CN112920187A - Method for simultaneously removing formaldehyde and synthesizing metal complex and application thereof - Google Patents
Method for simultaneously removing formaldehyde and synthesizing metal complex and application thereof Download PDFInfo
- Publication number
- CN112920187A CN112920187A CN202110108482.2A CN202110108482A CN112920187A CN 112920187 A CN112920187 A CN 112920187A CN 202110108482 A CN202110108482 A CN 202110108482A CN 112920187 A CN112920187 A CN 112920187A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- metal complex
- ammonium
- salt
- synthesizing
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/18—Bridged systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种同时去除甲醛和合成金属配合物的方法及其应用，将铵盐和可溶性金属盐加入到含甲醛的溶液中；或将含甲醛的气体通入到铵盐和可溶性金属盐的混合溶液中；经搅拌反应、结晶、纯化后即得金属配合物。本发明先采用铵盐将甲醛资源化为六次甲基四胺，再利用金属盐与六次甲基四胺的配位作用促进甲醛转化的同时形成稳定的金属配合物，用于高效催化CO2环加成反应。The invention discloses a method for simultaneously removing formaldehyde and synthesizing metal complexes and its application. The ammonium salt and the soluble metal salt are added to the solution containing formaldehyde; or the formaldehyde-containing gas is introduced into the ammonium salt and the soluble metal salt. in the mixed solution; the metal complex is obtained after stirring reaction, crystallization and purification. The method firstly uses ammonium salt to convert formaldehyde into hexamethylene tetramine, and then utilizes the coordination effect of metal salt and hexamethylene tetramine to promote the conversion of formaldehyde while forming stable metal complexes, which are used to efficiently catalyze CO 2 cycloaddition reactions.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a method for simultaneously removing formaldehyde and synthesizing a metal complex and application of the method in CO2Application in cycloaddition reactions.
Background
The formaldehyde treatment method mainly comprises an oxidation method, a biological treatment method, a blow-off method, a condensation method, a lime method and the like. Among them, a technique of capturing formaldehyde and then converting it into a resin [ CN201710494960.1], a methylal [ CN200910032554.9], or a urea-formaldehyde resin adhesive [ CN201210037079.6] by condensation has been receiving attention. However, no data report is available at present for the resource utilization of formaldehyde as a catalyst for catalyzing organic reactions.
In 5 months 2020, scientists monitored atmospheric CO2The concentration exceeds 417ppm, and the innovation of the product is high. By CO in industrial waste gas2The cyclic carbonate synthesized by cycloaddition reaction with epoxide has high added value, changes waste into valuable, and has important significance for relieving greenhouse effect from the aspect of replacing the original carbonate synthesis process. In addition, the process has the advantages of high atom utilization rate, few byproducts and the like, and conforms to the principle of green chemistry. At present, quaternary ammonium salt, metal salt and the like are mainly used for preparing cyclic carbonate in industry, the reaction conditions are harsh (high temperature and high pressure are needed), and the energy consumption is increased to cause indirect emission of more CO2。
After the metal salt reacts with the organic ligand to form the metal complex, the activity is improved, but the application of the catalyst in the cyclic carbonate process is limited by the complicated preparation process, high price, unsatisfactory stability and the like of the metal complex or the organic ligand.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for simultaneously removing formaldehyde and synthesizing a metal complex and application thereof2And (3) performing cycloaddition reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing formaldehyde and synthesizing metal complex at the same time, add ammonium salt and soluble metal salt into solution containing formaldehyde; or introducing formaldehyde-containing gas into a mixed solution of ammonium salt and soluble metal salt; the metal complex is obtained after stirring reaction, crystallization and purification.
Preferably, the ammonium salt is selected from one or more of ammonium nitrate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium acetate.
Preferably, the soluble metal salt is one or more of nitrate, chloride, bromide, iodide, fluoride, phosphate, hydrogen phosphate and dihydrogen phosphate of Zn, Fe, Ca or Mg.
Preferably, the molar ratio of the ammonium salt to the soluble metal salt is 4-20: 1.
preferably, in the formaldehyde-containing solution, the concentration of formaldehyde is 0.1-10 g/L, and the molar ratio of ammonium salt to formaldehyde is 1-10: 1.
preferably, in the formaldehyde-containing gas, the concentration of formaldehyde is 5-100 mg/L, and the molar ratio of ammonium salt to formaldehyde is 1-10: 1.
preferably, the stirring reaction time is 10 min-6 h.
The invention also provides the application of the metal complex, which is used for catalyzing epoxide and CO2Cycloaddition reaction to synthesize cyclic carbonate.
Preferably, the epoxide is one or more of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide and styrene oxide.
Preferably, the molar ratio of the metal complex to the epoxide is (0.005-0.05): 1.
with zinc bromide hexamethylenetetramine metal complex (ZnBr)22Hatm), formula (1) is the reaction process of formaldehyde removal and metal complex synthesis of the present invention:
ZnBr2+8NH4Br+12HCHO＝ZnBr2·2Hatm+8HBr+12H2O (1)
as is clear from the formula (1), the metal salt (ZnBr)2) Introduction of formaldehyde with ammonium salt (NH)4Br) is converted into more stable metal complex (ZnBr) in time2And 2Hatm), not only can improve the removal rate of formaldehyde, but also can avoid secondary pollution caused by the decomposition of hexamethylenetetramine into formaldehyde.
Compared with the prior art, the invention has the technical effects that:
(1) the method is suitable for treating the formaldehyde wastewater and the formaldehyde waste gas, and has the advantages of simple method for removing the formaldehyde, mild conditions, low cost, high efficiency and high speed.
(2) The invention adopts a coupling strategy to remove formaldehyde and simultaneously recycle to obtain high-efficiency CO2The cycloaddition catalyst saves resources and avoids secondary pollution of formaldehyde.
(3) The hexamethylene tetramine metal complex prepared by the invention is rich in basic sites (4 mol of tertiary amine is contained in 1mol of molecule), has a cage-shaped structure, is stable to water, and can catalyze CO with high selectivity and high yield under mild conditions2And epoxide cycloaddition reaction to synthesize the cyclic carbonate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
323g (3.3mol) of ammonium bromide and 1.12g (0.825mol) of zinc bromide are respectively added into 10L of water with 10g/L of formaldehyde concentration (3.3mmol), the mixture is stirred for 6 hours, the formaldehyde concentration is reduced to 1.4mg/L, then evaporation crystallization is carried out, crude products are obtained by suction filtration, and after washing by ethanol, 95 wt.% of ethanol is added for recrystallization, thus obtaining zinc bromide hexamethylenetetramine metal complex-1.
Example 2
177g (3.3mol) of ammonium chloride and 61g (0.55mol) of calcium chloride are respectively added into 100L of water with 0.5g/L of formaldehyde (1.65mol), the mixture is stirred for 10min, the concentration of the formaldehyde is reduced to 0.8mg/L, then evaporation crystallization is carried out, suction filtration is carried out to obtain a crude product, the crude product is washed by ethanol, and 95 wt.% of ethanol is added for recrystallization to obtain the calcium chloride hexamethylenetetramine metal complex.
Example 3
Respectively adding 32.3g (0.33mol) of ammonium bromide and 2.72g (20mmol) of zinc bromide into 1L of water for dissolving, introducing 30L (the gas flow rate is 100mL/min) of 100mg/L formaldehyde gas under stirring, reducing the formaldehyde concentration in the gas to 0.8mg/L, stirring for 6 hours, then obtaining the solution with the formaldehyde concentration of 0.6mg/L, evaporating for crystallization, carrying out suction filtration to obtain a crude product, washing with ethanol, adding 95 wt.% ethanol for recrystallization to obtain the zinc bromide hexamethylenetetramine metal complex-2.
Example 4
Respectively taking 17.7g (0.33mol) of ammonium chloride and 1.36g (10mmol) of zinc chloride, adding the ammonium chloride and the zinc chloride into 100mL of water for dissolving, introducing 50L (gas flow rate is 100mL/min) of 5mg/L of formaldehyde gas under stirring, reducing the formaldehyde concentration in the gas to 0.4mg/L, stirring for 2 hours, then, obtaining a crude product by evaporation crystallization and suction filtration, washing by using ethanol, and adding 95 wt.% of ethanol for recrystallization to obtain the zinc chloride hexamethylenetetramine metal complex.
Comparative example 1
177g (3.3mol) of ammonium chloride was added to 100L of water having a formaldehyde (1.65mol) concentration of 0.5g/L, and the mixture was stirred for 10 minutes to reduce the formaldehyde concentration to 0.1 g/L.
Comparative example 2
17.7g (0.33mol) of ammonium chloride was dissolved in 100mL of water, and 50L of 5mg/L formaldehyde gas was introduced with stirring (gas flow rate: 100mL/min), whereby the formaldehyde concentration in the gas was reduced to 3.2 mg/L.
Application example 1
At room temperature, sequentially adding 10.6 mmol of zinc bromide hexamethylenetetramine metal complex prepared in example 1, 0.15g of internal standard substance biphenyl and 30mmol of epoxy chloropropane into a 30mL high-pressure reaction kettle, and introducing 2MPa CO under stirring at room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 5 hours at the temperature of 80 ℃, and after the reaction is finished, putting the reaction kettle into a cold stateCooling in water and subsequent release of CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of cyclic carbonate was 92.8% with a selectivity of 99.8%.
Application example 2
At room temperature, 0.3mmol of calcium chloride hexamethylenetetramine metal complex prepared in example 2, 0.15g of internal standard substance biphenyl and 30mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle, and 1.5MPa of CO is introduced into the kettle under the condition of room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 10 hours at 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 96.3% with a selectivity of 99.7%.
Application example 3
At room temperature, the zinc bromide hexamethylenetetramine metal complex-21.5 mmol prepared in the example 3, 0.15g of internal standard substance biphenyl and 30mmol of propylene oxide are added in turn into a 10mL reaction tube, and the reaction tube and 1L of CO are added2Connecting the air bags, placing the reaction tube into an oil bath reactor with magnetic stirring to react for 24h at 30 ℃, and releasing CO after the reaction is finished2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 82.5% with a selectivity of 99.8%.
Application example 4
0.3mmol of zinc chloride hexamethylenetetramine metal complex prepared in example 4, 0.15g of internal standard substance biphenyl and 30mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle at room temperature, and 2MPa CO is introduced into the kettle under the condition of room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 12 hours at the temperature of 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 78.4% with a selectivity of 99.8%.
Application comparative example 1
At room temperature, 0.3mmol of zinc chloride, 0.15g of internal standard substance biphenyl and 30mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle,introducing 2MPa CO under stirring at room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 12 hours at the temperature of 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 32.1% with a selectivity of 99.8%.
Comparative application example 2
At room temperature, sequentially adding 0.3mmol of hexamethylenetetramine, 0.15g of internal standard substance biphenyl and 30mmol of propylene oxide into a 30mL high-pressure reaction kettle, and introducing 2MPa CO under the stirring at room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 12 hours at the temperature of 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 1.2% with a selectivity of 92.8%.
Claims (10)
1. A method for simultaneously removing formaldehyde and synthesizing a metal complex is characterized in that: adding an ammonium salt and a soluble metal salt to a formaldehyde-containing solution; or introducing formaldehyde-containing gas into a mixed solution of ammonium salt and soluble metal salt; the metal complex is obtained after stirring reaction, crystallization and purification.
2. The method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: the ammonium salt is selected from one or more of ammonium nitrate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium acetate.
3. The method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: the soluble metal salt is one or more of nitrate, chloride, bromide, iodide, fluoride, phosphate, hydrogen phosphate and dihydrogen phosphate of Zn, Fe, Ca or Mg.
4. The method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: the molar ratio of the ammonium salt to the soluble metal salt is 4-20: 1.
5. the method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: in the formaldehyde-containing solution, the concentration of formaldehyde is 0.1-10 g/L, and the molar ratio of ammonium salt to formaldehyde is 1-10: 1.
6. the method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: in the formaldehyde-containing gas, the concentration of formaldehyde is 5-100 mg/L, and the molar ratio of ammonium salt to formaldehyde is 1-10: 1.
7. the method of claim 1 for simultaneously removing formaldehyde and synthesizing a metal complex, wherein: the stirring reaction time is 10 min-6 h.
8. Use of a metal complex according to any one of claims 1 to 7, wherein: it is used to catalyze epoxides and CO2Cycloaddition reaction to synthesize cyclic carbonate.
9. Use of a metal complex according to claim 8, wherein: the epoxide is one or more of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide and styrene oxide.
10. Use of a metal complex according to claim 8, wherein: the molar ratio of the metal complex to the epoxide is 0.005-0.05: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110108482.2A CN112920187B (en) | 2021-01-27 | 2021-01-27 | A kind of method for removing formaldehyde and synthesizing metal complex simultaneously and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110108482.2A CN112920187B (en) | 2021-01-27 | 2021-01-27 | A kind of method for removing formaldehyde and synthesizing metal complex simultaneously and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112920187A true CN112920187A (en) | 2021-06-08 |
| CN112920187B CN112920187B (en) | 2022-04-29 |
Family
ID=76166729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110108482.2A Active CN112920187B (en) | 2021-01-27 | 2021-01-27 | A kind of method for removing formaldehyde and synthesizing metal complex simultaneously and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920187B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097414A (en) * | 1976-08-30 | 1978-06-27 | Texaco Development Corp. | Modified ethylene oxide catalyst and a process for its preparation |
| US4398914A (en) * | 1981-02-19 | 1983-08-16 | Basf Aktiengesellschaft | Process for discharge or reserve printing on synthetic fibers: formaldehyde sulfoxylate and hexamethylene tetramine |
| US20140086848A1 (en) * | 2002-10-25 | 2014-03-27 | Foamix Ltd. | Foamable compositions and methods for disorders of the skin or mucosal surfaces |
| RU2014129362A (en) * | 2012-11-12 | 2016-02-10 | Виктор Станиславович Поляков | Dermatological composition with indicator properties |
| CN105498780A (en) * | 2015-12-24 | 2016-04-20 | 大连工业大学 | A kind of Cu/ZnO catalyst and its preparation method and application in CO2 chemical conversion |
| CN108097309A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of CO2With the effective catalyst of propylene oxide synthesizing acrylic ester and preparation method thereof |
| CN109012682A (en) * | 2018-07-27 | 2018-12-18 | 新疆大学 | A kind of method of modifying of Fe-Mo catalyst for preparing formaldehyde through methanol oxidation |
| CN111185239A (en) * | 2020-02-21 | 2020-05-22 | 东南大学 | A kind of preparation method and application of CO2 epoxidation immobilized catalyst |
-
2021
- 2021-01-27 CN CN202110108482.2A patent/CN112920187B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097414A (en) * | 1976-08-30 | 1978-06-27 | Texaco Development Corp. | Modified ethylene oxide catalyst and a process for its preparation |
| US4398914A (en) * | 1981-02-19 | 1983-08-16 | Basf Aktiengesellschaft | Process for discharge or reserve printing on synthetic fibers: formaldehyde sulfoxylate and hexamethylene tetramine |
| US20140086848A1 (en) * | 2002-10-25 | 2014-03-27 | Foamix Ltd. | Foamable compositions and methods for disorders of the skin or mucosal surfaces |
| RU2014129362A (en) * | 2012-11-12 | 2016-02-10 | Виктор Станиславович Поляков | Dermatological composition with indicator properties |
| CN105498780A (en) * | 2015-12-24 | 2016-04-20 | 大连工业大学 | A kind of Cu/ZnO catalyst and its preparation method and application in CO2 chemical conversion |
| CN108097309A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of CO2With the effective catalyst of propylene oxide synthesizing acrylic ester and preparation method thereof |
| CN109012682A (en) * | 2018-07-27 | 2018-12-18 | 新疆大学 | A kind of method of modifying of Fe-Mo catalyst for preparing formaldehyde through methanol oxidation |
| CN111185239A (en) * | 2020-02-21 | 2020-05-22 | 东南大学 | A kind of preparation method and application of CO2 epoxidation immobilized catalyst |
Non-Patent Citations (4)
| Title |
|---|
| BHASKARAN ET AL.: "Synthetic, spectral, structural and catalytic activity of infinite 3-D and 2-D copper(II) coordination polymers for substrate size-dependent catalysis for CO2 conversion", 《DALTON TRANS》 * |
| MUTASIM I. KHALIL ET AL.: "A refined X-ray crystal structure of: silver nitrate hexamethylenetetramine", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》 * |
| 刘纲勇等: "工业木质素性质对LPF胶粘性能的影响", 《科技创新导报》 * |
| 张付宝 等: "酯交换法制备草酸二苯酯催化剂研究进展", 《工业催化》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112920187B (en) | 2022-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794400B (en) | A kind of cationic amino acid-containing ionic liquid containing amino acid and preparation method and application thereof | |
| CN112280052B (en) | Hierarchical pore ZIF-8 material and preparation method and application thereof | |
| CN110105321B (en) | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide through eutectic ionic liquid | |
| JP6719527B2 (en) | Method for preparing azoxystrobin intermediate | |
| CN102502690A (en) | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base | |
| CN105949129A (en) | Imidazolium bromide ionic liquid containing amine groups and preparation method and application of ionic liquid | |
| CN106045913B (en) | A kind of imidazoles perrhenate ions liquid and its preparation method and application with amino | |
| CN112409190B (en) | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst | |
| CN102125868A (en) | Method for preparing microporous-mesoporous composite Fe-ZSM-5 zeolite molecular sieve catalyst | |
| CN103191780A (en) | Functionalized carbon nitride photocatalyst capable of performing catalytic oxidization on benzene to synthesize phenol | |
| CN103182322A (en) | Treatment method of inactivated titanium silicon molecular sieve | |
| CN101591024A (en) | A kind of modification method of titanium silicon molecular sieve | |
| CN104402736B (en) | Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline | |
| CN101486000B (en) | Catalyst for synthesizing MIBK and preparation method thereof | |
| CN106916108B (en) | A kind of pyrazole ionic liquid and the method utilizing it to catalyze the synthesis of cyclic carbonate | |
| CN111185239A (en) | A kind of preparation method and application of CO2 epoxidation immobilized catalyst | |
| CN111116321A (en) | Green synthesis method for preparing phenol by benzene hydroxylation | |
| CN112920187A (en) | Method for simultaneously removing formaldehyde and synthesizing metal complex and application thereof | |
| CN114345410A (en) | Application of amine functionalized lignin-based catalyst in carbon dioxide cycloaddition reaction | |
| CN102675249B (en) | Method for synthesizing epoxide by catalysis of titanium-silicon molecular sieve | |
| CN112898349A (en) | Metal manganese complex with 4,4 '-diamino-2, 2' -bipyridine as ligand, synthetic method and photocatalytic application thereof | |
| CN104447353B (en) | A kind of benzene and hydroxylamine salt react the method directly preparing aniline | |
| CN104610064B (en) | One-pot method using carbonate as a catalyst for the preparation of dimethyl carbonate | |
| CN114602555A (en) | A kind of preparation method and application of chitosan Schiff base immobilized copper material | |
| CN103920531A (en) | Titanium-silicon molecular sieve catalyst, its preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |