CN106045850A - Method for catalytic synthesis of citrate through composite doped phosphowolframate - Google Patents
Method for catalytic synthesis of citrate through composite doped phosphowolframate Download PDFInfo
- Publication number
- CN106045850A CN106045850A CN201610376027.XA CN201610376027A CN106045850A CN 106045850 A CN106045850 A CN 106045850A CN 201610376027 A CN201610376027 A CN 201610376027A CN 106045850 A CN106045850 A CN 106045850A
- Authority
- CN
- China
- Prior art keywords
- citrate
- catalyst
- synthesizing
- ammonium
- alcohol
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for catalytic synthesis of citrate through composite doped phosphowolframate. Composite doped phosphowolframate serves as a catalyst, and citric acid and fatty alcohol are subjected to an esterification reaction to synthesize citrate. The condensed structural formula of composite doped phosphowolframate is (NH4)xAl(3-x-y)/3HyPW12O40, wherein x is equal to 0.4 to 1.1, and y is equal to 0.4 to 1.1. The method has the advantages that the catalyst is low in cost, easy to prepare and high in catalysis efficiency, the catalyst and a product are easy to separate, and the reuse performance of the catalyst is excellent.
Description
Technical field
A kind of method that the present invention relates to synthesizing citric acid ester, catalyzes and synthesizes particularly to a kind of composite mixed phosphotungstate
The method of citrate.
Background technology
Citrate is a kind of broad-spectrum nontoxic plasticizer, and it has nontoxic, and volatility is little, plasticizing efficiency height and phase
The advantages such as capacitive is good.One of green succedaneum as traditional phthalic ester plasticizer, U.S. food and medicine prison
Superintend and direct management board and have been approved by being applied to citric acid ester plasticizer packaging material for food, medical apparatus and personal hygiene article etc.
Aspect.In recent years, citric acid ester type has become environment-friendlyplasticizer plasticizer first.
In the traditional processing technology of citrate, main employing concentrated sulphuric acid is catalyst.The low price of concentrated sulphuric acid, and
Catalysis activity is higher.But, the by-product of reaction is more, causes bigger difficulty to the separating-purifying of product.Additionally, sulphuric acid pair
Equipment corrosion is serious, and produces a large amount of acid-bearing wastewater, causes serious environmental pollution.In order to overcome disadvantages described above, grind both at home and abroad
The person of studying carefully develops a series of solid acid catalyst for synthesizing citric acid ester, such as molecular sieve, solid super-strong acid, inorganic salt, sun
Ion exchange resin and heteropoly acid etc..Wherein, heteropoly acid has green non-poisonous, activity and selectivity high, extensively applies
In the reaction of synthesizing citric acid ester.But, heteropoly acid there is also that to be soluble in polar reaction medium, specific surface area low and thermally-stabilised
The problem such as property is poor.Solution to the problems described above be by immobilized for heteropoly acid or be transformed into insoluble heteropoly acid salt catalysis
Agent.Compared with carried heteropoly acid, heteropoly acid salt have acid strong, that surface acidity center density is high and easily prepared etc. is excellent
Gesture, is the class heavy duty detergent solid acid catalyst that obtains extensive concern, as aluminium phosphotungstic acid (old equality, Industrial Catalysis, 2007,
15,46-49), 1-(3-sulfonic group) propyl group-3-Methylimidazole. phosphotungstate (Yu Shengjian etc., Industrial Catalysis, 2012,20,
52-55) etc. heteropolyacid salt catalyst has been applied in the reaction system of synthesizing citric acid ester the most.But, above-mentioned heteropoly acid salt
Catalyst exists that activity is the highest, preparation process is complicated, large usage quantity or the defect such as repeat performance is poor.
CN 105061204 A uses molecular formula to be (NH4)xAgyH3-x-yPW12O40(x=0.3～0.8, y=0.3～0.8)
Ammonium, silver-colored composite mixed phosphotungstate catalyze and synthesize citrate, the activity of catalyst is higher than traditional unitary type ion doping
Phosphotungstic acid, the yield of product is high, and catalyst is easily separated, and repeat performance is preferable.But, owing to the price of silver is higher, make
Its application is restricted.Therefore, exploitation is applicable to the cheap, efficient, stable and easily prepared of industrialized production citrate
Solid acid catalyst is the technical problem that those skilled in the art is in the urgent need to address.
Summary of the invention
It is an object of the invention to provide a kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate, the method
There is production cost low, efficiently and the advantage such as environmental protection.
The method that the composite mixed phosphotungstate that the present invention provides catalyzes and synthesizes citrate, with composite mixed phosphotungstate
For catalyst, by citric acid and fatty alcohol generation esterification synthesizing citric acid ester, the structure of described composite mixed phosphotungstate
Skeleton symbol is: (NH4)xAl(3-x-y)/3 HyPW12O40, wherein, x=0.4 ~ 1.1, y=0.4 ~ 1.1.
Further, described fatty alcohol is C4~C16Straight or branched fatty alcohol, more preferably n-butyl alcohol, hexanol,
2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or lauryl alcohol.
Further, the preparation process of described composite mixed phosphotungstate catalyst includes step:
(1) ammonium salt, aluminium salt are mixed in solution with phosphotungstic acid；
(2) composite mixed phosphotungstate described in isolated after reaction.
Further, described step (1) particularly as follows:
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
Further, described ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
Further, described aluminium salt is aluminum nitrate, aluminum sulfate or aluminum chloride.
Further, the temperature of described esterification is 120 ~ 170 DEG C.
Further, citric acid is 1:2 ~ 5 with the ratio of the amount of the material of fatty alcohol.
Further, catalyst is 0.5 ~ 3:100 with the mass ratio of citric acid.
Further, the response time is 2 ~ 5 hours.
Technical scheme provided by the present invention has the advantage that in (1) catalytic component without noble metal, low cost
Honest and clean, it is easy to preparation, and catalytic efficiency is high；(2) catalyst separates with product simply, and catalyst can realize reusing；(3) lemon
The yield of lemon acid esters is high.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described in further detail.For those of skill in the art
For Yuan, from detailed description of the invention, the above and other objects, features and advantages of the present invention will be apparent to.
Embodiment 1:
The preparation of catalyst: weigh 0.375 mmol ammonium carbonate, 0.5 mmol aluminum nitrate and 1 mmol phosphotungstic acid and be dissolved in respectively
In 20 ml deionized waters；After dissolving, room temperature and continuously stirred under conditions of, aluminum nitrate solution is slowly added dropwise to phosphotungstic acid
In solution, react 0.5 hour, then be slowly added dropwise sal volatile, increasingly generate white precipitate；After dripping, it is further continued for stirring
React 0.5 hour, still aging 1 hour, after precipitation is separated by filtration, be dried, i.e. can get molecular formula for (NH4)0.75Al0.5H0.75PW12O40Composite mixed phosphotungstate.
Embodiment 2:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of ammonium carbonate into 0.2 mmol, available molecule
Formula is (NH4)0.4Al0.5H1.1PW12O40Composite mixed phosphotungstate.
Embodiment 3:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of ammonium carbonate into 0.55 mmol, available molecule
Formula is (NH4)1.1Al0.5H0.4PW12O40Composite mixed phosphotungstate.
Embodiment 4:
The preparation of catalyst: ammonium salt, with embodiment 1, is only changed into 0.6 mmol ammonium hydrogen carbonate, the addition of aluminum nitrate by preparation process
Amount changes 0.6 mmol into, and available molecular formula is (NH4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 5:
The preparation of catalyst: ammonium salt, with embodiment 4, is only changed into 0.6 mmol ammonium chloride by preparation process, and available molecular formula is
(NH4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 6:
The preparation of catalyst: aluminium salt, with embodiment 4, is only changed into 0.6 mmol aluminum chloride by preparation process, and available molecular formula is
(NH4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 7:
19.21 g citric acids (0.1 mol), 29.6 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube
(the NH of preparation in n-butyl alcohol (0.4 mol) and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40Catalyst, opens stirring,
It is warming up to 150 DEG C, starts timing when condensing tube starts to occur backflow phenomenon, react 3 h.Reaction system is cooled to room temperature
After, to filter and separate, filtrate uses gas chromatographic detection, and product yield is shown in Table 1.
Embodiment 8:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 2
(NH4)0.4Al0.5H1.1PW12O40, product yield is shown in Table 1.
Embodiment 9:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 3
(NH4)1.1Al0.5H0.4PW12O40, product yield is shown in Table 1.
Embodiment 10:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 4
(NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 11:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 5
(NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 12:
Use reaction condition same as in Example 7 and detection method, only catalyst is changed into preparation in embodiment 6
(NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 13:
19.21 g citric acids (0.1 mol), 26.05 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube
(the NH of preparation in n-octyl alcohol (0.2 mol), 5 mL water entrainer hexamethylene and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40
Catalyst, opens stirring, is warming up to 160 DEG C, starts timing when starting to occur backflow phenomenon in condensing tube, react 3 h.Reaction
After system is cooled to room temperature, filtering and separate, filtrate uses gas chromatographic detection, and product yield is shown in Table 1.
Embodiment 14:
Use the reaction condition identical with embodiment 13 and detection method, only raw material n-octyl alcohol is changed into 26.05 g isooctanol
(0.2 mol), product yield is shown in Table 1.
Embodiment 15:
19.21 g citric acids (0.1 mol), 37.26 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube
(the NH of preparation in lauryl alcohol (0.2 mol), 5 mL water entrainer hexamethylene and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40
Catalyst, opens stirring, is warming up to 165 DEG C, starts timing when starting to occur backflow phenomenon in condensing tube, react 4 h.Reaction
After system is cooled to room temperature, filtering and separate, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1.
Embodiment 16:
19.21 g citric acids (0.1 mol), 48.5 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube
(the NH of preparation in hexadecanol (0.2 mol), 5 mL water entrainer hexamethylene and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40
Catalyst, opens stirring, is warming up to 170 DEG C, starts timing when starting to occur backflow phenomenon in condensing tube, react 5 h.Reaction
After system is cooled to room temperature, filtering and separate, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1.
Embodiment 17:
Use reaction condition same as in Example 10 and detection method, only change the consumption of n-butyl alcohol into 14.8 g(0.2
Mol), product yield is shown in Table 1.
Embodiment 18:
Use reaction condition same as in Example 10 and detection method, only change the consumption of n-butyl alcohol into 22.2 g(0.3
Mol), product yield is shown in Table 1.
Embodiment 19:
Use reaction condition same as in Example 10 and detection method, only the consumption of n-butyl alcohol changed into 37 g(0.5 mol),
Product yield is shown in Table 1.
Embodiment 20:
Use the reaction condition identical with embodiment 11 and detection method, only change the consumption of catalyst into 0.1 g, product yield
It is shown in Table 1.
Embodiment 21:
Using the reaction condition identical with embodiment 11 and detection method, the consumption of catalyst only changes into 0.38 g, product is received
Rate is shown in Table 1.
Embodiment 22:
Using the reaction condition identical with embodiment 12 and detection method, only reaction temperature changes 130 DEG C into, product yield is shown in Table
1。
Embodiment 23:
Using reaction condition same as in Example 7 and detection method, only will change in the response time 5 hours, product yield is shown in Table
1。
Embodiment 24:
Catalyst after using in embodiment 7, filters after separating without any process, anti-for the circulation of next batch
Should, the reaction condition of circular response is same as in Example 7 with detection method, and after recycling 15 times, product yield is shown in Table 1.
Comparative example 1:
Use reaction condition same as in Example 10 and detection method, only change catalyst into (NH4)2.4H0.6PW12O40, produce
Thing yield is shown in Table 1.
Comparative example 2:
Use reaction condition same as in Example 10 and detection method, only change catalyst into Al0.8H0.6PW12O40, product is received
Rate is shown in Table 1.
Table 1: embodiment and the product yield of comparative example.
According to the result of table 1, the reaction of lactate synthesis citrate is had by the composite mixed phosphotungstate that the present invention relates to
Having the most excellent catalytic performance, its catalysis activity is better than traditional unitary type ion doping phosphotungstate, and catalyst is through 15 times
The phenomenon that activity is decreased obviously does not occurs after reusing.Additionally, catalyst is with low cost and easily prepared.Therefore, this
The bright technical scheme related to is suitable for industrial applications.It will be apparent to those skilled in the art that ammonium salt uses ammonium carbonate, bicarbonate
Ammonium, ammonium chloride or ammonium nitrate, aluminium salt uses aluminum nitrate, aluminum sulfate or aluminum chloride, all can realize the technique effect of the present invention.This
Bright applicable fatty alcohol includes the straight or branched fatty alcohol of C4 ~ C16.
Although should be appreciated that the present invention has carried out understanding explanation by above example, but without departing substantially from the present invention
Spirit and essence in the case of, person of ordinary skill in the field when can according to the present invention make various corresponding change and
Revise, but these corresponding variations and modifications all should belong to the scope of the claims of the present invention.
Claims (10)
1. the method that composite mixed phosphotungstate catalyzes and synthesizes citrate, with composite mixed phosphotungstate as catalyst,
By citric acid and fatty alcohol generation esterification synthesizing citric acid ester, it is characterised in that the knot of described composite mixed phosphotungstate
Structure skeleton symbol is: (NH4)xAl(3-x-y)/3 HyPW12O40, wherein, x=0.4 ~ 1.1, y=0.4 ~ 1.1.
The method catalyzing and synthesizing citrate the most according to claim 1, it is characterised in that described fatty alcohol is positive fourth
Alcohol, hexanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or lauryl alcohol.
The method catalyzing and synthesizing citrate the most according to claim 1, it is characterised in that described composite mixed phosphotungstic acid
The preparation process of salt catalyst includes step:
(1) ammonium salt, aluminium salt are mixed in solution with phosphotungstic acid；
(2) composite mixed phosphotungstate described in isolated after reaction.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described step (1) particularly as follows:
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described ammonium salt be ammonium carbonate,
Ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described aluminium salt be aluminum nitrate,
Aluminum sulfate or aluminum chloride.
7. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that described esterification is anti-
The temperature answered is 120 ~ 170 DEG C.
8. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that citric acid and fat
The ratio of the amount of the material of fat alcohol is 1:2 ~ 5.
9. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that catalyst and lemon
The mass ratio of lemon acid is 0.5 ~ 3:100.
10. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that the response time
It it is 2 ~ 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610376027.XA CN106045850B (en) | 2016-05-31 | 2016-05-31 | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610376027.XA CN106045850B (en) | 2016-05-31 | 2016-05-31 | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106045850A true CN106045850A (en) | 2016-10-26 |
| CN106045850B CN106045850B (en) | 2019-01-18 |
Family
ID=57171620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610376027.XA Expired - Fee Related CN106045850B (en) | 2016-05-31 | 2016-05-31 | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106045850B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187744A (en) * | 2018-01-27 | 2018-06-22 | 邵阳学院 | A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314075A (en) * | 1980-09-05 | 1982-02-02 | The Standard Oil Company | Process for the production of olefinic acids and esters |
| JP2002167359A (en) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | Method for producing aromatic carbonate |
| CN105061204A (en) * | 2015-07-31 | 2015-11-18 | 邵阳学院 | Method for catalytic synthesis of citric acid ester by (NH4)xAgyH3-x-yPW12O40 composite salt |
-
2016
- 2016-05-31 CN CN201610376027.XA patent/CN106045850B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314075A (en) * | 1980-09-05 | 1982-02-02 | The Standard Oil Company | Process for the production of olefinic acids and esters |
| JP2002167359A (en) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | Method for producing aromatic carbonate |
| CN105061204A (en) * | 2015-07-31 | 2015-11-18 | 邵阳学院 | Method for catalytic synthesis of citric acid ester by (NH4)xAgyH3-x-yPW12O40 composite salt |
Non-Patent Citations (2)
| Title |
|---|
| ATSUYUKI MIYAJI等: "Skeletal isomerization of n-heptane and hydroisomerization of benzene over bifunctional heteropoly compounds", 《CATALYSIS TODAY》 * |
| 农兰平: "活性炭负载磷钨酸铝催化合成柠檬酸三丁酯", 《精细化工中间体》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187744A (en) * | 2018-01-27 | 2018-06-22 | 邵阳学院 | A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal |
| CN108187744B (en) * | 2018-01-27 | 2020-08-04 | 邵阳学院 | Method for catalytic synthesis of furfural ethylene glycol acetal from ammonium aluminum phosphotungstate complex salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106045850B (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008207A (en) | Method for composite phosphotungstate catalyzed synthesis of citrate ester | |
| CN105061204B (en) | A kind of method that silver phosphotungstate ammonium compound salt catalyzes and synthesizes citrate | |
| CN100400159C (en) | Method for preparing solid acid catalyst from charing and sulfonating sugar compounds | |
| CN101927178B (en) | Solid super basic catalyst and preparation method and application thereof | |
| CN101723928A (en) | Ion liquid and preparation technology thereof | |
| CN110407779A (en) | The method for preparing 5 hydroxymethyl furfural as raw material using biomass | |
| CN102500382B (en) | Catalyst for synthesizing methanol and preparation method thereof | |
| CN101898946B (en) | Method for hydrogenolysis catalysis of glycerin | |
| CN104254549A (en) | A process for the production of methacrylic acid and its derivatives and polymers produced therefrom | |
| CN103627442A (en) | Biodiesel catalysis preparing method by employing solid catalyst | |
| CN102614919B (en) | Sulfonated cross-linked chitosan resin type solid acid catalyst and preparation method thereof | |
| CN106045850A (en) | Method for catalytic synthesis of citrate through composite doped phosphowolframate | |
| CN104001550B (en) | A kind of support type chirality amorphous catalyst and its preparation method and application | |
| CN103316696B (en) | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method | |
| CN101265180B (en) | Method for preparing lactic acid | |
| CN107188804B (en) | Method for catalytically synthesizing methyl oleate by using composite phosphotungstate | |
| CN111875493A (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN105384637A (en) | Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster | |
| CN108191814B (en) | Method for synthesizing cyclohexanone ethylene ketal under catalysis of titanium ammonium phosphotungstate composite salt | |
| CN104307558B (en) | A kind of it is catalyzed triose catalyst being isomerized to lactic acid and lactate and its preparation method and application | |
| CN104387238A (en) | Preparation method of branched alkyl phenol | |
| CN106748772B (en) | A kind of production method of methyl acetate | |
| CN103649037B (en) | Acid catalyst is adopted to be hydrolyzed and esterification | |
| CN103086894B (en) | Synthesis method of electroplating additive 3-methyl-3-aminobutyne | |
| CN108187744B (en) | Method for catalytic synthesis of furfural ethylene glycol acetal from ammonium aluminum phosphotungstate complex salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190118 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |