CN106674008A - Method for preparing tributyl citrate by using tubular reactor - Google Patents
Method for preparing tributyl citrate by using tubular reactor Download PDFInfo
- Publication number
- CN106674008A CN106674008A CN201611224447.2A CN201611224447A CN106674008A CN 106674008 A CN106674008 A CN 106674008A CN 201611224447 A CN201611224447 A CN 201611224447A CN 106674008 A CN106674008 A CN 106674008A
- Authority
- CN
- China
- Prior art keywords
- butanol
- tributyl citrate
- product
- tubular
- citric acid
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for green and continuous production of tributyl citrate. A tubular reactor (containing an efficient soil catalyst) is used to realize efficient conversion of citric acid and butanol and combined with a continuous impurity removal technology and a continuous rectification technology, continuous production of the product is realized, the purity of the product, namely, tributyl citrate, is higher than or equal to 99.0, and the yield of the main product, namely, tributyl citrate, is higher than 98.0%, and no pollution is caused in the whole process.
Description
Technical field
The invention belongs to chemosynthesis technical field, specifically related to a kind of to prepare tributyl citrate using tubular reactor
Method.
Background technology
DOP (dioctyl phthalate) (DBP) has good with most synthetic resin for industrially using and rubber
The good compatibility, also with good combination property, good mixing property, plasticizing efficiency is high, and volatility is relatively low, low-temperature pliability compared with
Well, the advantages of water-fast extraction, electric property height, thermostability and good weatherability, thus be that a kind of purposes is most commonly used general
Type plasticizer, processing, can be additionally used in ground resin, acetate resin, ABS resin and the rubber for being mainly used in polyvinyl chloride fat is contour
The processing of polymers, it can also be used to make paint, dyestuff, dispersant etc., the PVC of DOP plasticising can be used for manufacture artificial leather, agricultural film,
Packaging material, cable etc..Used as plasticizer, the Main Function of phthalic acid ester is the pliability for improving the products such as plastics, it
It is widely used in hundreds of products such as articles for children, toy, packaging material for food.But Recent study finds O-phthalic
Acid ester type plasticizer can produce harm to human body, and particularly to infants and children etc., it is a kind of global organic pollution,
It is generally acknowledged environmental hormone, hazardous chemical control register is clearly listed in European Union and the U.S. in." peak of the child in growth promoter
In the stage, if the toy for contacting contains excessive phthalic acid ester everyday, its reproductive system, immune system, digestive system can be made
Into harm, male reproductive function can be damaged, promote female precocious puberty, be likely to result in children's gender entanglement." it is badly in need of exploitation environment-friendly type
Plasticizer replace it, tri-n-butyl citrate is exactly the more excellent environment-friendlyplasticizer plasticizer of combination property.
Tri-n-butyl citrate, chemical name 3- hydroxyl -3- carboxyl 1,3-propanedicarboxylic acid tributyls, are a kind of ester type compounds, colourless
Transparent high boiling liquid, is slightly soluble in water, dissolves each other with most organic solvents.It is industrial to be formed with n-butyl alcohol reaction by citric acid, can
Plasticizer is directly used in, the plasticizer tributyl 2-acetylcitrate of function admirable can be also further processed into.This product low toxicity, visually
For nontoxic plasticizer, environment-friendlyplasticizer plasticizer is commonly called as, the phthalic ester plasticizer that can be restricted with alternate application scope.
Its production method is that citric acid acts on generation tributyl citrate with n-butyl alcohol in the presence of catalyst and water entrainer, and conventional urges
Agent is inorganic or organic acid (the most frequently used for concentrated sulphuric acid), water entrainer water preparation be n-butyl alcohol Jing dealcoholysis itself, neutralization, washing,
The operations such as stripping, decolouring, filter pressing, rectification obtain product;Although sulphuric acid low price, catalysis activity is high, and it has many shortcomings:
Long the production cycle, conversion ratio is low;And the dehydration due to sulphuric acid, esterification and Oxidation, by-product is more, and this is to product
Refined and recovery brings difficulty;The Study of optimization of anti-nontoxic plasticizer tributyl citrate answers the post processing of product to want Jing
Alkali neutralization, washing are crossed, and removes the sulphuric acid as catalyst, cause complex process, produce the three wastes, product is lost in;In addition, sulfur
Severe corrosion equipment is gone back in acid, increases production cost;In a word traditional handicraft does not only exist production procedure length, Batch Process, Er Qiehui
Produce three-waste pollution.In order to solve the deficiency of traditional handicraft presence, continual exploitation high efficiency continuously, free of contamination new technology road
Line.The present invention provides a kind of continuous production, greenization new preparation technology suitable for the product or similar products.
The content of the invention
Present invention aims to defect and deficiency present in existing tributyl citrate production technology, there is provided one
Plant continuous production, greenization new preparation technology and its implementation for being applied to the product or similar products.
Technical scheme:Tubular reactor of the present invention prepares tributyl citrate method, in solid catalyst effect
Lower employing tubular reactor continuity method prepares tributyl citrate, carries out according to the following steps:
1) butanol is continuously squeezed in tubular reactor with citric acid mixture and is reacted, be to promote citric acid further
Conversion, at rear 1/3rd of tubular reactor butanol is pumped into;
2) reacted mixture enters neutralization reaction kettle, is neutralized to remove by being added thereto to saturated limewater
Unreacted citric acid, the solid by-product Jing tubular filters of generation are removed;
3) the mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, such as
Purity is not enough contemplated that further rectification and purification, and tower top is butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column
With further separation water (tower top) and butanol (bottom of towe), butanol return system is reused, and water can be used to prepare saturated limewater
Deng.
Butanol and citric acid mixture in the step 1, both mol ratios are 3~4:1, both mix homogeneously insulations 80
Reactor is entered when~100 DEG C.Reaction temperature:80~170 DEG C, residence time of material be 0.5~2.0h, reaction pressure≤
3.0MPa.Butanol amount 1.0~1.5 (butanol and citric acid mol ratio) is pumped at rear 1/3rd of tubular reactor.It is described
Tubular reactor built with high-performance solid catalyst, the high-performance solid catalyst is with niobium pentaoxide, p-methyl benzenesulfonic acid, right
Toluenesulfonic acid copper, heteropoly acid, solid super-strong acid are main active component.
It is 7.0~9.0 that pH in reactor is controlled in described step 2.By the way of two tubular filter parallel connections, when
One tubular filter is filled after solidss, switches another tubular filter.
Rectification separation condition is in described step 3:First order rectifying column:Tower bottom product tributyl citrate purity >=
99.0%, yield >=98.0%;Second level rectifying column:Tower bottom product butanol purity >=99.0%, contains butanol in overhead product water
Deng≤0.05%.
Beneficial effect:Compared with prior art, the present invention has following features:Compared to existing batch tank response system
Production tributyl citrate, the method that this patent is provided have using using tubular reactor method equipment is simple, reaction efficiently, even
The easily operated, process of continuous reaction does not produce the three wastes substantially, and product quality is high and stable, and high degree of automation, employment is significantly reduced
Deng, produce into and be greatly lowered, thus not only there is significant economic benefit, and with obvious environmental benefit.
Tributyl citrate production method of the present invention, it is real using tubular reactor (built-in high-performance solid catalyst)
Existing citric acid with butanol Efficient Conversion, be equipped with continuous impurity removing technology, continuous rectification technology in combination with realize the production of the product
Serialization, wherein a small amount of calcium citrate side-product for producing is known calsium supplement, Jing simple process can become
Calsium supplement product, thus realize the greenization production of the production.
Specific embodiment:
Embodiment 1:
Butanol is continuously squeezed into into dress with citric acid mixture (its mol ratio is 3.0) (80 DEG C of insulations in storage tank are mixed homogeneously)
Have in the tubular reactors of Φ 6 × 10000 of 10% copper p-toluenesulfonate/A.C. solid catalysts (10~20 mesh) and reacted,
100 DEG C of reaction temperature, residence time of material is 1.5h, reaction pressure 1.0MPa;The pump at rear 1/3rd of tubular reactor
Enter butanol (its mol ratio is 1.5), citric acid conversion ratio 99.3% when reactant mixture leaves the tubular reactor;It is reacted
Mixture enters neutralization reaction kettle, is neutralized to remove unreacted micro Fructus Citri Limoniae by being added thereto to saturated limewater
Acid, it is 8.0 to control pH in retort.The solid by-product Jing tubular filters of generation are removed;Using two tubular filters simultaneously
The mode of connection, after a tubular filter is filled solidss, switches another tubular filter;Or filtered with continuous
Other equipment;Mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, tower top
For butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column with further separation water (tower top) and butanol (bottom of towe),
Butanol return system is reused, and water can be used to prepare saturated limewater, first order rectifying column:Tower bottom product tributyl citrate
Purity 99.8%, yield 99.4%;Second level rectifying column:Tower bottom product butanol purity 99.5%, contains butanol in overhead product water
0.01%;The device continuously runs 100h phenomenons without exception to be occurred.
Embodiment 2:
Butanol is continuously squeezed into into dress with citric acid mixture (its mol ratio is 4.0) (80 DEG C of insulations in storage tank are mixed homogeneously)
Have in the tubular reactors of Φ 6 × 10000 of 20% p-methyl benzenesulfonic acid/A.C. solid catalysts (10~20 mesh) and reacted, instead
80 DEG C of the temperature, residence time of material is answered to be, 2.0h, reaction pressure 3.0MPa;Pump at rear 1/3rd of tubular reactor
Butanol (its mol ratio is 1.0), citric acid conversion ratio 99.0% when reactant mixture leaves the tubular reactor;It is reacted mixed
Compound enters neutralization reaction kettle, is neutralized to remove unreacted micro Fructus Citri Limoniae by being added thereto to saturated limewater
Acid, it is 7.5 to control pH in retort.The solid by-product Jing tubular filters of generation are removed;Using two tubular filters simultaneously
The mode of connection, after a tubular filter is filled solidss, switches another tubular filter;Or filtered with continuous
Other equipment;Mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, tower top
For butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column with further separation water (tower top) and butanol (bottom of towe),
Butanol return system is reused, and water can be used to prepare saturated limewater, first order rectifying column:Tower bottom product tributyl citrate
Purity 99.5%, yield 99.0%;Second level rectifying column:Tower bottom product butanol purity 99.4%, contains butanol in overhead product water
0.02%;The device continuously runs 100h phenomenons without exception to be occurred.
Embodiment 3:
Butanol is continuously squeezed into into dress with citric acid mixture (its mol ratio is 3.5) (80 DEG C of insulations in storage tank are mixed homogeneously)
Have in the tubular reactors of Φ 6 × 10000 of niobium pentaoxide solid catalyst (10~20 mesh) and reacted, reaction temperature 170
DEG C, residence time of material is 0.5h, reaction pressure 1.0MPa;(it rubs to pump into butanol at rear 1/3rd of tubular reactor
You are than being 1.0) citric acid conversion ratio 99.6% when reactant mixture leaves the tubular reactor;Reacted mixture is entered
Neutralization reaction kettle, is neutralized to remove unreacted micro citric acid by being added thereto to saturated limewater, and control is anti-
PH in tank is answered to be 9.0.The solid by-product Jing tubular filters of generation are removed;By the way of two tubular filter parallel connections,
After a tubular filter is filled solidss, switch another tubular filter;Or with the continuous other equipment for filtering;
Mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, tower top be butanol and
Aqueous mixtures;, with further separation water (tower top) and butanol (bottom of towe), butanol is returned for butanol and aqueous mixtures second level rectifying column
System is reused, and water can be used to prepare saturated limewater, first order rectifying column:Tower bottom product tributyl citrate purity
99.2%, yield 98.5%;Second level rectifying column:Tower bottom product butanol purity 99.1%, contains butanol in overhead product water
0.01%;The device continuously runs 100h phenomenons without exception to be occurred.
Embodiment 4
Butanol is continuously squeezed into into dress with citric acid mixture (its mol ratio is 3.8) (80 DEG C of insulations in storage tank are mixed homogeneously)
Have in the tubular reactors of Φ 6 × 10000 of 15% tungsten system heteropoly acid/A.C. solid catalysts (10~20 mesh) and reacted, instead
Answer 130 DEG C of temperature, residence time of material is 1.0h, reaction pressure 0.1MPa;Pump at rear 1/3rd of tubular reactor
Butanol (its mol ratio is 1.5), citric acid conversion ratio 99.2% when reactant mixture leaves the tubular reactor;It is reacted mixed
Compound enters neutralization reaction kettle, is neutralized to remove unreacted micro Fructus Citri Limoniae by being added thereto to saturated limewater
Acid, it is 8.0 to control pH in retort.The solid by-product Jing tubular filters of generation are removed;Using two tubular filters simultaneously
The mode of connection, after a tubular filter is filled solidss, switches another tubular filter;Or filtered with continuous
Other equipment;Mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, tower top
For butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column with further separation water (tower top) and butanol (bottom of towe),
Butanol return system is reused, and water can be used to prepare saturated limewater, first order rectifying column:Tower bottom product tributyl citrate
Purity 99.3%, yield 98.1%;Second level rectifying column:Tower bottom product butanol purity 99.3%, contains butanol in overhead product water
0.01%;The device continuously runs 100h phenomenons without exception to be occurred.
Embodiment 5:
Butanol is continuously squeezed into into dress with citric acid mixture (its mol ratio is 3.3) (80 DEG C of insulations in storage tank are mixed homogeneously)
There is 10% sulfate radical/ZrO2Reacted in the tubular reactors of Φ 6 × 10000 of solid super acid catalyst (10~20 mesh),
150 DEG C of reaction temperature, residence time of material is, 1.8h, reaction pressure 0.5MPa;The pump at rear 1/3rd of tubular reactor
Enter butanol (its mol ratio is 1.0), citric acid conversion ratio 99.5% when reactant mixture leaves the tubular reactor;It is reacted
Mixture enters neutralization reaction kettle, is neutralized to remove unreacted micro Fructus Citri Limoniae by being added thereto to saturated limewater
Acid, it is 8.0 to control pH in retort.The solid by-product Jing tubular filters of generation are removed;Using two tubular filters simultaneously
The mode of connection, after a tubular filter is filled solidss, switches another tubular filter;Or filtered with continuous
Other equipment;Mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, tower top
For butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column with further separation water (tower top) and butanol (bottom of towe),
Butanol return system is reused, and water can be used to prepare saturated limewater, first order rectifying column:Tower bottom product tributyl citrate
Purity 99.4%, yield 98.5%;Second level rectifying column:Tower bottom product butanol purity 99.2%, contains butanol in overhead product water
0.02%;The device continuously runs 100h phenomenons without exception to be occurred.
Embodiment 6 (Reference Example 1):
Tributyl citrate is prepared using batch process technology of preparing, specific embodiment is:
(1) esterification:Enter in the four-hole bottle of belt stirrer, condenser, water knockout drum, constant pressure funnel and thermometer
OK, heating adopts controllable temperature electric heater, adds n-butyl alcohol and citric acid and concentrated sulphuric acid to be heated to reflux state toward four-hole bottle,
Backflow a period of time.Acid number is determined at regular intervals, and at reflux, with the carrying out of reaction, reacting liquid temperature is gradually
Raise, by the vacuum degree control reacting liquid temperature of heating appliances and systems at 120 DEG C or so;Reactant liquor after successive reaction 4.5h
Acid number it is substantially unchanged, cool down after completion of the reaction;(2) neutralization washing:With in 5% NaOH solution and, be washed to neutrality, point
Go water phase;(3) distill:Under 0.098MPa vacuums, control kettle liquid temperature is less than 140 DEG C to ester, and vacuum distillation was reclaimed
The n-butyl alcohol of amount;(4) decolourize:Under normal pressure, activated carbon, stirring 0.5h or so cooling is added, leach activated carbon, obtain citric acid three
Butyl ester product.Tributyl citrate purity 98.5%, yield 90.5%, and product colour are faint yellow.If it is nothing to be taken off
Color, then its yield be then reduced to 86.8%.
