CN102675161A - Method for preparing DSD acid - Google Patents
Method for preparing DSD acid Download PDFInfo
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Abstract
The invention belongs to the field of organic synthesis, and relates to a method for preparing DSD acid. The method includes using 4,4'-dinitrostilbene-2,2'-disulfonic acid as a raw material and water as solvent to carry out hydrogenation reduction in the presence of platinum, zinc and copper catalysts. The reaction conditions includes that the mass concentration of the raw material in the water ranges from 1% to 30%, the temperature ranges from 25 DEG C to 80 DEG C, the pressure ranges from 0.1MPa to 2.0MPa, the pH (potential of hydrogen) value ranges from 3 to 7, and the quantity of the catalysts added into each 100 grams of the raw material ranges from 0.3 gram to 3.0 grams. The method for preparing the DSD acid has the advantages that a process is simple, the operation conditions are moderate and are controlled easily, pollution is less, the catalysts used in reaction are high in activity and selectivity, low in cost and long in service life, and the like. Particularly, a DSD acid product is good in quality and low in chromaticity and benzyl substance content, and stilbene fluorescent brightener can be directly synthesized by sodium salt liquor of the DSD acid without acidification.
Description
Technical field
The invention belongs to the organic synthesis field, relate to a kind of preparation method of organic intermediate.Concrete, relate to the sour method of a kind of DSD of preparation.
Background technology
DSD acid (chemical name: 4; 4 '-diaminobenzil-2; 2 '-disulfonic acid) be the important intermediate of producing environmental protection type dye and white dyes, these white dyess are mainly used in papermaking, washing composition and textile and dyeing industry, and other 15% is used for synthetic stilbene based dye.Traditional preparation method (by 4,4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid (DNS acid) is through the iron powder reducing preparation) is eliminated because of the seriously polluted time limit that has been asked to.At present both at home and abroad all with the emphasis of shortening as research.
In the process of DNS acid catalysis hydrogenating reduction system DSD acid, require two nitros of DNS acid to be reduced into amido fully, must keep ethylenic linkage simultaneously.Because the complexity of hydrogenating reduction aromatic nitro and ethylenic linkage differs very little, when nitro was reduced, ethylenic linkage also possibly be reduced into the benzyl thing.The process of catalytic reduction nitro is a succession of multiple reaction, in reaction, also possibly generate azoxy compound, azo cpd, hydroformylation thing etc.If weaken activity of such catalysts, have the partial nitro reduction and not exclusively generate single nitroreduction thing, and these by products basically all are coloured compounds, are difficult to remove, thereby influence the colourity of product, cause quality product not reach requirement.
Main reaction:
Following side reaction takes place when catalyst activity is high:
Following side reaction takes place when time a little less than the catalyst activity:
Also possibly follow following side reaction simultaneously in main reaction:
In order to solve the problem that shortening exists, the method for domestic and foreign literature and patent report mainly contains: according to main catalyst component Pd, Pt, Ni, select for use to add the generation that different compounds (being commonly called as toxin) suppresses the side reaction thing.
Japan chemical drug company (US4070395,1978) uses Raney Ni to be catalyzer, and Dyhard RU 100 is a suppressor factor, and methyl alcohol is solvent, at 45-120 ℃, and under the 0.06-1.1MPa, DNS hydrogenating reduction system DSD acid.Japan chemical company (JP59118760,1984) adds sodium sulfite anhy 96 as suppressor factor in Raney Ni catalyzer, can suppress the generation of benzyl thing.
People (JP74127955,1974) such as the Naonori Hirata of Mitsubishi propose to make catalyzer with 5%Pd/C, and 85% DNS acid sodium-salt is soluble in water in pH value 7.2 times; Add KI; Under the hydrogen pressure of 0.1-0.2MPa, 50 ℃ of hydrogenating reductions get DSD acid, yield 97.8%.The Chen Hongbo of Dalian University of Technology etc. are catalyzer with 0.2%Pd/C, OVN (NH
4VO
3) be suppressor factor, 65 ℃, 0.8MPa makes DSD acid yield 95%, content 99%, benzyl thing 0.5%.
