CN107556205A - A kind of production method of diethanol monoisopropanolamine - Google Patents
A kind of production method of diethanol monoisopropanolamine Download PDFInfo
- Publication number
- CN107556205A CN107556205A CN201710981621.6A CN201710981621A CN107556205A CN 107556205 A CN107556205 A CN 107556205A CN 201710981621 A CN201710981621 A CN 201710981621A CN 107556205 A CN107556205 A CN 107556205A
- Authority
- CN
- China
- Prior art keywords
- diethanol
- expoxy propane
- acid
- diethanol monoisopropanolamine
- production method
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of production method of diethanol monoisopropanolamine, comprises the following steps：S1, diethanol amine, water and acid is added in reactor, opens agitating paddle and be well mixed each material；S2, under room temperature state, be slowly added to expoxy propane, and continue stirring expoxy propane and unclassified stores are uniformly mixed, reaction temperature is increased to 30~80 DEG C；S3, after treating that expoxy propane all adds, insulation reaction 30min is carried out to reactor, obtains finished product diethanol monoisopropanolamine.Due to diethanol amine and the diethanol monoisopropanolamine of expoxy propane reaction generation, part can also react generation quaternary amine alkali with expoxy propane in the presence of water.And this quaternary amine alkali is a kind of strong alkali catalyst, its hydroxyl that can be catalyzed on diethanol monoisopropanolamine and expoxy propane continue reaction and form ether.And acid can fast and effeciently play neutralization to quaternary amine alkali during the course of the reaction, reduce diethanol monoisopropanolamine and reacted to accessory substance ether direction.
Description
Technical field
The present invention relates to chemical building material field, more particularly to a kind of production method of diethanol monoisopropanolamine.
Background technology
The cement output of nationwide cement production enterprise above is more than 13.88 hundred million tons since 2008, and cement
The amount that agent usually requires to add is the 0.01~0.05% of cement, and therefore, cement grinding aid has sizable market demand.And
Diethanol monoisopropanolamine because it has numerous excellent characteristics, so, it gradually instead of three in grinding aid raw material
Monoethanolamine and triisopropanolamine.Also, more crucially diethanol monoisopropanolamine is that green new grinding aid is former
Material, it has fabulous grinding-aid effect.There is good compatibility with triethanolamine, triisopropanolamine and other alcohol, amine, lipid material
Performance, can be used alone when making grinding aid or with other material compatible uses.According to different cement material features, with diethyl
Alcohol monoisopropanolamine is core material, and after carrying out specific aim compatibility, be significantly increased characteristic to cement early stage and later strength.
Made grinding aid can improve 28 days intensity of cement while three days intensity of cement is improved.Suitable in actual use
In the case of Ying Xingqiang, early strength can raise also higher than triethanolamine.But generally, early strength compares triethanolamine
It is more lower slightly.It is confessedly to be, later strength can be increased substantially, it is typically more taller than triisopropanolamine.
In addition, as this large and relatively low profit product, if often lifting one in chromatographic content or chromatographic purity
Percentage point, then bigger benefit can be brought to production and selling type enterprise, therefore major scientific research institutions of incorporated business are also in product
The research and development of pole are to improve the content of diethanol monoisopropanolamine.But generally pass through the color of single step reaction method diethanol monoisopropanolamine
Spectrum content can only achieve 96% or so, some enterprises are even lower, and unnecessary impurity be mainly unreacted diethanol amine and
Height boiling, the presence of height boiling also can have certain negative effect to the performance of grinding aid simultaneously.But improving diethanol Dan Yi at present
In the chromatographic content of Propanolamine but encounter a bottleneck.So some enterprises are in order to obtain more than 98% chromatographic content
Product is often realized by the method for rectifying.
The side of low colourity diethanol monoisopropanolamine is produced as the Chinese patent of Application No. 201610413071.3 is a kind of
Method, its side for mainly passing through distillation with expoxy propane one-step synthesis method diethanol monoisopropanolamine 96% or so with diethanol amine
Method makes product content reach more than 98%.Although the chromatographic content of product can be improved by distillating method, energy is also increased
The triviality of consumption and technique, so being not easy to improve overall economic benefit.
The content of the invention
It is an object of the invention to provide a kind of production method of diethanol monoisopropanolamine, the diethanol Dan Yi produced
Not only purity is high for Propanolamine, while technique is also fairly simple and energy consumption is again few, so as to be advantageous to improve diethanol monoisopropanolamine
Whole economic efficiency.
The present invention above-mentioned purpose technical scheme is that：A kind of life of diethanol monoisopropanolamine
Production method, comprises the following steps：S1, diethanol amine, water and acid is added in reactor, is passed through nitrogen afterwards and put three times
Change, and open agitating paddle and be well mixed each material；S2, under room temperature state, be slowly uniformly added into expoxy propane, and continue to stir
Mix and expoxy propane and unclassified stores are uniformly mixed, reaction temperature is increased to 30~80 DEG C；S3, treat that expoxy propane is complete
After portion adds, insulation reaction 30min is carried out to reactor, obtains finished product diethanol monoisopropanolamine.
By using above-mentioned technical proposal, due to diethanol amine and the diethanol list isopropanol of expoxy propane reaction generation
Amine, it partly can also continue reaction generation quaternary amine alkali with expoxy propane in the case of the catalysis of water.And this quaternary amine alkali is a kind of
Strong alkaline substance, therefore, it can be as the catalyst of accessory substance.In the presence of this strong alkaline substance, diethanol Dan Yi
Hydroxyl on Propanolamine will continue reaction with expoxy propane and form ether i.e. high-boiling components.Shown in following reaction equation：
Main reaction：
Side reaction (generations of high-boiling components)：
Because under the catalytic action of quaternary amine alkali, whole course of reaction often produces substantial amounts of high-boiling components, so that also will be tight
The purity of diethanol monoisopropanolamine is had influence on again, so in order to improve the purity of diethanol monoisopropanolamine, then needs to put into
The substantial amounts of energy is simultaneously separated high-boiling components and diethanol monoisopropanolamine in a manner of rectifying, so not only wastes energy
Source, while production efficiency is also reduced, it is unfavorable for improving the economic benefit of diethanol monoisopropanolamine.
And acid and diethanol amine are charged first in reactor herein and mixed, it can so ensure acid in diethanol amine
Molecule is nearby uniformly disperseed, so as to fast and effeciently play neutralization to caused quaternary amine alkali, and then also
Diethanol monoisopropanolamine can be reduced to react to accessory substance ether direction.
Preferably, the mol ratio of the diethanol amine and expoxy propane is 1: 0.95~1.05.
By using above-mentioned technical proposal, so diethanol amine and expoxy propane can be avoided to occur during reaction
The problem of excessive, so as to be also beneficial to the probability that reduction diethanol monoisopropanolamine reacts to side reaction direction.
Preferably, the hydrionic mol ratio that diethanol amine and acid ionize out in S1 is 36.94~183.98: 1.
By using above-mentioned technical proposal, so during reaction, amount substantially can with quaternary amine alkali caused by acid
It is enough to neutralize completely, reacted so as to also avoid quaternary amine base catalysis diethanol monoisopropanolamine to side reaction direction.
Preferably, the acid is the mixture of one or both of glacial acetic acid or the concentrated sulfuric acid.
By using above-mentioned technical proposal, the convenience that on the one hand this two kinds acid materials compare, secondly, both acid all compare
Hydrogen ion easily is ionized out, so as to also just reduce the dosage of acid.
Preferably, the weight of diethanol amine and water ratio is 4.9~15: 1.
By using above-mentioned technical proposal, water can play a part of solvent during reaction, and it contributes to diethyl
Hydramine and expoxy propane are mixed, and are so also beneficial to reduce the viscosity of mixture after blending, improve the stream of mixture
Dynamic property, consequently facilitating agitating paddle stirs to mixture, it ensure that material can be all the time in mixing during reaction
Uniform state.
Preferably, in S3 the temperature control of insulation reaction at 60~80 DEG C.
By using above-mentioned technical proposal, reaction temperature is controlled at 60~80 DEG C, on the one hand can ensure diethanol amine
Generation diethanol monoisopropanolamine can be rapidly reacted with expoxy propane, on the other hand can also reduce the ring being dissolved in water
The probability that Ethylene Oxide vaporizes, so as to be advantageous to can fully react complete between diethanol amine and expoxy propane.
Preferably, S2 and S3 reactor pressure is 0.2~0.4Mpa.
By using above-mentioned technical proposal, be so on the one hand advantageous to accelerate the speed of reaction, be on the other hand also beneficial to
Ensure effectively to mix between material, the probability that partial material vaporizes is reduced, so as to be also beneficial to improve each reaction mass
Homogeneous blend.
In summary, the invention has the advantages that：
1. adding acid during reaction, be so advantageous to suppress the generation of quaternary amine alkali, so as to advantageously reduce high-boiling components
Generation, avoiding the purity of diethanol monoisopropanolamine reduces, and then also just eliminates and purified by rectifying mode；
2. the hydrionic mol ratio control that diethanol amine and acid are ionized out can be so protected 36.94~183.98: 1
Card acid can be neutralized fully with quaternary amine alkali, be carried out so as to avoid quaternary amine base catalysis diethanol monoisopropanolamine to side reaction direction
Reaction；
3. the temperature of reaction and pressure are controlled in 60~80 DEG C and 0.2~0.4Mpa respectively, so on the one hand it is favorably improved
The production efficiency of diethanol monoisopropanolamine, on the other hand also contributing to, which reduces the expoxy propane being dissolved in water, vaporizes,
And influence completeness of reaction.
Brief description of the drawings
Fig. 1 is a kind of flow sheet of diethanol monoisopropanolamine.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing 1.
Embodiment one,
Step 1：10046Kg diethanol amine, 2050Kg water and 31Kg glacial acetic acid are added in reactor, backward reactor
In be passed through nitrogen and replaced in triplicate, the air inside reactor is drained, agitating paddle is opened and is stirred, material is filled
Point mixing it is equal, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5272Kg, and is added
The temperature of reactor is stepped up to 30 DEG C by the speed control entered in 1171.6Kg/h or so in 30min；
Step 3：Treat that expoxy propane adds and then the temperature of reactor is increased into 60 DEG C in 30min, and be incubated and continue
30min, obtain finished product diethanol monoisopropanolamine.
Wherein, acid used herein can also be the various acid that can ionize out proton, can be various organic acids or nothing
Machine acid, such as, formic acid, acetic acid, lactic acid, the concentrated sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, nitric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, amino
Sulfonic acid, oxalic acid etc..
Embodiment two,
Step 1：10046Kg diethanol amine, 700Kg water and the 127Kg concentrated sulfuric acids are added in reactor, backward reactor
In be passed through nitrogen and replaced in triplicate, the air inside reactor is drained, agitating paddle is opened and is stirred, material is filled
Point mixing it is equal, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5827Kg, and is added
The temperature of reactor is stepped up to 80 DEG C by the speed control entered in 1295Kg/h in 30min；
Step 3：Treat that expoxy propane is added and then is incubated and continue 30min, obtain finished product diethanol monoisopropanolamine.
Embodiment three,
Step 1：10046Kg diethanol amine, 1010Kg water, 52Kg glacial acetic acid and the 26Kg concentrated sulfuric acids are added in reactor, it
Nitrogen is passed through in backward reactor to be replaced in triplicate, the air inside reactor is drained, and is opened agitating paddle and is stirred
Mix, material is sufficiently mixed, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5549Kg, and is added
The temperature of reactor is stepped up to 55 DEG C by the speed control entered in 1233Kg/h in 30min；
Step 3：Treat that expoxy propane adds and then the temperature of reactor is increased into 70 DEG C in 30min, and be incubated and continue
30min, obtain finished product diethanol monoisopropanolamine.
Example IV,
Step 1：10046Kg diethanol amine, 1010Kg water and 127Kg glacial acetic acid are added in reactor, backward reactor
In be passed through nitrogen and replaced in triplicate, the air inside reactor is drained, agitating paddle is opened and is stirred, material is filled
Point mixing it is equal, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5826Kg, and is added
The temperature of reactor is stepped up to 60 DEG C by the speed control entered in 1295Kg/h in 30min；
Step 3：Treat that expoxy propane adds and then the temperature of reactor is increased into 80 DEG C in 30min, and be incubated and continue
30min, obtain finished product diethanol monoisopropanolamine.
Embodiment five,
Step 1：10046Kg diethanol amine, 2050Kg water and the 78Kg concentrated sulfuric acids are added in reactor, backward reactor
In be passed through nitrogen and replaced in triplicate, the air inside reactor is drained, agitating paddle is opened and is stirred, material is filled
Point mixing it is equal, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5549Kg, and is added
The temperature of reactor is stepped up to 55 DEG C by the speed control entered in 1233Kg/h in 30min；
Step 3：Treat that expoxy propane adds and then the temperature of reactor is increased into 70 DEG C in 30min, and be incubated and continue
30min, obtain finished product diethanol monoisopropanolamine.
Comparative example one,
Step 1：10046Kg diethanol amine and 2050Kg water are added in reactor, backward reactor in be passed through nitrogen and enter
Row is replaced in triplicate, and the air inside reactor is drained, and is opened agitating paddle and is stirred, material is sufficiently mixed,
The rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5272Kg, and is added
The temperature of reactor is stepped up to 30 DEG C by the speed control entered in 1171.6Kg/h in 30min；
Step 3：Treat that expoxy propane adds and then the temperature of reactor is increased into 60 DEG C in 30min, and be incubated and continue
30min, obtain finished product diethanol monoisopropanolamine.
Comparative example two,
Step 1：10046Kg diethanol amine, 669.73Kg water and the 75Kg concentrated sulfuric acids are added in reactor, backward reaction
Nitrogen is passed through in kettle to be replaced in triplicate, the air inside reactor is drained, and is opened agitating paddle and is stirred, by material
It is sufficiently mixed, the rotating speed of agitating paddle is 500rpm；
Step 2：In the case of room temperature, expoxy propane is slowly uniformly added into, the amount that expoxy propane adds is 5826Kg, and is added
The temperature of reactor is stepped up to 80 DEG C by the speed control entered in 1295Kg/h in 30min；
Step 3：Treat that expoxy propane is added and then is incubated and continue 30min, obtain finished product diethanol monoisopropanolamine.
Using chromatograph and pH meter in embodiment one to embodiment five and comparative example one and comparative example two into
Product diethanol monoisopropanolamine is analyzed, and is obtained such as following table data：
From upper table it should be apparent that as the diethanol list obtained by the production method of diethanol monoisopropanolamine of the present invention
The purity of isopropanolamine is generally higher than the finished product of the same race of most of in the market.And also eliminated in whole generating process purification with
And the step of neutralizing spent acid, so as to also be considerably improved the production efficiency of diethanol monoisopropanolamine, reduce mass energy
Waste.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification of no creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the right of invention by Patent Law.
Claims (7)
1. a kind of production method of diethanol monoisopropanolamine, comprises the following steps：
S1, diethanol amine, water and acid is added in reactor, is passed through nitrogen afterwards and replaced three times, and open agitating paddle
Each material is well mixed；
S2, under room temperature state, be slowly uniformly added into expoxy propane, and continue stirring and enable expoxy propane and unclassified stores
Uniformly mixing, 30~80 DEG C are increased to by reaction temperature；
S3, after treating that expoxy propane all adds, insulation reaction 30min is carried out to reactor, obtains finished product diethanol list isopropyl
Hydramine.
A kind of 2. production method of diethanol monoisopropanolamine according to claim 1, it is characterised in that：The diethanol
The mol ratio of amine and expoxy propane is 1: 0.95~1.05.
A kind of 3. production method of diethanol monoisopropanolamine according to claim 1, it is characterised in that：Diethanol in S1
The hydrionic mol ratio that amine and acid ionize out is 36.94~183.98: 1.
A kind of 4. production method of diethanol monoisopropanolamine according to claim 3, it is characterised in that：The acid is ice
The mixture of one or both of acetic acid or the concentrated sulfuric acid.
A kind of 5. production method of diethanol monoisopropanolamine according to claim 1, it is characterised in that：Diethanol amine and
The weight ratio of water is 4.9~15: 1.
A kind of 6. production method of diethanol monoisopropanolamine according to claim 1, it is characterised in that：It is incubated in S3 anti-
The temperature control answered is at 60~80 DEG C.
A kind of 7. production method of diethanol monoisopropanolamine according to claim 1, it is characterised in that：S2's and S3 is anti-
It is 0.2~0.4Mpa to answer kettle pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710981621.6A CN107556205A (en) | 2017-10-19 | 2017-10-19 | A kind of production method of diethanol monoisopropanolamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710981621.6A CN107556205A (en) | 2017-10-19 | 2017-10-19 | A kind of production method of diethanol monoisopropanolamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107556205A true CN107556205A (en) | 2018-01-09 |
Family
ID=60985596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710981621.6A Pending CN107556205A (en) | 2017-10-19 | 2017-10-19 | A kind of production method of diethanol monoisopropanolamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107556205A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529715A (en) * | 2018-11-24 | 2019-03-29 | 宁波远利化工有限公司 | A kind of modified grease and preparation method thereof and the surfactant as made from the modified grease |
| CN109627177A (en) * | 2019-01-15 | 2019-04-16 | 四川鑫统领新材料有限公司 | A kind of preparation method of high-purity diethanol monoisopropanolamine |
| CN111646909A (en) * | 2020-04-23 | 2020-09-11 | 安徽海螺新材料科技有限公司 | Preparation method and application of alcohol amine compound capable of improving early strength of cement |
| CN111875509A (en) * | 2020-08-11 | 2020-11-03 | 安徽海螺新材料科技有限公司 | Preparation method of diethanolisopropanolamine |
| CN114835593A (en) * | 2022-05-06 | 2022-08-02 | 北京金隅水泥节能科技有限公司 | Production process of diethanolisopropanolamine |
| CN115073031A (en) * | 2022-05-20 | 2022-09-20 | 唐山冀东水泥外加剂有限责任公司 | Cement grinding aid and production process and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224453A (en) * | 2013-03-28 | 2013-07-31 | 宁波市联凯化学有限公司 | Method for preparing diethanol isopropanol amine |
| CN103998416A (en) * | 2011-12-21 | 2014-08-20 | 陶氏环球技术有限责任公司 | Improved process for making ethoxylated amine compounds |
-
2017
- 2017-10-19 CN CN201710981621.6A patent/CN107556205A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103998416A (en) * | 2011-12-21 | 2014-08-20 | 陶氏环球技术有限责任公司 | Improved process for making ethoxylated amine compounds |
| CN103224453A (en) * | 2013-03-28 | 2013-07-31 | 宁波市联凯化学有限公司 | Method for preparing diethanol isopropanol amine |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529715A (en) * | 2018-11-24 | 2019-03-29 | 宁波远利化工有限公司 | A kind of modified grease and preparation method thereof and the surfactant as made from the modified grease |
| CN109627177A (en) * | 2019-01-15 | 2019-04-16 | 四川鑫统领新材料有限公司 | A kind of preparation method of high-purity diethanol monoisopropanolamine |
| CN111646909A (en) * | 2020-04-23 | 2020-09-11 | 安徽海螺新材料科技有限公司 | Preparation method and application of alcohol amine compound capable of improving early strength of cement |
| CN111646909B (en) * | 2020-04-23 | 2022-09-06 | 安徽海螺新材料科技有限公司 | Preparation method and application of alcohol amine compound capable of improving early strength of cement |
| CN111875509A (en) * | 2020-08-11 | 2020-11-03 | 安徽海螺新材料科技有限公司 | Preparation method of diethanolisopropanolamine |
| CN111875509B (en) * | 2020-08-11 | 2022-05-20 | 安徽海螺新材料科技有限公司 | Preparation method of diethanolisopropanolamine |
| CN114835593A (en) * | 2022-05-06 | 2022-08-02 | 北京金隅水泥节能科技有限公司 | Production process of diethanolisopropanolamine |
| CN114835593B (en) * | 2022-05-06 | 2023-09-19 | 北京金隅节能科技有限公司 | Production process of diethanol monoisopropanolamine |
| CN115073031A (en) * | 2022-05-20 | 2022-09-20 | 唐山冀东水泥外加剂有限责任公司 | Cement grinding aid and production process and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107556205A (en) | A kind of production method of diethanol monoisopropanolamine | |
| CN101955330B (en) | Polycarboxylic acid-alcohol amine type high-molecular grinding aid and preparation method thereof | |
| CN104059230A (en) | Block amino silicone oil production method | |
| CN101549972B (en) | Concrete composite air entraining agent and method of preparing the same | |
| CN105793329A (en) | Method for processing cellulose-containing biomass | |
| CN106732768A (en) | A kind of solid-carrying type ionic-liquid catalyst for carbon dioxide cycloaddition reaction and preparation method thereof | |
| CN105753818B (en) | The method of synthesizing epoxy calcium succinate suspension and the method for production L (+) tartaric acid | |
| CN109928863B (en) | A kind of iso-butane and oxygen prepare the reaction unit and method of the tert-butyl alcohol and tert-butyl hydroperoxide | |
| CN105642325A (en) | Supported vanadium-based catalyst and preparation method thereof | |
| CN107089941A (en) | A kind of method for catalyzing and synthesizing vitamin B6 | |
| CN114316245A (en) | Method for improving content of dioxane in fatty alcohol polyoxyethylene ether sulfate | |
| CN104177231B (en) | A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid | |
| CN105800988A (en) | Method for synthesizing modified sulfamate water reducer by utilizing wastewater generated in H acid production process | |
| CN102898602A (en) | Method for synthesizing linear phenolic resin | |
| CN101245010B (en) | Method for producing civil dinitrotoluene | |
| CN110316891A (en) | A kind of preparation method of H acid waste water extraction process and modified aliphatic water reducing agent | |
| CN106278908A (en) | Large red-based g production new technique | |
| CN107663157A (en) | The production method of monoethanol diisopropanolamine (DIPA) | |
| CN108863874A (en) | A kind of method of continuous synthesis dibenzyl aminodithioformic acid sodium | |
| CN107759480A (en) | A kind of production method of triethanolamine | |
| CN103864575A (en) | Method for preparing 1,2-pentanediol | |
| CN103394371A (en) | Method for producing vinyl-4-hydroxybutyl ether through acetylene method, and catalyst thereof | |
| CN111470793B (en) | High-dispersity high-quality naphthalene-based high-efficiency water reducing agent and preparation method thereof | |
| CN103145562A (en) | N-ethyl aniline preparation method | |
| EP4029603A1 (en) | Catalytic oxidation catalyst, preparation method therefor, and method for deep treatment of organic matters in mdi saline |
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 |
Application publication date: 20180109 |
|
| RJ01 | Rejection of invention patent application after publication |