Claims (8)
1. a kind of tubular reactor prepares tributyl citrate method, it is characterised in that adopt tubular type under solid catalyst effect
Reactor continuity method prepares tributyl citrate, carries out according to the following steps:
1) butanol is continuously squeezed in tubular reactor with citric acid mixture and is reacted, be to promote citric acid further to turn
Change, at rear 1/3rd of tubular reactor butanol is pumped into;
2) reacted mixture enter neutralization reaction kettle, by be added thereto to saturated limewater be neutralized it is not anti-to remove
The citric acid answered, the solid by-product Jing tubular filters of generation are removed;
3) the mixed liquor Jing two stage rectifications Jing after remove impurity are obtained product:First order rectifier bottoms are product, such as purity
Not enough it is contemplated that further rectification and purification, tower top is butanol and aqueous mixtures;Butanol and aqueous mixtures second level rectifying column are entering
One step separation water and butanol, butanol return system is reused.
2. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that butanol and Fructus Citri Limoniae in the step 1
Acid blend, both mol ratios are 3~4:1, both mix homogeneously enter reactor when being incubated 80~100 DEG C.
3. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that reaction temperature in the step 1:
80~170 DEG C, residence time of material be 0.5~2.0h, reaction pressure≤3.0MPa.
4. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that in pipe reaction in the step 1
It is 1.0~1.5 that butanol amount is pumped at rear 1/3rd of device with citric acid mol ratio.
5. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that tubular reactor in the step 1
Built with high-performance solid catalyst, the high-performance solid catalyst with niobium pentaoxide, p-methyl benzenesulfonic acid, copper p-toluenesulfonate,
Heteropoly acid, solid super-strong acid are main active component.
6. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that control reaction in described step 2
PH is 7.0~9.0 in kettle.
7. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that two are adopted in described step 2
Tubular filter mode in parallel, after a tubular filter is filled solidss, switches another tubular filter.
8. it is according to claim 1 to prepare tributyl citrate method, it is characterised in that rectification in described step 3 is separated
Condition is:First order rectifying column:Tower bottom product tributyl citrate purity >=99.0%, yield >=98.0%;Second level rectification
Tower:Tower bottom product butanol purity >=99.0%, containing butanol etc.≤0.05% in overhead product water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611224447.2A CN106674008B (en) | 2016-12-27 | 2016-12-27 | A kind of tubular reactor preparation tributyl citrate method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611224447.2A CN106674008B (en) | 2016-12-27 | 2016-12-27 | A kind of tubular reactor preparation tributyl citrate method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106674008A true CN106674008A (en) | 2017-05-17 |
CN106674008B CN106674008B (en) | 2019-04-23 |
Family
ID=58871660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611224447.2A Active CN106674008B (en) | 2016-12-27 | 2016-12-27 | A kind of tubular reactor preparation tributyl citrate method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106674008B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107311867A (en) * | 2017-08-09 | 2017-11-03 | 山东万图高分子材料股份有限公司 | A kind of preparation method of citrate |
CN108031489A (en) * | 2017-12-01 | 2018-05-15 | 南京科技职业学院 | A kind of preparation method and applications of the immobilized copper p-toluene sulfonate catalysis of flyash |
CN109174180A (en) * | 2018-09-30 | 2019-01-11 | 浙江工业大学上虞研究院有限公司 | A kind of preparation method and applications of the loaded catalyst based on sulfonating reaction |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101735049A (en) * | 2009-12-18 | 2010-06-16 | 沈阳工业大学 | Method and equipment for producing C4-C6 diacid low-carbon alcohol ester |
