CN1952015A - Process for preparing lemon chrome - Google Patents
Process for preparing lemon chrome Download PDFInfo
- Publication number
- CN1952015A CN1952015A CN200510030644.6A CN200510030644A CN1952015A CN 1952015 A CN1952015 A CN 1952015A CN 200510030644 A CN200510030644 A CN 200510030644A CN 1952015 A CN1952015 A CN 1952015A
- Authority
- CN
- China
- Prior art keywords
- acid
- diazonium salt
- phase
- transfer catalyst
- reaction
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a preparing method of lemon yellow through condensing, coupling and hydrolyzing, which improves switching rate and production purity with lower organic impurity content.
Description
Technical field
The present invention relates to a kind of preparation method of food dye, relate to lemon yellow preparation method particularly.
Background technology
Foodstuff additive food dye can be divided into synthetic colour and natural pigment two big classes.Advantages such as relative natural pigment, synthetic colour have that lovely luster, tone are many, stable performance, strong coloring force, fastness are big, it is easy, easy to use, with low cost to mix colours, be widely used.Add various countries through the practice of centuries, from the most for a long time more than 100 kind to eliminating into thirties kinds.Foodstuff additive food dye is widely used in fields such as food, medicine, makeup, paper, daily necessities, toy, new packaging materials, we can say, allowed its security of synthetic colour of use quite reliable by various countries now, on food color, synthetic colour uses manyly more than natural pigment.Along with the national economy fast development, the market of edible synthesized coloring matter also increases thereupon fast, from 300 tons of the early 1990s in last century till now 3000 tons.
Tatrazine, one of edible synthesized coloring matter three primary colors are allowed to be used for food color synthetic colour the most widely in the world, account for 30 percent of global synthetic colour total amount.And in 3000 tons of years of edible synthesized coloring matter of China demands, lemon yellowly account for 1200 tons, account for 4 percent top ten.
Tatrazine claims FD﹠amp again; C Yellow No.5, E102, C.I.19140, CAS number is 1934-21-0, chemical molecular formula C
16H
9N
4Na
3O
9S
2, bright orange-yellow powder or particle, azo type heterocyclic structure (seeing formula 1),
Lemon yellow route of synthesis is two kinds:
One) phenyl hydrazine-p-sulfonic acid and two hydroxyl tartrate condensations;
Two) Sulphanilic Acid diazonium salt and 1-(4-sulphenyl)-3-carboxyl-5-pyrazolone or the basic ester coupling of its first (second) (or alcohol radical is sloughed in hydrolysis again).
Our company adopts tartrate technology the earliest, i.e. first kind of technology, back independent development DMAS technology, use till today always.DMAS (2-DMAS) technology (belonging to pyrazolone technology)---be that Sulphanilic Acid diazonium salt and DMAS (2-DMAS) condensation generates the pyrazolone methyl esters, get with the coupling of Sulphanilic Acid diazonium salt, hydrolysis again.
In sum, this area lacks a kind of reaction conversion ratio height, product purity height, lemon yellow preparation method that organic impurity content is low.Therefore, this area presses for exploitation a kind of reaction conversion ratio height, product purity height, lemon yellow preparation method that organic impurity content is low.
Summary of the invention
The object of the present invention is to provide reaction conversion ratio height, product purity height, lemon yellow preparation method that organic impurity content is low.
In a first aspect of the present invention, a kind of lemon yellow preparation method is provided, step comprises:
(a) 2-acetyl-malic acid dimethyl esters and mol ratio are 1: the Sulphanilic Acid diazonium salt of 0.90-1.10 is the phase-transfer catalyst of 0.05-0.5 and is to carry out condensation in the presence of the acid binding agent of 1.5-2.5 in the amount of substance mol ratio of 2-acetyl-malic acid dimethyl esters in the amount of substance mol ratio in 2-acetyl-malic acid dimethyl esters, obtain condenses, described phase-transfer catalyst comprises polyoxyethylene glycol, class of department, tween, peregal 0 or its combination;
(b) described condenses be coupling of Sulphanilic Acid diazonium salt and the hydrolysis of 0.90-1.10 in the amount of substance mol ratio of condenses, obtain lemon yellow.
In the preference of the present invention, phase-transfer catalyst is a poly(oxyethylene glycol) 400 described in the step (a).
In the preference of the present invention, acid binding agent is selected from Sodium phosphate dibasic, sodium bicarbonate described in the step (a).Preferably, described acid binding agent is a Sodium phosphate dibasic.
In the preference of the present invention, Sulphanilic Acid diazonium salt described in the step (a) carries out diazotization reaction by Sulphanilic Acid and makes, and described phase-transfer catalyst adds in diazotization reaction.
In the preference of the present invention, the Sulphanilic Acid diazonium salt of step (b) is regulated the pH value with the pH regulator agent before reaction be 1.0-2.0.Preferably, described pH regulator agent is a Sodium phosphate dibasic.
In the preference of the present invention, it is characterized in that also comprise separating step in the step (b), described separating step comprises roughing out and purification step, wherein said roughing out step adopts recrystallization method, and described purification step adopts membrane separation process.Preferably, adopting molecular weight cut-off in the described membrane separation process is 350 tubular type nanofiltration membrane.
Description of drawings
Fig. 1 is a lemon yellow preparation method's of the present invention process flow sheet, and DMAS is the 2-DMAS, and inferior sodium is Sodium Nitrite, is Sulphanilic Acid to acid.
Embodiment
The inventor by technological improvement production technique such as integrated use liquid-phase chromatographic analysis, phase-transfer catalysis, membrane sepn, meticulous reaction controls, forms the new production method of high purity Tatrazine through extensive and deep research.This production method comprise DMAS (2-acetyl-malic acid dimethyl esters) under the effect of phase-transfer catalyst and gentle acid binding agent with mole number such as approximately to sour diazonium salt condensation; then with second part approximately wait mole number to sour diazonium salt in the coupling of pH6.5-8.0 scope; again in PH9.0-9.5,75-85 ℃ hydrolysis, after recrystallization, membrane sepn purification step and high purity is lemon yellow.The contriver is surprised to find that, adopts method of the present invention, improves simultaneously except making lemon yellow product purity and reaction yield, can also significantly reduce the content of organic impuritys such as unreacted intermediate and secondary dyestuff, reduces pollutent simultaneously and produces and discharging.Finished the present invention on this basis.
Reaction process
Sulphanilic Acid (hereinafter referred to as to acid) diazotization reaction obtains the Sulphanilic Acid diazonium salt.
Then, 2-acetyl-malic acid dimethyl esters and mol ratio are 1: the Sulphanilic Acid diazonium salt of 0.90-1.10 is the phase-transfer catalyst of 0.05-0.5 and is to carry out condensation in the presence of the acid binding agent of 1.5-2.5 in the amount of substance mol ratio of 2-acetyl-malic acid dimethyl esters in the amount of substance mol ratio in 2-acetyl-malic acid dimethyl esters, obtain condenses, described phase-transfer catalyst comprises polyoxyethylene glycol, class of department, tween, paregal O or its combination;
Then, described condenses be coupling of Sulphanilic Acid diazonium salt and the hydrolysis of 0.90-1.10 in the amount of substance mol ratio of condenses, obtain lemon yellow.
The reaction conditions of coupling is a popular response condition well known to those skilled in the art, for example in the coupling of pH6.5-8.0 scope.
The reaction conditions of hydrolysis is a popular response condition well known to those skilled in the art, for example PH9.0-9.5, temperature 75-85 ℃ of following hydrolysis,
The equation of reaction is as follows:
1, chemical equation
1), diazotization
2), condensation
3), coupling
4), hydrolysis
2, process flow sheet
Fig. 1 is a lemon yellow preparation method's of the present invention process flow sheet, and DMAS is the 2-DMAS, and inferior sodium is Sodium Nitrite, is Sulphanilic Acid to acid.
As shown in Figure 1, realize that lemon yellow preparation method of the present invention comprises diazotization reaction, condensation reaction, coupled reaction, hydrolysis reaction and post-processing step, wherein each post-processing step comprises crystallisation step, membrane sepn step and drying step.
Phase-transfer catalyst
Phase-transfer catalyst is selected from ethanol, Si Ban-tween series, polyoxyethylene glycol series, paregal O auxiliary agents such as (as the paregal Os of being produced by the auxiliary reagent factory, Shanghai) or emulsifying agent, dispersion agent, preferred polyethylene glycols phase-transfer catalyst, more preferably poly(oxyethylene glycol) 400.Consumption is 0.1～2.0% of a whole reaction system weight.
DMAS (2-DMAS) is water insoluble, and minimum to sour diazonium salt solubleness in water, be suspension, so both condensation reactions are inhomogeneous reaction.Be to improve the molecular impact effect, thereby improve the effect that two-phase interface tension force is realized phase-transfer catalysis, tested auxiliary agent such as ethanol, Si Ban-tween series, polyoxyethylene glycol series, paregal O or emulsifying agent, dispersion agent the unitary reaction effect of condensation.Selected for use after the comprehensive evaluation to belong to foodstuff additive and have the poly(oxyethylene glycol) 400 of good result to make phase-transfer catalyst, the product that obtains is safer.
Phase-transfer catalyst adds in the time of can be in diazotization reaction or in condensation reaction, preferably adds when diazotization reaction, for example is to add when ending at feed intake initial stage or feed intake of reactant, also can add in the mid-term that feeds intake.For example when adding, add sour diazonium.To help when phase-transfer catalyst is added to doazo reaction in advance the diazonium salt particles that generates thinner, avoid acid is wrapped into wherein simultaneously, make the diazonium unit process complete.
Acid binding agent
When condensation reaction, need add acid binding agent to advance reaction.The acid binding agent that acid binding agent can adopt this area routine techniques to use is as soda ash, sodium bicarbonate, Sodium phosphate dibasic, sodium phosphate or its combination.It is strong and weak and different that consumption is looked its alkalescence.
Preferred sodium bicarbonate of method of the present invention or Sodium phosphate dibasic are as acid binding agent, and more preferably Sodium phosphate dibasic is as acid binding agent.Common acid binding agent soda ash alkalescence is slightly strong, follows the tracks of through liquid phase, finds that adding speed promptly can produce slightly soon to acid self conjugates, makes that impurity increases in the reaction.The contriver has selected for use sodium bicarbonate, Sodium phosphate dibasic to do the acid binding agent test, finds that impurity reduces in the reaction, and product purity improves, and has obtained good experimental result.
Consider that the concentration of saturated saleratus solution has only 8%, so the preferably phosphoric acid disodium hydrogen is as acid binding agent, with control reaction system volume.
The amount of the acid binding agent that adds is 1.5-2.5 in the amount of substance mol ratio of 2-acetyl-malic acid dimethyl esters, and preferred molar ratio is 1.8-2.2.
The control in advance of pH value in the coupling
Before carrying out coupling, diazonium salt pH can be adjusted to 0.8～3.0, preferably be adjusted into the mode of pH1.0～2.0, conditioning agent can be selected the common acidic ph modifier in this area for use, for example soda ash, sodium bicarbonate, Sodium phosphate dibasic or its combination, the preferably phosphoric acid disodium hydrogen.
PH is weakly alkaline top condition during for the coupling of maintenance hydroxyl ortho position, the PH of diazonium salt need adjust, the diazonium salt immediate reaction that the reaction final stage is added, do not generate sodium self conjugates, for this reason, the contriver is adjusted into diazonium salt in advance with Sodium phosphate dibasic the mode of pH1.0～2.0 coupling pH value has been carried out meticulous control before coupled reaction, pH forms comparatively ideal buffering range 6.5～8.0 when making coupling under the prerequisite of not destroying diazonium salt, finishes coupling smoothly.The result is quite desirable, shows that after tested the diazonium salt that adds in the final stage is immediate reaction.
Separate
Lemon yellowly adopt general post-treating method to separate, as recrystallization method etc.
Separation method can disposablely separate, and also can comprise roughing out and purification step, preferably carries out roughing out, the separation method of re-refining earlier.
The roughing out method can be selected salting-out process and recrystallization method for use, preferred recrystallization method.
Method for refining can be selected normal temperature salting-out process, hypothermic saline washing method and membrane separation process etc. or its combination for use.The preferred film partition method.
Membrane separation process comprises nanofiltration, ultrafiltration, reverse osmosis etc., can use the tubular type nanofiltration membrane of molecular weight cut-off 350-400 in the industrial production.Preferred molecular weight cut-off is 350 tubular type nanofiltration membrane, and for example molecular weight cut-off is 350 AFC 30 tubular type nanofiltration membrane (Xiamen three reaches company and produces).
Adopt membrane sepn to replace original refining step---low-temperature and low-concentration salt solution making beating press filtration, through the selection of film type, molecular weight cut-off, effectively remove most of small organic molecule and the salt in the reaction system, thereby reached the purpose of refining purification.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Embodiment
In the 500mL four-necked bottle, add 60 ℃ of hot water 180mL, add 20g poly(oxyethylene glycol) 400 (PEG-400), stir adding Sulphanilic Acid 34.6g (0.20mol) down fast, stirred ten minutes, be chilled to room temperature, add technical hydrochloric acid 32mL (31%).Continue to be chilled to 0-5 ℃, liquid drips down 30% sodium nitrite solution 47g (0.20mol), and holding temperature 5-10 ℃, about 20min finishes, and congo-red test paper blueness, potassium iodide starch test paper are light blue.Continue to stir 20min after finishing, add the excessive nitrous acid of little ammonia sulfonic acid cancellation.
In the above-mentioned diazonium liquid, thread adds DMAS (2-DMAS) 37.64g (0.20mol) behind the stirring 5min, and controlled temperature 10-15 ℃, slowly drip the 15wt% disodium phosphate soln and transfer pH to 5.0, system changes into transparent burgundy.After treating that diazonium salt disappears, restir half an hour, make condensated liquid.
The a diazonium salt of refabrication separately.Add 15% disodium phosphate soln behind the excessive nitrous acid of cancellation and transfer pH1.0-2.0.
Aforementioned condensated liquid goes in the 1000mL four-necked bottle, adds the 20wt% soda ash aqueous solution and transfers PH8.0-9.0.Stir second part of diazonium salt of thread adding down, temperature 15-20 ℃, about 20min adds, pH6.5-8.0.Add the back restir and make coupling solution half an hour.
Be sprinkled into soda ash in the coupling solution and transfer pH9.0-9.5, be warming up to 80-90 ℃, be incubated one hour.Spacer is cooled to 55 ℃, adds the about 20mL of hydrochloric acid and transfers PH6.5-7.5.Suction filtration, 10% amount by volume adds refined salt, is stirred to dissolving, continues slowly to be cooled to 5-10 ℃.Suction filtration.Filter cake is dissolved in the 2000mL water, advancing lab membrane tripping device (0.3Mpa, 45-50 ℃) desalination does not descend and material liquid volume 300mL ends to the feed liquid specific conductivity is constant, concentrated solution in baking oven 80 ℃ dry finished product 108.4g, content 90.1%, liquid phase purity 99.48% (238nm), yield 91.4%.
Replace 20g poly(oxyethylene glycol) 400 (PEG-400) with 15g cetomacrogol 1000 (PEG-1000), all the other are with embodiment 1.Get finished product 105.6g, content 90.5%, liquid phase purity 99.25% (238nm), yield 91.1%.
Replace 15% disodium phosphate soln with saturated saleratus solution, all the other are with embodiment 1.Get finished product 106.8g, content 90.3%, liquid phase purity 99.35% (238nm), yield 90.2%.
Replace 20g poly(oxyethylene glycol) 400 (PEG-400) with 20g 5% polysorbate60-Si Ban 60 (20: 1) aqueous solution, all the other are with embodiment 1.Get finished product 105.6g, content 89.6%, liquid phase purity 99.06% (238nm), yield 88.5%.
Replace 20g poly(oxyethylene glycol) 400 (PEG-400) with 20g 5% tween 80-Si Ban 80 (20: 1) aqueous solution, all the other are with embodiment 1.Get finished product 107.6g, content 90.3%, liquid phase purity 99.38% (238nm), yield 90.9%.
Technique effect
It is lemon yellow to adopt method of the present invention to prepare, overcome the defective that is easy to generate sodium self conjugates, make that respectively to go on foot unit process complete substantially, reduced the content of organic impuritys such as unreacted intermediate and secondary dyestuff, yield is obviously improved, reach 91.4%, (HPLC 238nm) reaches 99.5% to purity simultaneously.Quality index reaches U.S. FCC standard comprehensively.Thereby the lemon yellow product that method of the present invention makes is as foodstuff additive, and its detrimental impurity content is few, therefore has higher food safety.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (9)
1. lemon yellow preparation method is characterized in that step comprises:
(a) 2-acetyl-malic acid dimethyl esters and mol ratio are 1: the Sulphanilic Acid diazonium salt of 0.90-1.10 is the phase-transfer catalyst of 0.05-0.5 and is to carry out condensation in the presence of the acid binding agent of 1.5-2.5 in the amount of substance mol ratio of 2-acetyl-malic acid dimethyl esters in the amount of substance mol ratio in 2-acetyl-malic acid dimethyl esters, obtain condenses, described phase-transfer catalyst comprises polyoxyethylene glycol, class of department, tween, peregal 0 or its combination;
(b) described condenses be coupling of Sulphanilic Acid diazonium salt and the hydrolysis of 0.90-1.10 in the amount of substance mol ratio of condenses, obtain lemon yellow.
2. the method for claim 1 is characterized in that, phase-transfer catalyst is a poly(oxyethylene glycol) 400 described in the step (a).
3. the method for claim 1 is characterized in that, acid binding agent is selected from Sodium phosphate dibasic, sodium bicarbonate described in the step (a).
4. the method for claim 1 is characterized in that, acid binding agent is a Sodium phosphate dibasic described in the step (a).
5. the method for claim 1 is characterized in that, Sulphanilic Acid diazonium salt described in the step (a) carries out diazotization reaction by Sulphanilic Acid and makes, and described phase-transfer catalyst adds in diazotization reaction.
6. the method for claim 1 is characterized in that, the Sulphanilic Acid diazonium salt of step (b) is regulated the pH value with the pH regulator agent before reaction be 1.0-2.0.
7. method as claimed in claim 6 is characterized in that, described pH regulator agent is a Sodium phosphate dibasic.
8. the method for claim 1 is characterized in that, also comprises separating step in the step (b), and described separating step comprises roughing out and purification step, and wherein said roughing out step adopts recrystallization method, and described purification step adopts membrane separation process.
9. method as claimed in claim 8 is characterized in that, the employing molecular weight cut-off is 350 tubular type nanofiltration membrane in the described membrane separation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100306446A CN100429280C (en) | 2005-10-19 | 2005-10-19 | Process for preparing lemon chrome |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100306446A CN100429280C (en) | 2005-10-19 | 2005-10-19 | Process for preparing lemon chrome |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1952015A true CN1952015A (en) | 2007-04-25 |
| CN100429280C CN100429280C (en) | 2008-10-29 |
Family
ID=38058578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100306446A Expired - Fee Related CN100429280C (en) | 2005-10-19 | 2005-10-19 | Process for preparing lemon chrome |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100429280C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333339B (en) * | 2007-06-26 | 2010-12-08 | 上海染料研究所有限公司 | Preparation method for enhancing yield of edible sunset yellow |
| CN102311345A (en) * | 2010-09-09 | 2012-01-11 | 河北华戈化学集团有限公司 | Continuous synthesis method of dimethyl acetylsuccinate |
| CN103483261A (en) * | 2013-09-10 | 2014-01-01 | 中国乐凯集团有限公司 | Preparation method of 1-substitued phenyl-3-carboxymethyl-5-pyrazolone |
| WO2015188401A1 (en) * | 2014-06-10 | 2015-12-17 | 苏州大学张家港工业技术研究院 | Solvent medium for diazotization reaction |
| CN105199423A (en) * | 2015-08-25 | 2015-12-30 | 上海化工研究院 | Synthesizing method for prohibited pigment labeled by stable isotope |
| CN106831588A (en) * | 2017-01-19 | 2017-06-13 | 南通海之阳膜化工有限公司 | A kind of synthetic method of food additives lemon yellow |
| CN106928146A (en) * | 2015-12-29 | 2017-07-07 | 湖北神舟化工有限公司 | A kind of purification process of lemon yellow |
| CN109971203A (en) * | 2019-04-24 | 2019-07-05 | 沈阳感光化工研究院有限公司 | A kind of preparation method of pigment lemon yellow |
| CN112111171A (en) * | 2020-09-21 | 2020-12-22 | 恒升化工有限公司 | C.I. acid yellow 23 dye and clean production process thereof |
| CN114262281A (en) * | 2021-12-20 | 2022-04-01 | 郑州大学 | Method for separating pyrazoline isomer mixture by using polar solvent-resistant nanofiltration membrane |
| CN114588866A (en) * | 2022-05-09 | 2022-06-07 | 山东彩客新材料有限公司 | Diazotization reaction device for lemon yellow production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1615230A1 (en) * | 1988-12-05 | 1990-12-23 | Буйский Химический Завод | Solution for passivating zinc-coated steel |
-
2005
- 2005-10-19 CN CNB2005100306446A patent/CN100429280C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333339B (en) * | 2007-06-26 | 2010-12-08 | 上海染料研究所有限公司 | Preparation method for enhancing yield of edible sunset yellow |
| CN102311345A (en) * | 2010-09-09 | 2012-01-11 | 河北华戈化学集团有限公司 | Continuous synthesis method of dimethyl acetylsuccinate |
| CN103483261A (en) * | 2013-09-10 | 2014-01-01 | 中国乐凯集团有限公司 | Preparation method of 1-substitued phenyl-3-carboxymethyl-5-pyrazolone |
| WO2015188401A1 (en) * | 2014-06-10 | 2015-12-17 | 苏州大学张家港工业技术研究院 | Solvent medium for diazotization reaction |
| US9926263B2 (en) | 2014-06-10 | 2018-03-27 | Nantong Textile & Silk Industrial Technology Research Institute | Solvent medium for diazotization reaction |
| CN105199423A (en) * | 2015-08-25 | 2015-12-30 | 上海化工研究院 | Synthesizing method for prohibited pigment labeled by stable isotope |
| CN106928146A (en) * | 2015-12-29 | 2017-07-07 | 湖北神舟化工有限公司 | A kind of purification process of lemon yellow |
| CN106831588A (en) * | 2017-01-19 | 2017-06-13 | 南通海之阳膜化工有限公司 | A kind of synthetic method of food additives lemon yellow |
| CN109971203A (en) * | 2019-04-24 | 2019-07-05 | 沈阳感光化工研究院有限公司 | A kind of preparation method of pigment lemon yellow |
| CN112111171A (en) * | 2020-09-21 | 2020-12-22 | 恒升化工有限公司 | C.I. acid yellow 23 dye and clean production process thereof |
| CN112111171B (en) * | 2020-09-21 | 2022-04-08 | 恒升化工有限公司 | C.I. acid yellow 23 dye and clean production process thereof |
| CN114262281A (en) * | 2021-12-20 | 2022-04-01 | 郑州大学 | Method for separating pyrazoline isomer mixture by using polar solvent-resistant nanofiltration membrane |
| CN114262281B (en) * | 2021-12-20 | 2023-05-23 | 郑州大学 | Separation method of pyrazoline isomer mixture by using polar solvent-resistant nanofiltration membrane |
| CN114588866A (en) * | 2022-05-09 | 2022-06-07 | 山东彩客新材料有限公司 | Diazotization reaction device for lemon yellow production |
| CN114588866B (en) * | 2022-05-09 | 2022-07-15 | 山东彩客新材料有限公司 | Lemon yellow production is with diazotization reaction unit |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100429280C (en) | 2008-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100429280C (en) | Process for preparing lemon chrome | |
| CN101535271B (en) | Process for producing 5-aminopyrazole derivative, and azo dye | |
| JPS5945013B2 (en) | Disazo compound | |
| CN100491480C (en) | Colored image-forming composition containing phthalocyanine compound, inks, inkjet inks, inkjet recording method and method of improving tolerance to decolorization due to ozone gas | |
| CN102391663B (en) | Preparation method of C.I. pigment yellow 151 | |
| CN101429344B (en) | Process for producing hexa-sulphonic acid liquid fluorescent whitening agents | |
| JP2559758B2 (en) | Pigment additive composition and disazo pigment composition | |
| CN100595236C (en) | Preparation process of direct-blending navy D-R dye | |
| TW200934830A (en) | Watersoluble naphthalocyanine pigment and aqueous ink containing same | |
| CN101333339B (en) | Preparation method for enhancing yield of edible sunset yellow | |
| JPS5910392B2 (en) | Pigment composition and its manufacturing method | |
| TW527403B (en) | Method of producing disazo pigment | |
| JP4816219B2 (en) | Method for producing disazo pigment composition | |
| JPH0645762B2 (en) | Pigment preparation | |
| CN103351645A (en) | Reactive blue dye and preparation method thereof | |
| JPS63178169A (en) | Disazo pigment composition | |
| CN102558906A (en) | Yellow disazo mixed pigment with high tinting strength | |
| CN104559320A (en) | Composite active brilliant orange dye composition | |
| CN105038312B (en) | A kind of red reactive dyes compound and its preparation and application | |
| JP2010095562A (en) | Colorant compound and ink comprising the colorant compound | |
| CN103160135A (en) | Strong green light yellow disazo organic pigment | |
| CN117024990B (en) | Application of polyether amine-crown ether compound in azo pigment modification | |
| CN100387656C (en) | Preparation process of direct blending purple dye | |
| US499216A (en) | Fabriken | |
| CN102337044A (en) | Reactive dye and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081029 Termination date: 20211019 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |