CN104785297B - A kind of catalyst for being used to prepare aviation fuel antiwear additive - Google Patents
A kind of catalyst for being used to prepare aviation fuel antiwear additive Download PDFInfo
- Publication number
- CN104785297B CN104785297B CN201510134538.6A CN201510134538A CN104785297B CN 104785297 B CN104785297 B CN 104785297B CN 201510134538 A CN201510134538 A CN 201510134538A CN 104785297 B CN104785297 B CN 104785297B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ionic liquid
- antiwear additive
- inner salt
- 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.)
- Active
Links
Abstract
The present invention relates to a kind of catalyst for being used to prepare aviation fuel antiwear additive, which is ionic liquid I or ionic liquid II with following structural formula,
Description
Technical field
The present invention relates to a kind of catalyst for being used to prepare aviation fuel antiwear additive, especially a kind of ionic liquid.
Background technology
At present, the antiwear additive added in domestic air mail fuel is T1602, and the active principle of T1602 is aphthenic acids, aphthenic acids
The component of removing is wished in being processed for jet fuel, and rejoining aphthenic acids can cause the acidity of aviation fuel to increase, and can also
The corrosivity of jet fuel is caused to increase.And the colourity of T1602 additives is deeper, the colour index of aviation fuel is influenced, separately
Outside, the unstable product quality of T1602.
Aviation fuel mainly uses acid-alkali refining, hydrofinishing or is hydrocracked in process of production so that in cut
Natural wear-resistant component is removed, and causes the reduction of aviation fuel abrasion resistance, it is therefore necessary to antiwear additive is added in aviation fuel, is prevented
The only heavy wear of fuel system.
The content of the invention
For overcome the deficiencies in the prior art, the present invention proposes a kind of catalyst for being used to prepare aviation fuel antiwear additive,
A kind of antiwear additive of the aviation fuel of excellent performance can be synthesized using the catalyst, is particularly suitable for the wear-resistant of jet fuel
Agent, and the unexpected antiwear additive synthesized using the catalyst, greatly improve the corrosivity of former cycloalkanes acid type additive
Energy.
A kind of antiwear additive of aviation fuel, including C36 unrighted acid dimers, the C36 unrighted acid dimerization
Thing includes：Compound more than 65% shown in general formula (1), the compound 25-30% shown in general formula (2), the change shown in general formula (3)
Compound is less than 10%, in mass.
What above-mentioned C36 unrighted acids dimer was prepared as follows：
(A) preparation of fatty acid mixed：Soap is carried out including vegetable oil is mixed with excessive aqueous slkali and suitable ethanol
Glycerine is sloughed in change, generates soap, soap is acidified to pH=2~3, and using petroleum ether extraction oil phase, oil phase is through water
Wash, after anhydrous sodium sulfate drying, petroleum ether is removed using rotary evaporation, fatty acid mixed can be obtained after vacuum drying；
(B1) synthesis of C36 unrighted acids dimer, includes the following steps：
(1) it is placed in using the fatty acid mixed obtained by linoleic acid or step (A) as raw material in autoclave, adds 9-
15% catalyst and the auxiliary agent of 0.5-1.5%, the quality meter based on linoleic acid or above-mentioned fatty acid mixed, install high pressure
Kettle, and examine air-tightness, wherein catalyst are treated earth, and auxiliary agent is lithium carbonate, the preferred 10-13% of usage amount of catalyst,
More preferably 12%, the usage amount preferred 0.8-1.2% of auxiliary agent, more preferably 1.0%；
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen to 2.0MPa, close high
Press kettle intake valve；
(3) 230-240 DEG C of reaction temperature is heated under conditions of stirring, starts timing when reaching reaction temperature, makees
To react zero point；
(4) after when reaction 5-6 is small, heating is stopped, autoclave autoclave body is placed in cold water, autoclave body is dropped to room rapidly
Temperature, drives kettle, and pours out reaction product；
(5) crude product is diluted with isometric petroleum ether, and is added excessive hydrochloric acid and be acidified to pH=2~3；
(6) after being acidified, mixture is centrifuged, removes catalyst and solid impurity；
(7) supernatant liquor is washed with deionized water to neutrality, liquid separation, upper oil phase and is dried with anhydrous sodium sulfate, stands overnight,
It is filtered to remove anhydrous sodium sulfate；
(8) rotary evaporation in vacuo removes petroleum ether, most removes unreacted monomer acids through vacuum distillation afterwards, vacuum distillation
Condition is：Gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products.
Step B1 can use step B2 to replace, and step B2 includes the following steps：
(1) it is placed in using the fatty acid mixed obtained by linoleic acid or step (A) as raw material in autoclave, adds 9-
For 15% ionic liquid as catalyst, the quality meter based on linoleic acid or above-mentioned fatty acid mixed, installs autoclave, and examine
Test air-tightness, the usage amount preferred 10-13% of catalyst, more preferably 12%, ionic liquid is the ion with following structural formula
Liquid I or ionic liquid II,
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen to 2.0MPa, close high
Press kettle intake valve；
(3) 230-240 DEG C of reaction temperature is heated under conditions of stirring, starts timing when reaching reaction temperature, makees
To react zero point；
(4) after when reaction 5-6 is small, heating is stopped, autoclave autoclave body is placed in cold water, autoclave body is dropped to room rapidly
Temperature, drives kettle, and pours out reaction product；
(5) crude product is diluted with isometric petroleum ether, and is added excessive hydrochloric acid and be acidified to pH=2~3；
(6) after being acidified, supernatant liquor is washed with deionized water to neutrality, liquid separation, upper oil phase and is done with anhydrous sodium sulfate
It is dry, stand overnight, be filtered to remove anhydrous sodium sulfate, the recyclable recycling of ionic liquid of lower floor；
(7) rotary evaporation in vacuo removes petroleum ether, most removes unreacted monomer acids through vacuum distillation afterwards, vacuum distillation
Condition is：Gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products.
The synthesis of ionic liquid I：
Ionic liquid I specifically uses following preparation method：
(1) trimethylamine solution is mixed with 1,3-propane sultone equimolar in conical flask, reaction is stirred at 60 DEG C
24h；
(2) after reaction, rotary distillation removes water, obtains white solid；
(3) re-crystallizing in ethyl acetate is used, is filtered, and is washed three times；
(4) vacuum drying (80 DEG C) 4h obtains the solid inner salt of white；
(5) inner salt is dissolved with the water of 3 times of quality；
(6) hydrochloric acid that equimolar mass concentration is 37% is added dropwise to be acidified, is added dropwise, is warming up to 80 DEG C, stirring reaction
3h。
(7) rotary distillation removes water, is dried in vacuo (80 DEG C) 4h, obtains light yellow viscous liquid, that is, be acidified inner salt；
(8) a certain amount of acidifying inner salt is taken, is 1 with molar ratio:2 zinc chloride mixing, under nitrogen protection, is warming up to 100
DEG C, stir to solid and all dissolve；
(9) (80 DEG C) 8h is dried in vacuo, up to thick ionic liquid I.
The synthesis of ionic liquid II：
The specific synthesis step of ionic liquid II is as follows：
(1) a certain amount of 1,3-propane sultone is dissolved in the ethyl acetate that its mass number is 5~10 times, is warming up to 40
~60 DEG C, equimolar N- methylimidazoles are added dropwise.It is added dropwise, 3~5h of insulation reaction；
(2) after reaction, filter, obtain white filter cake, filter cake is washed three times with ethyl acetate；
(3) vacuum drying (100 DEG C) 2h obtains white solid inner salt 3- (1- methylimidazole -3- alkyl)-propyl sulfonic acid salt
(mim-PS)；
(4) a certain amount of inner salt mim-PS is taken, is dissolved in the deionized water that its mass number is 2~4 times；
(5) hydrochloric acid that equimolar mass concentration is 37% is added dropwise, acidifying finishes, and is warming up to 70~90 DEG C, stirring reaction 2
~3h；
(6) rotary distillation removes water, is dried in vacuo (80 DEG C) 4h, obtains light yellow viscous liquid, that is, is acidified inner salt chlorination
1- (3- sulfonic acid)-propyl group -3- methylimidazole salts [HO3S-(CH2)3-mim]Cl；
(7) a certain amount of acidifying inner salt is taken, is 1 with molar ratio:2 zinc chloride mixing, under nitrogen protection, it is warming up to 90~
110 DEG C, stir to solid and all dissolve；
(8) (80 DEG C) 8h is dried in vacuo, up to thick ionic liquid II.
Figure of description
Fig. 1 is that catalyst reuses influence of the number to C36 unrighted acids dimer (KM3) yield
Embodiment
Embodiment 1
Prepare fatty acid mixed：
(1) 100g sunflower oils accurately are weighed in 250mL three-necked flasks.
(2) 40g KOH, 80g deionized water (or 40ml 50%KOH solution) and 95% ethanol solution of 160ml are added.
(3) under the conditions of 90 DEG C of glycerol baths, saponification 2h is stirred at reflux, saponification liquor is obtained and (takes a small amount of saponification liquor to be dissolved in water, stand
It is if complete without oil reservoir, saponification).
(4) treat that saponification liquor is cooled to room temperature, add dilute hydrochloric acid to be acidified to pH=2~3, with a small amount of petroleum ether extraction oil phase.
(5) acidifying finishes, and is washed with deionized water to neutrality, liquid separation.Upper oil phase is dried with anhydrous sodium sulfate, is stood
Night.
(6) it is filtered to remove anhydrous sodium sulfate.
(7) rotary evaporation in vacuo removes petroleum ether, vacuum drying, up to fatty acid mixed.
Embodiment 2
The synthesis of C36 unrighted acid dimers：
(1) it is placed in using the fatty acid mixed of the gained of embodiment 1 as raw material in autoclave, adds 12% catalysis
Agent and 1% auxiliary agent, the quality meter based on above-mentioned fatty acid mixed, install autoclave, and examine air-tightness, wherein catalyst
For treated earth, auxiliary agent is lithium carbonate；
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen to 2.0MPa, close high
Press kettle intake valve；
(3) 240 DEG C of reaction temperature is heated under conditions of stirring, starts timing when reaching reaction temperature, as anti-
Answer zero point；
(4) after when reaction 6 is small, heating is stopped, autoclave autoclave body is placed in cold water, autoclave body is dropped to room temperature rapidly,
Kettle is driven, and pours out reaction product；
(5) crude product is diluted with isometric petroleum ether, and is added excessive hydrochloric acid and be acidified to pH=2~3；
(6) after being acidified, mixture is centrifuged, removes catalyst and solid impurity；
(7) supernatant liquor is washed with deionized water to neutrality, liquid separation, upper oil phase and is dried with anhydrous sodium sulfate, stands overnight,
It is filtered to remove anhydrous sodium sulfate；
(8) rotary evaporation in vacuo removes petroleum ether, most removes unreacted monomer acids through vacuum distillation afterwards, vacuum distillation
Condition is：Gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products, C36 unrighted acid dimers
Yield be 67.6%.
Embodiment 3
The synthesis of C36 unrighted acid dimers：
(1) it is placed in using linoleic acid as raw material in autoclave, adds 12% catalyst and 1% auxiliary agent, base
In above-mentioned linoleic quality meter, autoclave is installed, and examines air-tightness, wherein catalyst is treated earth, and auxiliary agent is carbon
Sour lithium；
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen to 2.0MPa, close high
Press kettle intake valve；
(3) 230 DEG C of reaction temperature is heated under conditions of stirring, starts timing when reaching reaction temperature, as anti-
Answer zero point；
(4) after when reaction 6 is small, heating is stopped, autoclave autoclave body is placed in cold water, autoclave body is dropped to room temperature rapidly,
Kettle is driven, and pours out reaction product；
(5) crude product is diluted with isometric petroleum ether, and is added excessive hydrochloric acid and be acidified to pH=2~3；
(6) after being acidified, mixture is centrifuged, removes catalyst and solid impurity；
(7) supernatant liquor is washed with deionized water to neutrality, liquid separation, upper oil phase and is dried with anhydrous sodium sulfate, stands overnight,
It is filtered to remove anhydrous sodium sulfate；
(8) rotary evaporation in vacuo removes petroleum ether, most removes unreacted monomer acids through vacuum distillation afterwards, vacuum distillation
Condition is：Gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products, C36 unrighted acid dimers
Yield be 88.7%.
Embodiment 4
The synthesis of C36 unrighted acid dimers：
(1) it is placed in using the fatty acid mixed of the gained of embodiment 1 as raw material in autoclave, adds 10% ion
For liquid I as catalyst, the quality meter based on above-mentioned fatty acid mixed, installs autoclave, and examine air-tightness
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen to 2.0MPa, close high
Press kettle intake valve；
(3) 230 DEG C of reaction temperature is heated under conditions of stirring, starts timing when reaching reaction temperature, as anti-
Answer zero point；
(4) after when reaction 5 is small, heating is stopped, autoclave autoclave body is placed in cold water, autoclave body is dropped to room temperature rapidly,
Kettle is driven, and pours out reaction product；
(5) crude product is diluted with isometric petroleum ether, and is added excessive hydrochloric acid and be acidified to pH=2~3；
(6) after being acidified, supernatant liquor is washed with deionized water to neutrality, liquid separation, upper oil phase and is done with anhydrous sodium sulfate
It is dry, stand overnight, be filtered to remove anhydrous sodium sulfate, the recyclable recycling of ionic liquid of lower floor；
(7) rotary evaporation in vacuo removes petroleum ether, most removes unreacted monomer acids through vacuum distillation afterwards, vacuum distillation
Condition is：Gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products, C36 unrighted acid dimers
Yield be 63.3%.
Embodiment 5
The synthesis of C36 unrighted acid dimers：
Using ionic liquid II as catalyst, other conditions are same as Example 5, refined products are prepared, C36 is not
The yield of saturated fatty acid dimer is 64.9%.
Embodiment 6
The synthesis of C36 unrighted acid dimers：
Using linoleic acid as raw material, other conditions are same as Example 5, obtain refined products, C36 unrighted acid dimerization
The yield of thing is 86.5%.
Embodiment 8
The synthesis of C36 unrighted acid dimers：
Using linoleic acid as raw material, using ionic liquid II as catalyst, other conditions are same as Example 5, are prepared into
To refined products, the yield of C36 unrighted acid dimers is 87.4%.
Embodiment 9
In the case of identical with the reaction condition of embodiment 4, ion I liquid investigated and has reused number to C36 insatiable hungers
With the influence of dimer fatty acid yield, as a result as shown in Figure 1：
After ionic liquid I it can be seen from attached drawing 1 reuses 5 times, the yield base of C36 unrighted acid dimers
This holding is stablized, and illustrates that ionic liquid has good repeat performance.This can be explained in terms of two：(1) ionic liquidAcid centre is the alkyl sulfonic acid being connected on its cation with covalent bond, and Lewis acid centres are then pair
Water andAnion [the Zn that acidic materials are stablized2Cl5]-, therefore the acid centre of ionic liquid not easily runs off；(2)
ZnCl2Introducing make the viscosity of ionic liquid and proportion all larger, be conducive to it and separated with reaction mixture, ionic liquid is existed
Loss very little in separation process.
Wear-resistant and corrosion resistant test data：Unsaturated acids, because the presence of double bond, is more easy to be formed in metal surface and adsorbs
Film, therefore abrasion resistance is better than linear saturated fatty acids.The corrosivity of aphthenic acids is bigger than dimeric dibasic acid.
The agent, which is added in No. 3 jet fuels of hydrogenation technique production, should meet following index (15~23mg/L of addition)：
1. lubricity：Wear scar diameter (WSD) is less than 0.65mm.(SH/T 0687) representative value 0.59mm
2. water separation index：MSEP≥75.(SH/T 0616) representative value 85~95
3. copper corrosion：Less than or equal to 1 grade (GB/T5096)
Claims (5)
- A kind of 1. purposes for the catalyst for preparing jet fuel antiwear additive, it is characterised in that：The catalyst is used to prepare jet combustion Expect antiwear additive, the jet fuel antiwear additive includes C36 unrighted acid dimers, the C36 unrighted acid dimers Including the compound more than 65% shown in general formula (1), the compound 25-30% shown in general formula (2), the chemical combination shown in general formula (3) Thing is less than 10%, in mass；General formula (1) is without ring structureGeneral formula (2) single ring architectureGeneral formula (3) twin nuclei；The preparation method of above-mentioned C36 unrighted acids dimer comprises the following steps：(A) preparation of fatty acid mixed：Taken off including vegetable oil is mixed progress saponification with excessive aqueous slkali and suitable ethanol Glycerine is removed, generates soap, soap is acidified to pH=2~3, and using petroleum ether extraction oil phase, oil phase is through washing, nothing After aqueous sodium persulfate drying, petroleum ether is removed using rotary evaporation, fatty acid mixed can be obtained after vacuum drying；(B) it is placed in using the fatty acid mixed obtained by linoleic acid or step (A) as raw material in autoclave, adds 9-15% Catalyst, the quality meter based on linoleic acid or above-mentioned fatty acid mixed, 230-240 DEG C of reaction temperature；The catalyst be with The ionic liquid I or ionic liquid II of following structural formula,
- 2. the purposes of the catalyst for preparing jet fuel antiwear additive described in claim 1, it is characterised in that：The ionic liquid I's synthesizes following process：
- 3. the purposes of the catalyst of jet fuel antiwear additive is prepared described in claim 1, it is characterised in that：The ionic liquid I Specifically use following preparation method：(1) trimethylamine solution is mixed with 1,3-propane sultone equimolar in conical flask, stirring reaction 24h at 60 DEG C；(2) after reaction, rotary distillation removes water, obtains white solid；(3) re-crystallizing in ethyl acetate is used, is filtered, and is washed three times；(4) 80 DEG C of vacuum drying 4h obtain the solid inner salt of white；(5) inner salt is dissolved with the water of 3 times of quality；(6) hydrochloric acid that equimolar mass concentration is 37% is added dropwise to be acidified, is added dropwise, is warming up to 80 DEG C, stirring reaction 3h；(7) rotary distillation removes water, and 80 DEG C of vacuum drying 4h, obtain light yellow viscous liquid, that is, be acidified inner salt；(8) a certain amount of acidifying inner salt is taken, is 1 with molar ratio:2 zinc chloride mixing, under nitrogen protection, is warming up to 100 DEG C, stirs Mix to solid and all dissolve；(9) 80 DEG C of vacuum drying 8h, up to thick ionic liquid I.
- 4. the purposes of the catalyst of jet fuel antiwear additive is prepared described in claim 1, it is characterised in that：The ionic liquid II Synthesize following process：
- 5. the purposes of the catalyst of jet fuel antiwear additive is prepared described in claim 1, it is characterised in that：The ionic liquid II Specific synthesis step it is as follows：(1) a certain amount of 1,3-propane sultone is dissolved in the ethyl acetate that its mass number is 5~16 times, is warming up to 40~60 DEG C, equimolar N- methylimidazoles are added dropwise, are added dropwise, 3~5h of insulation reaction；(2) after reaction, filter, obtain white filter cake, filter cake is washed three times with ethyl acetate；(3) 100 DEG C of vacuum drying 2h obtain white solid inner salt 3- (1- methylimidazole -3- alkyl)-propyl sulfonic acid salt, i.e. mim- PS；(4) a certain amount of inner salt mim-PS is taken, is dissolved in the deionized water that its mass number is 2~4 times；(5) hydrochloric acid that equimolar mass concentration is 37% is added dropwise, acidifying finishes, and is warming up to 70~90 DEG C, stirring reaction 2~ 3h；(6) rotary distillation removes water, and 80 DEG C of vacuum drying 4h, obtain light yellow viscous liquid, that is, be acidified inner salt chlorination 1- (3- sulphurs Acid)-propyl group -3- methylimidazole salts [HO3S-(CH2)3-mim]Cl；(7) a certain amount of acidifying inner salt is taken, is 1 with molar ratio:2 zinc chloride mixing, under nitrogen protection, is warming up to 90~110 DEG C, stir to solid and all dissolve；(8) 80 DEG C of vacuum drying 8h, up to thick ionic liquid II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510134538.6A CN104785297B (en) | 2015-03-25 | 2015-03-25 | A kind of catalyst for being used to prepare aviation fuel antiwear additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510134538.6A CN104785297B (en) | 2015-03-25 | 2015-03-25 | A kind of catalyst for being used to prepare aviation fuel antiwear additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104785297A CN104785297A (en) | 2015-07-22 |
| CN104785297B true CN104785297B (en) | 2018-04-27 |
Family
ID=53550751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510134538.6A Active CN104785297B (en) | 2015-03-25 | 2015-03-25 | A kind of catalyst for being used to prepare aviation fuel antiwear additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104785297B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009224097A (en) * | 2008-03-14 | 2009-10-01 | Panasonic Corp | Nonaqueous electrolyte secondary battery |
| CN101348448A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of ion liquid having B acid center and L acid center |
| CN101613273B (en) * | 2009-07-25 | 2014-04-16 | 青岛科技大学 | Method for preparing dimeric acid methyl ester |
-
2015
- 2015-03-25 CN CN201510134538.6A patent/CN104785297B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104785297A (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104804782B (en) | Method for preparing anti-wear agent for aircraft fuel | |
| CN105237371B (en) | Method for preparing vanillin through catalytic oxidation degradation of lignin | |
| Yang et al. | Synthesis of biodiesel via transesterification of tung oil catalyzed by new Brönsted acidic ionic liquid | |
| CN104789298B (en) | A kind of method for preparing aviation fuel antiwear additive | |
| CN104845685B (en) | A kind of antiwear additive of aviation fuel | |
| CN104785297B (en) | A kind of catalyst for being used to prepare aviation fuel antiwear additive | |
| CN106543998B (en) | Hydrothermal cracking catalytic viscosity reducer and preparation method thereof | |
| CN107556224A (en) | The preparation method of dialkyl dithio amino formate and wear-resistant antirust complexing agent | |
| CN101187032A (en) | P-aminoanisole electrochemical synthesis method | |
| CN101880228A (en) | Clean preparation method for butyl acetate | |
| CN102839026B (en) | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component | |
| CN102807505A (en) | Method for producing phenylhydrazine | |
| US9878967B2 (en) | Method of converting levulinic acid or a derivative thereof to hydrocarbons and hydrogen, and methods of the production of hydrocarbons and hydrogen | |
| CN101787303A (en) | Method for preparing alkane from acidized oil | |
| CN103386366B (en) | A kind of preparation method of phosphotidic beneficiation collecting agent | |
| CN105985366A (en) | Method of preparing propyl silicate | |
| EP3268342B1 (en) | Production of terephthalic acid via reductive coupling of propiolic acid or propiolic acid derivatives | |
| CN105272916B (en) | A kind of new rosin base imidazoline corrosion inhibitor | |
| CN103145562B (en) | N-ethyl aniline preparation method | |
| CN105777537B (en) | A kind of alkylation of salicylic acid method | |
| CN102746180B (en) | Preparation method for hydroxyethyl dual fatty acid amide | |
| CN102417444A (en) | Process for producing fatty acid calcium based on one-step water method | |
| CN101544564A (en) | Chemical synthetic method for para-methyl catechol diacetoxyl dimethyl ester | |
| CN104744319A (en) | Production method of heavy alkyl benzene sulfonic acid for producing oil-displacing agent | |
| CN110194751A (en) | A kind of preparation method of thiadiazoles derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |