CN110156233A - A method of processing Cu-SSZ-13 molecular sieve waste liquid - Google Patents
A method of processing Cu-SSZ-13 molecular sieve waste liquid Download PDFInfo
- Publication number
- CN110156233A CN110156233A CN201910500264.6A CN201910500264A CN110156233A CN 110156233 A CN110156233 A CN 110156233A CN 201910500264 A CN201910500264 A CN 201910500264A CN 110156233 A CN110156233 A CN 110156233A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- ssz
- molecular sieve
- processing
- template
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical industry to be recycled technical field, and in particular to a method of processing Cu-SSZ-13 molecular sieve waste liquid.The present invention handles the method for Cu-SSZ-13 molecular sieve waste liquid by adjusting pH value, extraction, chromatographic column chromatography, removes the pollutant in waste liquid, while recycling the template of high value.The present invention abolishes the complexing of Cu-TEPA using acid waste liquid, is separated using TEPA and TMADaOH polarity difference, and impurity anions are exchanged into OH first with strong-base anion-exchange resin‑Reuse the separation that low pole macroporous absorbent resin realizes TEPA and TMADaOH, process is simple, and equipment cost is low, can be widely applied to the processing of Cu-SSZ-13 Zeolite synthesis waste liquid, the template N of recycling, N, N- trimethyl -1- adamantyl ammonium hydroxide value are high, and agents useful for same can be recycled, pollution can be reduced, production cost is reduced.
Description
Technical field
The invention belongs to chemical industry to be recycled technical field, and in particular to a kind of processing Cu-SSZ-13 molecular sieve is useless
The method of liquid.
Background technique
Cu-SSZ-13 molecular sieve is a kind of mesopore molecular sieve with chabasie (CHA) structure, in vehicle exhaust nitrogen oxidation
Object purification aspect is widely used.But template N used in synthesis process, N, N- trimethyl -1- adamantyl hydrogen
Amine-oxides (TMADaOH) are at high price, and cost problem significantly limits the use of Cu-SSZ-13 molecular sieve.Cu-SSZ- at present
13 method mainly has conventional synthetic methods and one-step synthesis.One-step synthesis, can due to introducing Cu-TEPA as template
To reduce the dosage of TMADaOH, and process is shorter, and cost is relatively low, is the hot spot studied at present.
One-step method is by copper sulphate, tetraethylenepentamine (TEPA), sodium hydroxide, sodium aluminate, silica solution, N, N, N- front three
Base -1- adamantyl ammonium hydroxide (TMADaOH) and water mixing, synthesize Cu-SSZ-13 molecular sieve under hydrothermal conditions.Because needing
The content for controlling Cu species in product cannot be too high, so there is still a need for more TMADaOH.Due in each molecular sieve cage only
The template of 2 molecules can be accommodated, so every 1g Cu-SSZ-13 for preparing only has the template of 0.39g or so to be fixed on molecular sieve
In cage.And in fact, the product excellent for processability, high mould silicon ratio is all selected in current Cu-SSZ-13 synthesis technology
Feeding mode.For example, the silicon mould ratio up to 0.7 to feed intake in patent CN104812469 A, i.e., every preparation 1g Cu-SSZ-13
Molecular sieve need to consume the TMADaOH of 2.52g or so, and TMADaOH is at concentrations up to 10.36mol/L in waste liquid.In the waste liquid of one-step method
Other than some inorganic ions, also containing Cu-TEPA, tetraethylenepentamine and more TMADaOH, these itrogenous organic substance properties
Stablize, it is larger to water pollution, and can not be removed by conventional means such as sedimentations.
The country is seldom about the related patents of Zeolite synthesis liquid waste processing, mostly the waste liquid of phosphor-silicon-aluminum molecular sieve (SAPO)
Processing, waste liquid composition and template nature difference are larger, do not have reference value；Other about Cu-TEPA, tetraethylenepentamine and
The document of TMADaOH physicochemical property is also seldom.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of processing Cu-
The method of SSZ-13 molecular sieve waste liquid.The present invention abolishes the complexing of Cu-TEPA using acid waste liquid, utilizes TEPA and TMADaOH
Polarity difference is separated, and process is simple, and equipment cost is low, when can be widely applied to one-step method preparation Cu-SSZ-13 molecular sieve
The processing of the waste liquid of generation, the N of recycling, N, N- trimethyl -1- adamantyl ammonium hydroxide template value is high, and agents useful for same
It can be recycled, pollution can be reduced, reduce production cost.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of processing Cu-SSZ-13 molecular sieve waste liquid
Method, which is characterized in that the method for processing Cu-SSZ-13 molecular sieve waste liquid has the feature that
A method of processing Cu-SSZ-13 molecular sieve waste liquid, comprising the following steps:
(1) be added acid waste liquid into Cu-SSZ-13 molecular sieve waste liquid, adjust the pH value of Cu-SSZ-13 molecular sieve waste liquid to 5 ~
8, suction filtration or filters pressing are carried out, filtrate is collected；
(2) filtrate that step (1) obtains is extracted using organic solvent, collected organic layer；
(3) organic layer of step (2) is evaporated, obtained crystal is dissolved in water；
(4) aqueous solution for obtaining step (3) obtains template weak solution by chromatographic column；
(5) the template weak solution of step (4) is heated to concentration at 80 DEG C ~ 200 DEG C, obtains template concentrated solution.
Acid waste liquid described in step (1) contains one of hydrochloric acid, sulfuric acid, nitric acid or a variety of.
The mass ratio to feed intake in step (2) is filtrate: organic solvent=100:50 ~ 100:1.
Organic solvent described in step (2) is toluene, dimethylbenzene or chloroform.
Chromatographic column filling described in step (4) has low pole macroporous absorbent resin and strong-base anion-exchange resin, weak
Polar macroporous adsorption resin and strong-base anion-exchange resin packing volume ratio are 1:10 ~ 1:1.
Aqueous solution described in step (4) first passes through strong-base anion-exchange resin, then passes through low pole macroporous absorption tree
Rouge.
Template described in step (4) and step (5) is N, N, N- trimethyl -1- adamantyl ammonium hydroxide.
Heating concentration described in step (5) is carried out in the heating and evaporating unit with condensing plant.
After template concentrated solution described in step (5) quantitatively measures template agent content, it can be used for synthesis of molecular sieve again.
It is generated when the waste liquid is using one-step synthesis method Cu-SSZ-13 molecular sieve.
Compared with prior art, the invention has the following advantages:
The present invention abolishes the complexing of Cu-TEPA using acid waste liquid, is separated using TEPA and TMADaOH polarity difference, first
Impurity anions are exchanged into OH using strong-base anion-exchange resin-, reuse the realization of low pole macroporous absorbent resin
The separation of TEPA and TMADaOH, process is simple, and equipment cost is low, can be widely applied to one-step method preparation Cu-SSZ-13 molecular sieve
When the processing of synthesis waste liquid that generates, template N, N, the N- trimethyl -1- adamantyl ammonium hydroxide of recycling is worth high, and institute
It can be recycled with reagent, pollution can be reduced, reduce production cost.
Further description of the technical solution of the present invention With reference to embodiment.
Specific embodiment
Embodiment 1
A method of processing Cu-SSZ-13 molecular sieve waste liquid, comprising the following steps:
(1) (molar ratio of synthesis is Cu- to the waste liquid generated to 1000g using one-step synthesis method Cu-SSZ-13 molecular sieve
TEPA:Na2O:Al2O3: SiO2: TMADaOH:H2O=1.1:1:1:15:4.5:400) in be added the acid waste liquid containing hydrochloric acid, adjust
PH=7 for saving waste liquid obtain mixing turbid, filter, and collect filtrate, following reaction occurs in this step:
[Al(OH)4]- + H+ = Al(OH)3 + H2O
[Cu-TEPA]2+ + 5H+ = Cu2+ + C8H28N5 5+
TEPA + 5H+ = C8H28N5 5+
OH- + H+ = H2O；
(2) 400g toluene is added in the filtrate obtained to step (1) to extract, collected organic layer, it is in water layer and alkaline waste liquor and heavy
Direct emission after drop；
(3) organic layer that step (2) obtains is heated in the flask equipped with condenser pipe, obtains 37g and contains TMADa+With
TEPA5+Mixture, the dissolution of 111g water is added, condenses the recycling in extraction next time of the toluene of collection；
(4) solution for obtaining step (3) is with the amount of 1.1 times of bed volumes, successively by being filled with strong alkalinity anion exchange
The chromatographic column of resin and Ls-40 low pole macroporous absorbent resin, Ls-40 low pole macroporous absorbent resin and strong alkalinity anion are handed over
The packing volume ratio for changing resin is 1.3:7, is eluted using deionized water to leacheate and is in neutrality, obtains the template comprising leacheate
Agent weak solution 400g, chromatographic column are regenerated using the sodium hydrate aqueous solution that concentration is 8%, and the volume of sodium hydrate aqueous solution is bed
3 times of layer volume, and be in neutrality using deionized water washing chromatographic column to chromatographic solution；
(5) the template weak solution heating concentration obtained step (4), obtains the aqueous solution of 107g TMADaOH, uses total nitrogen
It is 26.77% that analyzer, which measures TMADaOH mass fraction, can be directly used for synthesis of molecular sieve again.
Embodiment 2
A method of processing Cu-SSZ-13 molecular sieve waste liquid, comprising the following steps:
(1) (molar ratio of synthesis is Cu- to the waste liquid generated to 500g using one-step synthesis method Cu-SSZ-13 molecular sieve
TEPA:Na2O:Al2O3: SiO2: TMADaOH:H2O=0.8:3:1:10:5:200) in be added the acid waste liquid containing nitric acid, adjust
PH=6 of waste liquid obtain mixing turbid, and filters pressing collects filtrate, following reaction occurs in this step:
[Al(OH)4]- + H+ = Al(OH)3 + H2O
[Cu-TEPA]2+ + 5H+ = Cu2+ + C8H28N5 5+
TEPA + 5H+ = C8H28N5 5+
OH- + H+ = H2O；
(2) 100g xylene extraction, collected organic layer are added in the filtrate obtained to step (1), water layer and alkaline waste liquor neutralize
Direct emission after sedimentation；
(3) organic layer that step (2) obtains is heated in the flask equipped with condenser pipe, obtains 32g and contains TMADa+With
TEPA5+Mixture, the dissolution of 96g water is added, condenses the recycling in extraction next time of the dimethylbenzene of collection；
(4) solution for obtaining step (3) is with the amount of 1.1 times of bed volumes, successively by being filled with strong alkalinity anion exchange
The chromatographic column of resin and Ls-40 low pole macroporous absorbent resin, Ls-40 low pole macroporous absorbent resin and strong alkalinity anion are handed over
The packing volume ratio for changing resin is 1.3:7, is eluted using deionized water to leacheate and is in neutrality, obtains the template comprising leacheate
Agent weak solution 387g, chromatographic column are regenerated using the sodium hydrate aqueous solution that concentration is 8%, and the volume of sodium hydrate aqueous solution is bed
3 times of layer volume, and be in neutrality using deionized water washing chromatographic column to chromatographic solution；
(5) the template weak solution heating concentration obtained step (4), obtains the aqueous solution of 92g TMADaOH, uses total nitrogen point
It is 24.96% that analyzer, which measures TMADaOH mass fraction, can be directly used for synthesis of molecular sieve again.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by present specification, or directly/it is used in other indirectly
Relevant technical field is included in scope of patent protection of the invention.
Claims (10)
1. a kind of method for handling Cu-SSZ-13 molecular sieve waste liquid, which comprises the following steps:
(1) be added acid waste liquid into Cu-SSZ-13 molecular sieve waste liquid, adjust the pH value of Cu-SSZ-13 molecular sieve waste liquid to 5 ~
8, suction filtration or filters pressing are carried out, filtrate is collected；
(2) filtrate that step (1) obtains is extracted using organic solvent, collected organic layer；
(3) organic layer of step (2) is evaporated, obtained crystal is dissolved in water；
(4) aqueous solution for obtaining step (3) obtains template weak solution by chromatographic column；
(5) the template weak solution of step (4) is heated to concentration at 80 DEG C ~ 200 DEG C, obtains template concentrated solution.
2. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (1)
It states acid waste liquid and contains one of hydrochloric acid, sulfuric acid, nitric acid or a variety of.
3. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that thrown in step (2)
The mass ratio of material is filtrate: organic solvent=100:50 ~ 100:1.
4. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (2)
Stating organic solvent is toluene, dimethylbenzene or chloroform.
5. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (4)
Stating chromatographic column filling has low pole macroporous absorbent resin and a strong-base anion-exchange resin, low pole macroporous absorbent resin and strong
Alkalescence anion-exchange resin packing volume ratio is 1:10 ~ 1:1.
6. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (4)
It states aqueous solution and first passes through strong-base anion-exchange resin, then pass through low pole macroporous absorbent resin.
7. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that step (4) and step
Suddenly template described in (5) is N, N, N- trimethyl -1- adamantyl ammonium hydroxide.
8. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (5)
Stating heating concentration is carried out in the heating and evaporating unit with condensing plant.
9. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that institute in step (5)
It states after template concentrated solution quantitatively measures template agent content, can be directly used for synthesis of molecular sieve again.
10. the method for processing Cu-SSZ-13 molecular sieve waste liquid according to claim 1, which is characterized in that the waste liquid is
It is generated when using one-step synthesis method Cu-SSZ-13 molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910500264.6A CN110156233A (en) | 2019-06-11 | 2019-06-11 | A method of processing Cu-SSZ-13 molecular sieve waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910500264.6A CN110156233A (en) | 2019-06-11 | 2019-06-11 | A method of processing Cu-SSZ-13 molecular sieve waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110156233A true CN110156233A (en) | 2019-08-23 |
Family
ID=67628402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910500264.6A Pending CN110156233A (en) | 2019-06-11 | 2019-06-11 | A method of processing Cu-SSZ-13 molecular sieve waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110156233A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477653A (en) * | 2022-02-24 | 2022-05-13 | 陕西煤业化工技术研究院有限责任公司 | Method and system for treating wastewater in molecular sieve production process |
| CN115521012A (en) * | 2022-10-08 | 2022-12-27 | 合肥中科弘逸环保科技有限责任公司 | Method for treating in-situ synthesized Cu-SSZ-13 molecular sieve waste liquid |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1110607A2 (en) * | 1999-12-21 | 2001-06-27 | Chemiewerk Bad Köstritz GmbH | Modification process of a ion exchangable material |
| CN102688608A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | Method for recovering mesoporous molecular sieve organic template |
| CN103787370A (en) * | 2013-12-31 | 2014-05-14 | 中国天辰工程有限公司 | Recycling method for template agent in preparation process of molecular sieve |
| CN105130082A (en) * | 2015-09-17 | 2015-12-09 | 博天环境集团股份有限公司 | Method for treating triethylamine-contained wastewater |
| CN105198147A (en) * | 2015-09-15 | 2015-12-30 | 博天环境集团股份有限公司 | Treatment method for organic amine waste water generated by producing molecular sieve and carrier catalyst thereof |
| CN106238092A (en) * | 2016-07-13 | 2016-12-21 | 无锡威孚环保催化剂有限公司 | The method of one-step synthesis method Cu SSZ 13 molecular sieve catalyst |
| CN106495205A (en) * | 2016-11-18 | 2017-03-15 | 东莞市新意工业废物处理有限公司 | A kind of cupric sulfate purified and its production technology |
| US10151017B2 (en) * | 2016-04-24 | 2018-12-11 | Yadian Xie | Method for extracting ultra high purity alumina from wasterwater |
-
2019
- 2019-06-11 CN CN201910500264.6A patent/CN110156233A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1110607A2 (en) * | 1999-12-21 | 2001-06-27 | Chemiewerk Bad Köstritz GmbH | Modification process of a ion exchangable material |
| CN102688608A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | Method for recovering mesoporous molecular sieve organic template |
| CN103787370A (en) * | 2013-12-31 | 2014-05-14 | 中国天辰工程有限公司 | Recycling method for template agent in preparation process of molecular sieve |
| CN105198147A (en) * | 2015-09-15 | 2015-12-30 | 博天环境集团股份有限公司 | Treatment method for organic amine waste water generated by producing molecular sieve and carrier catalyst thereof |
| CN105130082A (en) * | 2015-09-17 | 2015-12-09 | 博天环境集团股份有限公司 | Method for treating triethylamine-contained wastewater |
| US10151017B2 (en) * | 2016-04-24 | 2018-12-11 | Yadian Xie | Method for extracting ultra high purity alumina from wasterwater |
| CN106238092A (en) * | 2016-07-13 | 2016-12-21 | 无锡威孚环保催化剂有限公司 | The method of one-step synthesis method Cu SSZ 13 molecular sieve catalyst |
| CN106495205A (en) * | 2016-11-18 | 2017-03-15 | 东莞市新意工业废物处理有限公司 | A kind of cupric sulfate purified and its production technology |
Non-Patent Citations (2)
| Title |
|---|
| 张兴丽: "《生物化学实验指导》", 31 August 2017, 中国轻工业出版社 * |
| 李丽华: "《天然药物化学实验教程》", 30 June 2017, 中国医药科技出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477653A (en) * | 2022-02-24 | 2022-05-13 | 陕西煤业化工技术研究院有限责任公司 | Method and system for treating wastewater in molecular sieve production process |
| CN115521012A (en) * | 2022-10-08 | 2022-12-27 | 合肥中科弘逸环保科技有限责任公司 | Method for treating in-situ synthesized Cu-SSZ-13 molecular sieve waste liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111039832B (en) | Method for producing taurine and method for removing impurities from reaction system for preparing taurine | |
| EP3786153B1 (en) | Method and system for removing impurities out of taurine mother liquor and taurine mother liquor recovery | |
| CN102001635B (en) | Process for preparing ultrapure nitric acid | |
| CN103991847A (en) | Preparation method for electron-grade hydrofluoric acid | |
| CN102320629B (en) | Method for producing reagent grade sodium sulfate by using white carbon black mother solution | |
| CN112340703B (en) | Method for preparing anhydrous hydrogen fluoride and nano silicon dioxide by using fluosilicic acid | |
| CN102910853B (en) | A kind of method using H acid Sewage treatments liquid production naphthalene series high-efficiency water-reducing agent | |
| CN110156233A (en) | A method of processing Cu-SSZ-13 molecular sieve waste liquid | |
| CN111413441B (en) | Acetonitrile purification method for improved ultra-high liquid chromatography-mass spectrometer | |
| CN103601163B (en) | A kind of preparation method of high pure nitric acid | |
| CN112480035A (en) | N-methylmorpholine and purification method thereof, methylmorpholine oxide and preparation method thereof | |
| CN112174209A (en) | Green molybdenum smelting ion exchange process | |
| CN101033231A (en) | Method of preparing high-purity medical xanthonumic acid | |
| CN205473144U (en) | Heavy metal ammonia nitrogen wastewater can be high salt tungstenic of simultaneous processing contained and resource integrated processing system of ammonia waste gas is contained | |
| CN108607500A (en) | A kind of gel adsorber and preparation method carrying lithium for salt lake brine with high magnesium-lithium ratio | |
| CN110156610B (en) | Method for recovering template from SSZ-13 molecular sieve synthesis waste liquid | |
| CN103288135A (en) | Method for recycling all chemical components in filament melting molybdenum-containing waste acid | |
| CN107128955B (en) | A method of extracting lithium carbonate from thermal water | |
| RU2506331C1 (en) | Method for obtaining ammonium tungstate | |
| RU2528692C2 (en) | Method of extracting rare-earth elements from wet-process phosphoric acid when processing khibiny apatite concentrates | |
| JP2013245159A (en) | Method for comprehensively treating claus tail gas and producing manganese sulfate | |
| RU2544731C2 (en) | Method of extracting rare earth elements from extraction phosphoric acid | |
| CN110451463A (en) | The method for removing iron of titanium dioxide waste acid by sulfuric acid process | |
| CN105174236B (en) | A kind of phosphoric acid by wet process prepares the method and apparatus of potassium phosphate | |
| CN1551854A (en) | An improved process for manufacturing highly concentrated hydroxylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190823 |