CN107721878A - A kind of method using fusion-crystallization technology separating-purifying succinonitrile - Google Patents
A kind of method using fusion-crystallization technology separating-purifying succinonitrile Download PDFInfo
- Publication number
- CN107721878A CN107721878A CN201710995556.2A CN201710995556A CN107721878A CN 107721878 A CN107721878 A CN 107721878A CN 201710995556 A CN201710995556 A CN 201710995556A CN 107721878 A CN107721878 A CN 107721878A
- Authority
- CN
- China
- Prior art keywords
- succinonitrile
- sweating
- crystallization
- fusion
- purity
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method using fusion-crystallization technology separating-purifying succinonitrile, succinonitrile crude product is added in melting crystallizer, be heated to 59 DEG C it is complete it is molten after, then start program is cooled to 45 DEG C~52 DEG C, after stablizing 10~180min, crystalline mother solution is released, obtains succinonitrile coarse crystal；Then start program heats up, and carries out sweating, and stablizes 10~180min after sweating final temperature is reached, and obtains high-purity succinonitrile crystal of purity more than 99.95%.The inventive method uses the separation method of fusion-crystallization, it is not necessary to solvent, it is not required that vacuum drying, operating time are short；It is simple to operate, green, product purity is high, crystalline mother solution and sweating can again be reclaimed by fusion-crystallization and continue to purify；Compared to existing intermittent rectification under vacuum method, energy consumption is low, operation temperature is low, cost is low, does not have polymerization coking phenomenon in operating process, does not influence yield and quality.
Description
Technical field
The invention belongs to lithium ion battery succinonitrile production technical field, and in particular to one kind uses fusion-crystallization technology
The method of separating-purifying succinonitrile.
Background technology
Electronics industry is developed rapidly so that we have been enter into information-based digital times, so that people produce to electronics
The demand of product is also increasing, and this also causes us the demand to lithium ion battery also to increase year by year.Japan
Bridgestone companies improve in the electrolysis additive for developing first generation lithium ion battery in 2002, this additive part
The high-temperature behavior of lithium ion battery, cycle performance and security performance, and lay a good foundation for this.Lithium-ion battery electrolytes add
Add agent that there is the characteristics of with strong points and dosage is few, can show under conditions of not changing production technology and not improving production cost
Write the performance for improving battery.Succinonitrile has anti-inflatable, improves electrochemical stability windows, improves battery high-temperature cycle performance
And the advantages that security performance, the important source material of lithium-ion battery electrolytes additive is increasingly becoming in recent years, and gradually receives state
The attention of electrolyte inside manufacturer.Succinonitrile purity is larger for the performance impact of lithium ion battery：When succinonitrile purity exists
When more than 99.95%, the efficiency first and specific capacity of lithium ion battery are all bigger.When purity is more than 99.95%, fourth two
When the addition of nitrile is 3%, the electrical property of composite positive pole is preferable.Research work on succinonitrile synthesis both at home and abroad at present
Less, only partial monopoly discloses its production method, substantially using Material synthesis such as succinic acid, acrylonitrile, and gained fourth
Dintrile purity is more than 99%, and with some crocus.No matter the succinonitrile of which kind of technique productions is used, and its purity all exists
Less than 99.95%, it is unable to reach the requirement of the additive as lithium-ion battery electrolytes.
The existing purifying technique of succinonitrile has following three kinds：(1) crystallisation purification prepares high-purity succinonitrile；(2) absorption method
Purification prepares high-purity succinonitrile；(3) intermittent rectification under vacuum method prepares high-purity succinonitrile.Crystallisation purification succinonitrile needs to consume greatly
Solvent is measured, and higher, it is necessary to be high neat solvent, energy consumption is big is required to solvent purity；Absorption method purifies succinonitrile to succinonitrile
Purity is less than 99.95% after purification, and adsorbs strict to adsorbent requirement in purification process, and adsorbent is miscellaneous without any solubility
Matter, adsorbent are difficult regeneration, and caused solid waste is difficult to handle and causes new environmental pollution, and operation is more multiple
Miscellaneous, operating cost is high；Simple to operate using intermittent rectification under vacuum method, cost is low, but temperature is higher in purification process, easily causes
Polymerization coking etc., influences product yield and quality.
Fusion-crystallization technology is a kind of new separation method to grow up the 1970s.Fused junction crystallization is basis
The difference of freezing point between separate substance and the method for realizing material separation and purification, are mainly used in the separation of organic compound.
With the features such as product purity is high, energy consumption is low, need not add other solvents, and environmental pollution is small.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of simple to operate, it is not necessary to the height of other solvents
The method of pure succinonitrile fusion-crystallization, more than 99.95% product is can obtain by this method.
Technical scheme is as follows:
A kind of method of purification of fusion-crystallization technology separating-purifying succinonitrile, its step are as follows:Succinonitrile crude product is added
In melting crystallizer, it is heated to complete molten, then starts to be cooled to 45 DEG C~52 DEG C of final temperature of crystallization, after stable, release crystalline mother solution,
Obtain succinonitrile coarse crystal；Then start to warm up, carry out sweating, and it is stable after sweating final temperature is reached, obtain succinonitrile crystal.
Described heat to full solubility temperature is preferably 59 DEG C.
Described stabilization time is preferably 10~180min.
Described rate of temperature fall is preferably 0.001~0.2 DEG C/min.
Described rate of temperature fall is preferably 0.01~0.08 DEG C/min.
Described heating rate is preferably 0.001~0.1 DEG C/min.
Described heating rate is preferably 0.005~0.05 DEG C/min.
Described sweating final temperature is preferably 55 DEG C~58 DEG C.
Described crystallization final temperature is preferably 47 DEG C~51 DEG C.
The present invention obtains high-purity succinonitrile crystal, and its purity is higher than 99.95%.
It is of the invention compared with existing purification technique, its advantage is as follows：
(1) the inventive method uses the separation method of fusion-crystallization, compared to existing solvent crystallization method, it is not necessary to molten
Agent, it is not required that vacuum drying, operating time are short；
(2) existing absorption method is compared, simple to operate, green, product purity high (can reach more than 99.99%),
Crystalline mother solution and sweating can be reclaimed again by fusion-crystallization to be continued to purify；
(3) existing intermittent rectification under vacuum method is compared, energy consumption is low, operation temperature is low, cost is low, without poly- in operating process
Coking phenomenon is closed, does not influence yield and quality.
Embodiment
The present invention is described in more detail below, but the invention is not limited in this.
Embodiment 1
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.01 DEG C/
Min speed start program is cooled to 52.0 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 180min and is released, to liquid
No longer flow out；Then sweating is started to warm up to 55.0 DEG C with 0.01 DEG C/min speed, and keeps 10min, pick out sweating.Most
Final products are obtained after the succinonitrile in crystallizer is dissolved by heating afterwards, yield is about 40.1%, and product purity reaches
99.96%.
Embodiment 2
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.005 DEG C/
Min speed start program is cooled to 51.0 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 120min and is released, to liquid
No longer flow out；Then sweating is started to warm up to 56.0 DEG C with 0.05 DEG C/min speed, and keeps 30min, pick out sweating.Most
Final products are obtained after the succinonitrile in crystallizer is dissolved by heating afterwards, yield is about 45.6%, and product purity reaches
99.97%.
Embodiment 3
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.008 DEG C/
Min speed start program is cooled to 50.0 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 60min and is released, to liquid
No longer flow out；Then sweating is started to warm up to 57.0 DEG C with 0.1 DEG C/min speed, and keeps 60min, pick out sweating.Most
Final products are obtained after the succinonitrile in crystallizer is dissolved by heating afterwards, yield is about 45.6%, and product purity reaches
99.97%.
Embodiment 4
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.005 DEG C/
Min speed start program is cooled to 49.0 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 30min and is released, to liquid
No longer flow out；Then sweating is started to warm up to 57 DEG C with 0.03 DEG C/min speed, and keeps 60min, pick out sweating.Finally
Final products are obtained after succinonitrile in crystallizer is dissolved by heating, yield is about 40.6%, and product purity reaches 99.97%.
Embodiment 5
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.001 DEG C/
Min speed start program is cooled to 48 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 60min and is released, to liquid not
Flow out again；Then sweating is started to warm up to 58 DEG C with 0.01 DEG C/min speed, and keeps 10min, pick out sweating.Finally will
Succinonitrile in crystallizer obtains final products after dissolving by heating, and yield is about 45.6%, and product purity reaches 99.97%.
Embodiment 6
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.05 DEG C/
Min speed start program is cooled to 47 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 30min and is released, to liquid not
Flow out again；Then sweating is started to warm up to 56 DEG C with 0.008 DEG C/min speed, and keeps 60min, pick out sweating.Finally
Final products are obtained after succinonitrile in crystallizer is dissolved by heating, yield is about 62.9%, and product purity reaches 99.96%.
Embodiment 7
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.1 DEG C/
Min speed start program is cooled to 46 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 30min and is released, to liquid not
Flow out again；Then sweating is started to warm up to 56 DEG C with 0.005 DEG C/min speed, and keeps 120min, pick out sweating.Finally
Final products are obtained after succinonitrile in crystallizer is dissolved by heating, yield is about 53.6%, and product purity reaches 99.97%.
Embodiment 8
100.0g succinonitrile raw materials are weighed, succinonitrile crude product purity is 99.81%, light component impurity content 0.08%, weight
Composition impurity content 0.11%.Succinonitrile crude product is put into melting crystallizer, be heated to 59.0 DEG C it is complete it is molten after, with 0.2 DEG C/
Min speed start program is cooled to 45 DEG C, and it is crystalline mother solution that bottom stopper is taken out after stable 10min and is released, to liquid not
Flow out again；Then sweating is started to warm up to 57 DEG C with 0.001 DEG C/min speed, and keeps 120min, pick out sweating.Finally
Final products are obtained after succinonitrile in crystallizer is dissolved by heating, yield is about 63.6%, and product purity reaches 99.96%.
A kind of method using fusion-crystallization technology separating-purifying succinonitrile that the present invention is disclosed and proposed, art technology
Personnel can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although the method and technology of preparing of the present invention
It is described by preferred embodiment, person skilled can substantially not depart from present invention, spirit and scope
It is interior that methods and techniques described herein route is modified or reconfigured, to realize final technology of preparing.Especially need
, it is noted that all similar replacements and change are apparent to those skilled in the art, they are considered as
It is included in spiritual, scope and content of the invention.
Claims (9)
1. a kind of method of purification of fusion-crystallization technology separating-purifying succinonitrile, it is characterised in that step is as follows:Succinonitrile is thick
Product are added in melting crystallizer, are heated to complete molten, are then started to be cooled to 45 DEG C~52 DEG C of final temperature of crystallization, after stable, are released knot
Brilliant mother liquor, obtain succinonitrile coarse crystal；Then start to warm up, carry out sweating, and it is stable after sweating final temperature is reached, obtain fourth two
Nitrile crystal.
2. the method as described in claim 1, it is characterized in that heat to full solubility temperature is 59 DEG C.
3. the method as described in claim 1, it is characterized in that stabilization time is 10~180min.
4. the method as described in claim 1, it is characterized in that rate of temperature fall is 0.001~0.2 DEG C/min.
5. the method as described in claim 1, it is characterized in that rate of temperature fall is 0.01~0.08 DEG C/min.
6. the method as described in claim 1, it is characterized in that heating rate is 0.001~0.1 DEG C/min.
7. the method as described in claim 1, it is characterized in that heating rate is 0.005~0.05 DEG C/min.
8. the method as described in claim 1, it is characterized in that sweating final temperature is 55 DEG C~58 DEG C.
9. the method as described in claim 1, it is characterized in that crystallization final temperature is 47 DEG C~51 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710995556.2A CN107721878A (en) | 2017-10-23 | 2017-10-23 | A kind of method using fusion-crystallization technology separating-purifying succinonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710995556.2A CN107721878A (en) | 2017-10-23 | 2017-10-23 | A kind of method using fusion-crystallization technology separating-purifying succinonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107721878A true CN107721878A (en) | 2018-02-23 |
Family
ID=61212356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710995556.2A Pending CN107721878A (en) | 2017-10-23 | 2017-10-23 | A kind of method using fusion-crystallization technology separating-purifying succinonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107721878A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535028A (en) * | 2018-11-15 | 2019-03-29 | 天津科技大学 | The method that levitation melting crystallisation prepares aniline-acetonitrile sterling |
| CN109761793A (en) * | 2019-03-08 | 2019-05-17 | 河北工业大学 | A kind of method of solution-fusion-crystallization integrated separation purification mixed dibasic acid |
| CN112679385A (en) * | 2020-12-31 | 2021-04-20 | 河北诚信集团有限公司 | Purification method of malononitrile |
| CN113651699A (en) * | 2021-08-05 | 2021-11-16 | 天津科技大学 | Method for preparing high-purity 2, 4-dinitrochlorobenzene by layer-type melt crystallization |
| CN114181113A (en) * | 2021-12-20 | 2022-03-15 | 无锡殷达尼龙有限公司 | Refining process of long-carbon-chain dinitrile |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3132039A (en) * | 1960-12-22 | 1964-05-05 | Monsanto Chemicals | Heat responsive recording sheet |
| US3839408A (en) * | 1971-10-05 | 1974-10-01 | Basf Ag | Continuous purification of adiponitrile |
| JPS53116321A (en) * | 1977-02-23 | 1978-10-11 | Ihara Chem Ind Co Ltd | Purification of organocyano compounds |
| EP0711752A2 (en) * | 1994-11-08 | 1996-05-15 | Hoechst Aktiengesellschaft | Cis-4-(2,2,3,3-tetrafluoropropoxy)cinnamic acid nitrile and trans-4-(2,2,3,3-tetrafluoro)cinnamic acid nitrile and process for their preparation |
| CN1656060A (en) * | 2002-05-28 | 2005-08-17 | 巴斯福股份公司 | Method for reducing the content of an unsaturated amine in a mixture containing an amino nitrile, a diamine, a dinitrile or mixtures thereof |
| CN102939276A (en) * | 2010-05-19 | 2013-02-20 | 生物琥珀酸有限公司 | Processes for producing diaminobutane (dab), succinic dinitrile (sdn) and succinamide (dam) |
| CN103342661A (en) * | 2013-07-19 | 2013-10-09 | 中国海洋石油总公司 | Crystal purifying method of high purity butanedinitrile |
| CN103360280A (en) * | 2013-07-19 | 2013-10-23 | 中国海洋石油总公司 | Adsorption purification method for high-purity butanedinitrile |
| CN106957245A (en) * | 2015-11-30 | 2017-07-18 | 赢创德固赛有限公司 | Cyan-3,5,5-trimethyl cyclohexanone is finely purified by fusion-crystallization |
-
2017
- 2017-10-23 CN CN201710995556.2A patent/CN107721878A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3132039A (en) * | 1960-12-22 | 1964-05-05 | Monsanto Chemicals | Heat responsive recording sheet |
| US3839408A (en) * | 1971-10-05 | 1974-10-01 | Basf Ag | Continuous purification of adiponitrile |
| JPS53116321A (en) * | 1977-02-23 | 1978-10-11 | Ihara Chem Ind Co Ltd | Purification of organocyano compounds |
| EP0711752A2 (en) * | 1994-11-08 | 1996-05-15 | Hoechst Aktiengesellschaft | Cis-4-(2,2,3,3-tetrafluoropropoxy)cinnamic acid nitrile and trans-4-(2,2,3,3-tetrafluoro)cinnamic acid nitrile and process for their preparation |
| CN1656060A (en) * | 2002-05-28 | 2005-08-17 | 巴斯福股份公司 | Method for reducing the content of an unsaturated amine in a mixture containing an amino nitrile, a diamine, a dinitrile or mixtures thereof |
| CN102939276A (en) * | 2010-05-19 | 2013-02-20 | 生物琥珀酸有限公司 | Processes for producing diaminobutane (dab), succinic dinitrile (sdn) and succinamide (dam) |
| CN103342661A (en) * | 2013-07-19 | 2013-10-09 | 中国海洋石油总公司 | Crystal purifying method of high purity butanedinitrile |
| CN103360280A (en) * | 2013-07-19 | 2013-10-23 | 中国海洋石油总公司 | Adsorption purification method for high-purity butanedinitrile |
| CN106957245A (en) * | 2015-11-30 | 2017-07-18 | 赢创德固赛有限公司 | Cyan-3,5,5-trimethyl cyclohexanone is finely purified by fusion-crystallization |
Non-Patent Citations (6)
| Title |
|---|
| LAN, C. W.ETAL: "Interface control mechanisms in horizontal zone-melting with slow rotation", 《JOURNAL OF CRYSTAL GROWTH》 * |
| LIU, J.ETAL: "A unique zone refining apparatus for purification of low melting point organic materials", 《 CRYSTAL PROPERTIES AND PREPARATION》 * |
| UTTER, B.ETAL: "Experimental apparatus and sample preparation techniques for directional solidification", 《REVIEW OF SCIENTIFIC INSTRUMENTS》 * |
| 叶铁林: "《化工结晶过程原理及应用》", 31 December 2006 * |
| 陈志: "相场法模拟丁二腈枝晶生长研究", 《特种铸造及有色合金》 * |
| 雷松鹤: "晶体凝固过程微流动的实时观察研究", 《西北工业大学硕学位论文》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535028A (en) * | 2018-11-15 | 2019-03-29 | 天津科技大学 | The method that levitation melting crystallisation prepares aniline-acetonitrile sterling |
| CN109535028B (en) * | 2018-11-15 | 2021-10-08 | 天津科技大学 | Method for preparing pure anilinoacetonitrile by suspension melting crystallization method |
| CN109761793A (en) * | 2019-03-08 | 2019-05-17 | 河北工业大学 | A kind of method of solution-fusion-crystallization integrated separation purification mixed dibasic acid |
| CN109761793B (en) * | 2019-03-08 | 2022-03-22 | 河北工业大学 | Method for separating and purifying mixed dibasic acid by solution-melt crystallization coupling |
| CN112679385A (en) * | 2020-12-31 | 2021-04-20 | 河北诚信集团有限公司 | Purification method of malononitrile |
| CN113651699A (en) * | 2021-08-05 | 2021-11-16 | 天津科技大学 | Method for preparing high-purity 2, 4-dinitrochlorobenzene by layer-type melt crystallization |
| CN113651699B (en) * | 2021-08-05 | 2023-11-21 | 天津科技大学 | Method for preparing high-purity 2, 4-dinitrochlorobenzene by layered melt crystallization |
| CN114181113A (en) * | 2021-12-20 | 2022-03-15 | 无锡殷达尼龙有限公司 | Refining process of long-carbon-chain dinitrile |
| CN114181113B (en) * | 2021-12-20 | 2024-04-16 | 无锡殷达尼龙有限公司 | Refining process of long carbon chain dinitrile |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107721878A (en) | A kind of method using fusion-crystallization technology separating-purifying succinonitrile | |
| CN104291347B (en) | Preparation method of lithium tetrafluoroborate | |
| CN106882819B (en) | A kind of lithium hexafluoro phosphate prepares purification process | |
| WO2018113478A1 (en) | Method for producing lithium hydroxide monohydrate using lithium carbonate as raw material | |
| CN110668411B (en) | Purification method of lithium bis (fluorosulfonyl) imide | |
| CN104310421A (en) | Preparation method of high-purity lithium tetrafluoroborate | |
| CN104555959A (en) | Method for preparing lithium hexafluorophosphate quickly | |
| KR20230110677A (en) | Method for purifying vinylene carbonate by rectification-melting crystallization bonding technique | |
| CN105541782A (en) | Vinylene carbonate purifying method | |
| CN103342372B (en) | Method for preparing lithium tetrafluoroborate | |
| CN102643169A (en) | Method for purifying resorcinol by means of continuous crystallization | |
| CN104447828A (en) | Method for synthesizing and purifying lithium bis(oxalato)borate | |
| CN103466664A (en) | Fully-automatic production line type potassium nitrate recovering process | |
| CN103113344A (en) | Purification method of high-purity fluoroethylene carbonate | |
| CN107827865A (en) | A kind of method of purification of 1,3 propane sultone | |
| CN101570337A (en) | Production method of battery- grade lithium fluoride | |
| CN104211029B (en) | A kind of preparation method of lithium hexafluoro phosphate | |
| CN103342661A (en) | Crystal purifying method of high purity butanedinitrile | |
| CN109110774B (en) | Preparation method of lithium tetrafluoroborate | |
| CN102766151A (en) | Method for purifying lithium bis(oxalate)borate | |
| CN103232402B (en) | A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material | |
| CN102780014A (en) | Method for regenerating manganese sulfate from waste alkaline zinc-manganese battery | |
| CN105481887A (en) | Preparation method of lithium oxalyldifluroborate | |
| CN102502565B (en) | Preparation method of lithium hexafluorophate | |
| CN107162889B (en) | Method for preparing and purifying 2-tert-amylanthraquinone |
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: 20180223 |