-
2016
- 2016-12-27 CN CN201611224447.2A patent/CN106674008B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101735049A (en) * | 2009-12-18 | 2010-06-16 | 沈阳工业大学 | Method and equipment for producing C4-C6 diacid low-carbon alcohol ester |
Non-Patent Citations (1)
Title |
---|
晓铭: "柠檬酸三丁酯合成技术新进展", 《精细化工原料及中间体》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107311867A (en) * | 2017-08-09 | 2017-11-03 | 山东万图高分子材料股份有限公司 | A kind of preparation method of citrate |
CN108031489A (en) * | 2017-12-01 | 2018-05-15 | 南京科技职业学院 | A kind of preparation method and applications of the immobilized copper p-toluene sulfonate catalysis of flyash |
CN109174180A (en) * | 2018-09-30 | 2019-01-11 | 浙江工业大学上虞研究院有限公司 | A kind of preparation method and applications of the loaded catalyst based on sulfonating reaction |
CN109174180B (en) * | 2018-09-30 | 2021-08-06 | 浙江工业大学上虞研究院有限公司 | Preparation method and application of supported catalyst based on sulfonation reaction |
Also Published As
Publication number | Publication date |
---|---|
CN106674008B (en) | 2019-04-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106674008B (en) | A kind of tubular reactor preparation tributyl citrate method | |
CN103613501B (en) | Method with macropore strong acid cation exchanger resin for catalyst preparing tributyl citrate | |
CN111960943A (en) | Process for producing dioctyl terephthalate by semi-continuous method | |
CN103113617A (en) | Novel plasticizer and preparation method thereof | |
CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
CN100404495C (en) | Tributyl citrate preparation method using ion liquid catalysis | |
CN103319307A (en) | Method for preparing sodium soap | |
CN109134198A (en) | A kind of method of separation of extractive distillation tetrafluoropropanol and water azeotropic mixture | |
CN105418699A (en) | Method and production device for continuously producing alkyl glucoside | |
CN109535104B (en) | A kind of production method of epoxidized soybean oil | |
CN106748839A (en) | A kind of glycine and the clean preparation method of iminodiacetic acid coproduction | |
CN108164416B (en) | Novel process for preparing monomethyl azelate based on biodiesel | |
CN105384629A (en) | Energy-saving and environment-friendly production process of isobutyl lactate | |
CN104892669A (en) | Continuous preparation method of diphenyl isooctyl phosphate | |
CN108069820A (en) | A kind of trifluoroethanol synthesis technology | |
CN103113992A (en) | Method for selectively oxidizing and synthesizing epoxy cottonseed oil plasticizer by utilizing industrial coarse cottonseed oil | |
CN103436562B (en) | Preparation method of oxalic acid epoxy vegetable oil acid glyceride | |
CN105749967A (en) | Method for preparing tributyl citrate in presence of bamboo-charcoal-based solid sulfonic acid catalyst | |
CN111072473A (en) | Preparation method of dimethyl adipate | |
CN108203385B (en) | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone | |
CN103936588A (en) | Green and clean process for preparing malonate | |
CN104529774A (en) | Preparation method for tributyl citrate | |
CN101239911A (en) | Method for synthesizing tributyl acetcitrate | |
CN208732973U (en) | A kind of synthesizer of triisononyl trimellitate plasticizer | |
CN106478401A (en) | The method that methyl glycollate prepares ethanol acid crystal |
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 | ||
CP02 | Change in the address of a patent holder |
Address after: Room d8403-34, 4th floor, No.818 Huayuan Road, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: NANJING POLYTECHNIC INSTITUTE Address before: 210048 Jiangsu city of Nanjing Province along the Yangtze River Industrial Development Zone geguan Road No. 625 Patentee before: NANJING POLYTECHNIC INSTITUTE |
|
CP02 | Change in the address of a patent holder |