CN101823003A - Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same - Google Patents
Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same Download PDFInfo
- Publication number
- CN101823003A CN101823003A CN201010173366A CN201010173366A CN101823003A CN 101823003 A CN101823003 A CN 101823003A CN 201010173366 A CN201010173366 A CN 201010173366A CN 201010173366 A CN201010173366 A CN 201010173366A CN 101823003 A CN101823003 A CN 101823003A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- complex
- hydrotalcite
- dns
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst and a method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using the same, belongs to the technical field of chemical engineering, and relates to dye and a method for preparing a fluorescent whitening agent intermediate thereof. The method is characterized in that: a metal phthalocyanine complex or metal porphyrin complex-loading hydrotalcite catalyst is added into 4-nitrotoluene-2-sulfonic acid serving as a raw material to substitute for the conventional manganese sulfate and ferrous sulfate catalyst, and an oxidative condensation reaction is performed in an alkaline aqueous solution by using air or oxygen as oxidant so as to prepare the 4,4'-dinitrostilbene-2,2'-disulfonic acid (DNS). The catalyst has the advantages that the metal phthalocyanine complex or metal porphyrin complex-loading hydrotalcite catalyst not only has more catalytic activity centers as the homogeneous catalyst, but also can be reclaimed and recycled as a non-homogeneous catalyst; and when the catalyst is used for preparing DNS, the yield is higher than the conventional industrial production process, and wastewater containing transitional metal salt is not generated.
Description
Technical field
The invention belongs to technical field of chemical engineering, relate to the preparation method of dyestuff and fluorescent brightener intermediate thereof, specially refer to a kind of catalyst and be used to prepare 4,4 '-dinitro talan-2, the method for 2 '-disulfonic acid and salt thereof (DNS).
Background technology
DNS is a raw material of producing DSD acid (4,4 '-diaminobenzil-2,2 '-disulfonic acid), and DSD acid is a kind of important intermediate, is widely used in fluorescent whitening agent and direct dyes industry.The fluorescent whitening agent of making based on DSD acid has kind more than 100, and kind surplus the direct dyes 70 is so DSD acid market demand amount is very big.
Synthesizing of DSD acid mainly comprised for three steps: para-nitrotoluene generates 4-p-nitrotoluene-o-sulfonic acid 4-(NTS) through sulfonating reaction, and NTS is oxidized to DNS then, at last DNS is reduced to DSD acid.In this three-step reaction, it is a very crucial step of preparation DSD acid that NTS is oxidized to DNS.
The manufacture method of DNS is raw material with NTS normally, carries out oxidative condensation and gets, and used oxidant can be oxygen, air, clorox or chlorine etc.This oxidizing process was made up of two steps: at first bimolecular NTS oxidizedly is condensed into 4 in alkaline medium, 4 '-dinitro diphenylethane-2, and 2 '-disulfonic acid (DND), DND further is oxidized to DNS then.
The production technology of industrial preparation DNS routine is: in the strong alkaline water medium, be raw material with NTS, the explained hereafter DNS with the air oxidation condensation can add transition metal salt and make catalyst, as manganese sulfate or ferrous sulfate.The shortcoming that this method exists is that side reaction is many, product yield is low, yield about 70%, and generate the waste water of a large amount of transition-containing metal ions, be difficult to satisfy currently save energy and reduce the cost, the requirement of cleaner production.
In recent years, people explore the improvement to the DNS synthetic method in many aspects.As in DE3409171, replace NaOH as alkaline agent with lithium hydroxide, the DNS yield can bring up to 86.5%, but because lithium hydroxide is relatively more expensive, in the industrial advantage that do not have.In CS216132, change oxidant into clorox or chlorine, though can make the DNS yield bring up to 85%, clorox and chlorine accumulating inconvenience, and have the chlorine pollution problem, industrial poor operability.Also the someone advises that solvent uses aprotic polar solvent instead, as DMF or DMSO, this method can be brought up to reaction yield (US4952725) more than 95% significantly, but need waterless operation when being to use aprotic polar solvent, the existence of water can reduce yield greatly, and solvent need reclaim and re-use, therefore, do not have advantage from the economic interests angle, realize difficulty of industrial production.Document (Dyes and Pigments is also arranged, 44 (2000) 155-159) report, use metal phthalocyanine to be imitative enzyme catalyst, oxidation NTS prepares DNS, but because the water insoluble and organic solvent of metal phthalocyanine that uses, metal phthalocyanine exists with the form of solid particle, thereby the catalytic active center negligible amounts, has influenced activity of such catalysts.
Summary of the invention
The catalyst that the object of the invention provides the method for a kind of DNS of preparation and is used to prepare DNS, it is characterized in that: be raw material with NTS, with the metal phthalocyanine or the metal porphyrin complex that load on the hydrotalcite is catalyst, with the air or oxygen is oxidant, in alkaline aqueous solution, carry out oxidative dimerization; Being used to prepare the catalyst of DNS, is a kind of supported homogeneous catalyst, is to use hydrotalcite supported metal phthalocyanine or metalloporphyrin class complex compound as catalyst specifically.
The present invention is achieved by the following technical solutions:
A kind of catalyst and be used to prepare the method for DNS, this catalyst is the hydrotalcite of metal phthalocyanine complex or metal porphyrin complex load, the method for preparing DNS is to be raw material with NTS, with the metal phthalocyanine complex or the metal porphyrin complex that load on the hydrotalcite is catalyst, with the air or oxygen is oxidant, the oxidative dimerization that carries out in alkaline aqueous solution.Reaction temperature is at 30～80 ℃, preferred 40～65 ℃.After reaction was finished, reactant liquor obtained the DNS solid through acid neutralization, the crystallization of saltouing, filtration, and the DNS solid that obtains is dissolved in the water again, filters out catalyst, obtains DNS solution.DNS solution can be used as product and is directly used in next step reduction reaction, also can obtain the pure product of DNS through the secondary crystallization of saltouing.The catalyst that filters out can be reused in the operation of back batch.
The quantity of above-mentioned reaction catalyst system therefor is: for the NTS of every kilogram of free acid type, spendable catalytic amount is 0.005～0.2 kilogram, preferred 0.01～0.06 kilogram; The used alkaline aqueous solution of above-mentioned reaction is that alkaline agent adds and forms in the entry with the alkali metal hydroxide, and preferred alkaline agent is a NaOH.The consumption of this alkaline agent depends on that NTS is the free acid or the pattern of salt.When the NTS that uses is free acid, in need coming more than the alkaline agent of 1 equivalent and sulfonate radical.The preferred amounts of this alkaline agent is that every mole of free acid NTS needs 1～6 mole of alkaline agent, more preferably 1.2～4 moles of alkaline agents.
Catalyst used in the present invention is the metal phthalocyanine class complex compound or the metalloporphyrin class complex compound of hydrotalcite load, and the hydrotalcite that constitutes this catalyst can be magnesium/aluminum hydrotalcite, also can be the hydrotalcite that contains other metal.Constitute the metal phthalocyanine class complex compound or the metalloporphyrin class complex compound of this catalyst, can be to contain various substituent metal phthalocyanines and metal porphyrin complex, to contain water-soluble substituent metal phthalocyanine and metal porphyrin complex is the best, comprises containing water-soluble substituent textile dyestuff C.I. directly indigo plant 199 and C.I. direct blue 86.Metal ion in metal phthalocyanine and the metal porphyrin complex can be Co, Cr, Fe, Ni, Cu, Nb, Ta, Ru, Mn or V, is the best with copper, manganese, iron, cobalt.
Catalyst used in the present invention can adopt immersion process for preparing, is about to hydrotalcite and is immersed in the solution of metal phthalocyanine class complex compound or metalloporphyrin class complex compound, obtains hydrotalcite supported metal phthalocyanine class complex compound or metalloporphyrin class complex compound catalyst.
Catalyst used in the present invention also can adopt the method preparation of magnesium/aluminum composite metal oxide structural remodeling, promptly earlier metal phthalocyanine complex or metal porphyrin complex are loaded to magnesium/aluminum composite metal oxide surface, the method by structural remodeling obtains hydrotalcite supported metal phthalocyanine complex compound or metal porphyrin complex catalyst again.When adopting the method, load can there be the magnesium/aluminum composite metal oxide of metal phthalocyanine complex or metal porphyrin complex to be directly used in the oxidation reaction of NTS, in 15 minutes of initial reaction stage, load has the magnesium/aluminum composite metal oxide of metal phthalocyanine complex or metal porphyrin complex to gradate structure into hydrotalcite, participates in the catalytic oxidation of NTS then.
Catalyst used in the present invention also can promptly when the preparation hydrotalcite, directly add metal phthalocyanine complex or metal porphyrin complex with directly synthetic method, prepares the hydrotalcite catalyst that load has metal phthalocyanine or metal porphyrin complex.
Effect of the present invention and benefit are: use hydrotalcite supported metal phthalocyanine or metal porphyrin complex to make catalyst, can have more catalytic active center as homogeneous catalyst, can reclaim repeated use as heterogeneous catalysis again.Hydrotalcite has certain alkalescence, can the instead of part alkaline agent.Carry out the oxidation reaction of NTS with hydrotalcite supported metal phthalocyanine complex compound or metal porphyrin complex catalyst, yield is higher than existing industrial manufacture process, and can not produce the sewage that contains transition metal ions, is a kind of eco-friendly production technology.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment one:
Mg (NO with 0.108 mole
3)
26H
2Al (the NO of O and 0.036 mole
3)
39H
2O is dissolved in the 120ml water, is mixed with salting liquid; Again with 0.288 mole NaOH and 0.018 mole Na
2CO
3Be dissolved in the 120ml water, be mixed with aqueous slkali.Under vigorous stirring, above-mentioned salting liquid and aqueous slkali are added drop-wise in the there-necked flask simultaneously, keeping the pH of solution in the there-necked flask is 10, after being added dropwise to complete, with the slurries that obtain in 65 ℃ of crystallization 24h.Filter then, filter cake is washed to neutrality, in 80 ℃ of vacuum drying 8h, obtains the Mg/Al hydrotalcite.The Mg/Al hydrotalcite that obtains is calcined 8h down at 500 ℃, obtain magnesium/aluminum composite metal oxide.Get C.I. that magnesium/aluminum composite metal oxide 5g is immersed in 100mg directly in blue 199 the methanol solution, dipping is 24 hours under the room temperature, filtration then, methanol wash, drying, and obtaining load has direct magnesium/aluminum composite metal oxide of blue 199.
Embodiment two:
The free acid NTS of 4.48g (0.15mol) is dissolved in the deionized water of 30ml, again with the 2g dissolution of sodium hydroxide in the deionized water of 10ml, sodium hydroxide solution slowly is added drop-wise in the aqueous solution of NTS, adds direct blue 199 the Al-Mg composite metal oxide of load C .I. of 100mg embodiment one preparation then.Continuous aerating oxygen, and temperature slowly risen to 67 ℃, at 67 ℃ of insulation 9h.After reaction finishes, with the reactant liquor cooling, be neutralized to neutrality with hydrochloric acid, add sodium chloride and saltout, crystallization goes out crystal DNS, filters to obtain the DNS solid.The DNS solid is dissolved in the water, filters out catalyst, obtain the aqueous solution of DNS.DNS yield 83.1%.
Embodiment three:
Operating process is identical with example two with the raw material consumption.Different is, catalyst is the catalyst of filtered and recycled in the example two, and the yield of the DNS that obtains is 80%.
Embodiment four:
Operating process is identical with example two with the raw material consumption.Different is, catalyst consumption is 50mg, and the DNS yield that obtains is 78%.
Embodiment five:
Operating process is identical with example two with the raw material consumption.Different is that oxidant is an air, DNS yield 70%.
Embodiment six:
Operating process is identical with example two with the raw material consumption.Different is, the catalyst of adding is the magnesium/aluminum hydrotalcite of tetrasulfonic acid base cobalt phthalocyanine load, and catalyst amount is 50mg, DNS yield 84%.
Embodiment seven:
Operating process is identical with example two with the raw material consumption.Different is, the catalyst of adding is the directly magnesium/aluminum hydrotalcite of blue 86 loads of C.I., and catalyst amount is 50mg, DNS yield 80%.
Embodiment eight:
Operating process is identical with example two with the raw material consumption.Different is, the catalyst of adding is the Al-Mg composite metal oxide of tetrasulfonic acid base iron-phthalocyanine load, and catalyst amount is 100mg, DNS yield 85%.
Claims (7)
1. catalyst, this catalyst is used to prepare 4,4 '-dinitro talan-2,2 '-disulfonic acid and salt thereof (DNS), it is characterized in that: this catalyst is the metal phthalocyanine class complex compound or the metalloporphyrin class complex compound of hydrotalcite load, and the hydrotalcite that constitutes this catalyst is magnesium/aluminum hydrotalcite or the hydrotalcite that contains other metal; Constitute the metal phthalocyanine class complex compound and the metalloporphyrin class complex compound of this catalyst, include the metal phthalocyanine complex and the metal porphyrin complex of different substituents, comprise and contain water-soluble substituent textile dyestuff C.I. directly indigo plant 199 and C.I. direct blue 86; Metal ion in metal phthalocyanine and the metal porphyrin complex is Co, Cr, Fe, Ni, Cu, Nb, Ta, Ru, Mn or V.
2. the method for preparing the described catalyst of claim 1, it is characterized in that adopting infusion process, be about to hydrotalcite and be immersed in the solution of metal phthalocyanine complex or metal porphyrin complex, obtain hydrotalcite supported metal phthalocyanine complex compound and hydrotalcite carried metal porphyrin complex catalyst respectively.
3. the method for preparing the described catalyst of claim 1, it is characterized in that adopting the structural remodeling method, promptly earlier with the method for flooding, metal phthalocyanine complex or metal porphyrin complex are loaded on the surface of magnesium/aluminum composite metal oxide, by the method for structural remodeling, there is the magnesium/aluminum composite metal oxide of metal phthalocyanine complex or metal porphyrin complex to be converted into the structure of hydrotalcite load again; When adopting the method to prepare catalyst, load has the magnesium/aluminum composite metal oxide of metal phthalocyanine complex or metal porphyrin complex, do not need to carry out structural remodeling in advance, directly join in the oxidation liquid of 4-nitrotoleune-2 sulfonic acid (NTS), in 15 minutes of reaction beginning, load has the magnesium/aluminum composite metal oxide of metal phthalocyanine complex or metal porphyrin complex to gradate structure into hydrotalcite, participates in the catalytic oxidation of NTS then.
4. the method for preparing the described catalyst of claim 1, it is characterized in that adopting direct synthesis technique, promptly when the preparation hydrotalcite, directly add metal phthalocyanine complex or metal porphyrin complex, prepare the hydrotalcite catalyst that hydrotalcite catalyst that load has metal phthalocyanine complex or load have metal porphyrin complex.
5. the described catalyst of claim 1 is used to prepare 4,4 '-dinitro talan-2, the method of 2 '-disulfonic acid and sodium salt thereof and sylvite, it is characterized in that, this method is to be raw material with NTS, is catalyst with metal phthalocyanine or the metalloporphyrin class complex compound that loads on the hydrotalcite, is oxidant with the air or oxygen, the oxidative dimerization that in alkaline aqueous solution, carries out, reaction temperature is at 30～80 ℃; After reaction was finished, reactant liquor obtained the solid of DNS through acid neutralization, the crystallization of saltouing, filtration, and the solid of the DNS that obtains is dissolved in the water again, filtered out catalyst, obtained DNS solution; The DNS solution that obtains is directly used in reduction reaction as the raw material of next step reduction reaction, or saltouts and the method for crystallization obtains the pure product of DNS by secondary.
6. according to the preparation method of claim 5, it is characterized in that described catalyst consumption is: for every kilogram of NTS acid, the use amount of catalyst is 0.005～0.2 kilogram.
7. according to the preparation method of claim 5, it is characterized in that wherein said alkaline aqueous solution is that alkaline agent adds and forms in the entry with the alkali metal hydroxide; The consumption of this alkaline agent depends on that NTS is the free acid or the form of salt, when the NTS that uses is free acid, in need coming more than the alkaline agent of 1 equivalent and sulfonate radical; The consumption of this alkali is that every mole of free acid NTS needs 1～6 mole of alkaline agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010173366A CN101823003A (en) | 2010-05-10 | 2010-05-10 | Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010173366A CN101823003A (en) | 2010-05-10 | 2010-05-10 | Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101823003A true CN101823003A (en) | 2010-09-08 |
Family
ID=42687290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010173366A Pending CN101823003A (en) | 2010-05-10 | 2010-05-10 | Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101823003A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
| CN102516136A (en) * | 2011-10-31 | 2012-06-27 | 天津大学 | Method for preparing 4,4 '- diaminostilbene- 2,2' - disulfonic acid by using DNS sodium salt(4,4 '- dinitrostilbene-2,2' - disulfonic acid sodium salt) |
| CN102824907A (en) * | 2012-07-21 | 2012-12-19 | 大连理工大学 | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst |
| CN104190428A (en) * | 2014-07-24 | 2014-12-10 | 大连理工大学 | Catalyst for preparing DNS acid and salts as well as preparation method and application of catalyst |
| CN109675602A (en) * | 2018-12-25 | 2019-04-26 | 西安近代化学研究所 | A kind of supported cobalt-nitrogen-doped carbon catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10152593A (en) * | 1996-09-30 | 1998-06-09 | Zeon Kasei Co Ltd | Vinyl chloride resin composition and vinyl chloride resin molding product |
| US20070040883A1 (en) * | 2005-08-22 | 2007-02-22 | Fuji Photo Film Co., Ltd., | Ink unit containing ink and ink-contacting member |
| CN101250409A (en) * | 2007-12-14 | 2008-08-27 | 福建师范大学 | Rear earth containing hydrotalcite having high fluorescence and preparation method thereof |
-
2010
- 2010-05-10 CN CN201010173366A patent/CN101823003A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10152593A (en) * | 1996-09-30 | 1998-06-09 | Zeon Kasei Co Ltd | Vinyl chloride resin composition and vinyl chloride resin molding product |
| US20070040883A1 (en) * | 2005-08-22 | 2007-02-22 | Fuji Photo Film Co., Ltd., | Ink unit containing ink and ink-contacting member |
| CN101250409A (en) * | 2007-12-14 | 2008-08-27 | 福建师范大学 | Rear earth containing hydrotalcite having high fluorescence and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《J. Reaetivity of Solids》 19981231 Sato.T et al. Synthesis of hydrotaleite-like ompounds and their physieo- chemieal properties , 2 * |
| 《中国博士学位论文全文数据库》 20020630 高文涛 催化氧化饱和碳原子功能化研究 , 2 * |
| 《中国博士学位论文全文数据库》 20081115 熊志刚 金属酞菁负载化及其可见光敏化降解氯苯酚 , 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
| CN102389807B (en) * | 2011-09-09 | 2013-06-12 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
| CN102516136A (en) * | 2011-10-31 | 2012-06-27 | 天津大学 | Method for preparing 4,4 '- diaminostilbene- 2,2' - disulfonic acid by using DNS sodium salt(4,4 '- dinitrostilbene-2,2' - disulfonic acid sodium salt) |
| CN102824907A (en) * | 2012-07-21 | 2012-12-19 | 大连理工大学 | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst |
| CN102824907B (en) * | 2012-07-21 | 2014-07-23 | 大连理工大学 | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst |
| CN104190428A (en) * | 2014-07-24 | 2014-12-10 | 大连理工大学 | Catalyst for preparing DNS acid and salts as well as preparation method and application of catalyst |
| CN109675602A (en) * | 2018-12-25 | 2019-04-26 | 西安近代化学研究所 | A kind of supported cobalt-nitrogen-doped carbon catalyst and its preparation method and application |
| CN109675602B (en) * | 2018-12-25 | 2021-12-21 | 西安近代化学研究所 | Supported cobalt-nitrogen doped carbon catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101823003A (en) | Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same | |
| US3738988A (en) | Process for oxidation of dihydroquinacridones to quinacridones | |
| CN101624476A (en) | Production process of pigment red HT | |
| CN102397794A (en) | Complex catalyst system and application thereof to decomposition of naphthene hydrogen peroxide | |
| CN107915644A (en) | A kind of method that p-aminophenyl ether is prepared using paranitrochlorobenzene as raw material | |
| CN101671266B (en) | Synthetic method of 2,6-dibromo-4-nitroaniline diazosalt | |
| CN102031018A (en) | Composite reactive grey for printing and dyeing and clean production process thereof | |
| CN113387851B (en) | Preparation method of 4, 4' -dichlorodiphenyl sulfone | |
| CN102824907B (en) | Catalyst for preparing DNS (4, 4'-dinitrostilbene-2, 2'-disulfonic acid) acid and salt of DNS acid and preparation method of catalyst | |
| CN101466664B (en) | Method for preparing metallic dixhydroxybenzenedisulfonates | |
| CN101745411B (en) | Catalyst using ruthenium based halogen to substitute hydroxyapatite and preparation and application thereof | |
| CN101423224A (en) | Potassium borofluoride preparation method based on fluosilicic acid and boron rock | |
| CN103193690A (en) | Method for preparing 4, 4'-diamido stilbene-2, 2'-disulfonic acid | |
| CN102070552B (en) | Method for preparing 3-amino-5-nitro-2,1-benzisothiazole and diazonium salt thereof | |
| CN113402379B (en) | Green production method of 1,1 '-binaphthyl-8,8' -dicarboxylic acid | |
| CN101538413B (en) | Active black K-BR and nonpolluting production technology thereof | |
| CN105367454A (en) | Method for producing metanilic acid by utilizing quinacridone pigment byproduct | |
| AU5061399A (en) | 1:2 chromium complex dyes, their production and use | |
| CN111848459A (en) | Clean and efficient preparation method of 1,6 and 1, 7-clevuric acid | |
| CN1289803A (en) | Temporarily water-soluble disperse dye containing carboxymethyl sulfonyl and its synthesis process | |
| CN104190428A (en) | Catalyst for preparing DNS acid and salts as well as preparation method and application of catalyst | |
| CN114534729B (en) | Catalyst, preparation method thereof and application of catalyst in preparation of beta-carotene by electrochemical method | |
| CN103012223B (en) | Method of recovering waste slag in quinacridone production course to prepare 2,2'-disulfonic acid ethyl benzidine | |
| US20120165532A1 (en) | One-Step Synthesis Method of 2,9-Dimethyl-4,7-Diphenyl-1,10- Phenanthroline | |
| CN112094276A (en) | Equipment and process for preparing metal phthalocyanine by using urea-choline chloride eutectic solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100908 |