+: 40mg/L, KH
2PO
4550mg/L.
Aeration tank operational condition: hydraulic detention time 20～24h, oxygen dissolving value 3.0～5.0mg/L, 15～25 ℃ of service temperatures, pH 7.0～8.5.
After the second pond sedimentation, mud refluxes, and result is seen table 2.
Table 2
Embodiment 2
Certain Cu-series catalyst for synthesizing methanol factory effluent water quality: pH 7.9～8.5, COD 5～25mg/L; NH
4 +-N 180～280mg/L; NO
3 --N 1200～2000mg/L; Cu
2+30～80mg/L; Zn
2+50～125mg/L; Al
3+120～380mg/L; 25 ℃ of water temperatures;
A, waste water introduce the homogeneous pond by pump, behind the homogeneous overflow to reaction tank, in reaction tank according to S: (Cu+Zn)=(0.5～1.5): 1 (mol ratio) adds precipitation agent, and hydraulic detention time is 0.5～1.5h in the reaction tank, and reaction back overflow is to settling tank.
Through 0.5～1.5h post precipitation, the supernatant overflow gets into biochemistry pool, recycles after the precipitate and separate at settling tank for b, processing rear catalyst waste water.
Waste water quality after the precipitate and separate: pH 7.9～8.9, COD 5～20mg/L; NH
4 +-N180～280mg/L; NO
3 --N 1200～2000mg/L; Cu
2+0～0.2mg/L; Zn
2+0～0.5mg/L; Al
3+0～0.5mg/L; 20 ℃ of water temperatures;
C, supernatant overflow get into the biochemistry pool aeration, after biochemical treatment reaches national grade one discharge standard, discharge.
Add biological respinse nutrition: Ca in the biochemistry pool
2+: 15mg/L, Mg
2+: 15mg/L, Fe
2+: 28mg/L, KH
2PO
4520mg/L.
Aeration tank operational condition: hydraulic detention time 12～20h, oxygen dissolving value 0.5～3.5mg/L, 15～25 ℃ of service temperatures, pH 6.8～8.2.
After the second pond sedimentation, mud refluxes, and result is seen table 3
Table 3
Claims (5)
1. the treatment process of copper, zinc in the Cu-series catalyst for synthesizing methanol waste water, such wastewater treatment method may further comprise the steps:
A, in waste water, add the calcium polysulfide precipitation agent;
B, reaction and separation;
C, biochemical treatment.
2. method according to claim 1, the water quality situation such as the following table of wherein said waste water are said.
3. method according to claim 1 and 2, wherein in step a, precipitation agent calcium polysulfide (CaS
x) through the ordinary method preparation, wherein x is 2～4; At former water according to S: (Cu+Zn)=(0.5～2): 1 (mol ratio), in waste water, add calcium polysulfide solution, temperature is a normal temperature, adopts machinery or aeration type to stir, adding the precipitation agent afterreaction time is 0.5～2h.
4. method according to claim 1 and 2 wherein in step b, staticly settles 0.5～2h behind the waste water reaction, the throw out Separation and Recovery, and supernatant liquid overflow to biochemistry pool is handled.
5. method according to claim 1 and 2 wherein in step c, gets into biochemistry pool waste water quality pH 6～9, COD 5～60mg/L; NH
4 +-N 2.5～390mg/L, NO
3 --N 1000～3000mg/L; Cu
2+0～0.3mg/L; Zn
2+0～0.8mg/L; Al
3+0～0.5mg/L; Through biochemical treatment the time, the waste water hydraulic detention time is that 6～24h, pH 6.5～8.0, dissolved oxygen 0.5～5.5mg/L, water temperature are normal temperature; The nutritive salt dosage is in the waste water: Ca
2+10～25mg/L, Mg
2+10～25mg/L, Fe
3+30～60mg/L, KH
2PO
4500～800mg/L; Waste water is qualified discharge after biochemical treatment.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102897962A (en) * | 2012-08-23 | 2013-01-30 | 西南化工研究设计院有限公司 | Zero-discharge water recycling process used in copper-based catalyst co-precipitation production |
| CN107629796A (en) * | 2017-10-10 | 2018-01-26 | 中国科学院烟台海岸带研究所 | A kind of cadmium pollution soil efficient stable renovation agent and its preparation and application |
| CN109136553A (en) * | 2018-10-29 | 2019-01-04 | 新疆金川矿业有限公司 | A kind of your liquid impurity-removing method of indirect heap leaching of gold ores technique |
| CN113371909A (en) * | 2021-06-08 | 2021-09-10 | 中石化南京化工研究院有限公司 | Method for recycling wastewater generated in methanol synthesis catalyst production |
| CN115385477A (en) * | 2022-08-23 | 2022-11-25 | 长春黄金研究院有限公司 | Method for removing arsenic in contaminated acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897962A (en) * | 2012-08-23 | 2013-01-30 | 西南化工研究设计院有限公司 | Zero-discharge water recycling process used in copper-based catalyst co-precipitation production |
| CN107629796A (en) * | 2017-10-10 | 2018-01-26 | 中国科学院烟台海岸带研究所 | A kind of cadmium pollution soil efficient stable renovation agent and its preparation and application |
| CN109136553A (en) * | 2018-10-29 | 2019-01-04 | 新疆金川矿业有限公司 | A kind of your liquid impurity-removing method of indirect heap leaching of gold ores technique |
| CN113371909A (en) * | 2021-06-08 | 2021-09-10 | 中石化南京化工研究院有限公司 | Method for recycling wastewater generated in methanol synthesis catalyst production |
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Application publication date: 20120111 |