People (US6096924,2000) such as the Matin Studer of Switzerland Novartis AG company adopt Pt/C catalyzer, NH
4VO
3Be suppressor factor, add activated carbon and come the band look by product that generates in the absorption reaction process, hydroformylation thing 1.0%, azo 0.4%, benzyl thing 0.3%.Japan chemical drug company is a raw material with DNS, and Pt/C exists down, and iron(ic)chloride is suppressor factor, water as solvent, and 60 ℃ of temperature of reaction, pressure 0.6MPa makes DSD acid, DSD acid content 97.8%, benzyl thing content 0.45%.
Though above method can prepare the higher DSD acid of purity, all has some shortcomings.At first; It is qualified that the colourity of product is difficult to; Though suppressor factor be added on the generation that has suppressed the benzyl thing to a certain extent; Reaction is complete inadequately, the red intermediate product azo cpd of generation but also make simultaneously, and the chromaticity index of the DSD acid of generation seriously surpasses the use standard of white dyes and can't be applied to prepare white dyes; Secondly, because the adding of suppressor factor brings difficulty to postprocessing working procedures, increased labour cost; The 3rd, acid out DSD acid after-filtration gained waste water color is yellow or deep yellow, and the COD value is higher, about about 2000mg/L.
Summary of the invention
The object of the present invention is to provide a kind of new DSD acid preparation method,, make indexs such as its colourity, benzyl thing content all can reach the requirement of the high-quality product of preparation (for example white dyes) to improve DSD acid quality; Reduce the COD value of waste water simultaneously, reduce the pressure that the three wastes are handled.
Through a large amount of research trials, the present invention proposes to adopt a kind of three-way catalyst shortening with concerted catalysis effect to prepare DSD acid first, and this catalyzer is that Primary Catalysts, copper and zinc are suppressor factor with platinum; And be carried on Primary Catalysts and suppressor factor on the carrier simultaneously; Under suitable reaction conditions, with 4,4 '-dinitrobenzene toluylene-2; 2 '-disulfonic acid is the feedstock production title product, thereby has realized the object of the invention.
Technical scheme of the present invention is following:
A kind of method for preparing DSD acid, with 4,4 '-dinitrobenzene toluylene-2; 2 '-disulfonic acid is that raw material, water are solvent, in the presence of platinum, zinc, copper catalyst, carries out hydrogenating reduction, reaction conditions: 4; 4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid initial mass concentration in solvent is 1-30%, temperature 25-80 ℃; Pressure 0.1-2.0MPa, pH value 3-7, the catalyzer add-on is 0.3-3.0 gram/100 gram raw materials.
Catalyzer of the present invention with activated carbon as carrier, simultaneously platinum, copper, three kinds of components of zinc on carrier, charge capacity is respectively 0.1-10% (mass percent).Suitable charge capacity is 1-10% for the platinum consumption, copper consumption 0.1-1.0%, zinc consumption 0.1-1.0%.Used platinum, copper, the zinc of preparation supported catalyst both can be that elemental metals also can be its salt; The selection of carrier and the carrying method of catalyzer all are known in those skilled in the art, for example select for use specific surface area greater than 500m
2/ g, particle diameter are that 15-30 μ m, total pore volume are made carrier greater than the cocos active carbon of 0.5ml/g.Reaction no longer drops to terminal point with hydrogen pressure.After reaction finishes, filter and tell the catalyst recirculation use.Generally after recycling 8 times, for guaranteeing certain reaction speed, should add the part raw catalyst, additional amount is the 5-20% of initial add-on usually, for example adds the raw catalyst of initial adding quality about 10%.
The contriver has confirmed the influence of differential responses condition to quality product through a large amount of condition checkings and optimization Test:
When raw material when initial mass concentration is higher than 30% in solvent (water), speed of response is slow excessively, the DSD acid colourity severe overweight that reaction generates; And raw material initial mass concentration in water is lower than at 1% o'clock, and speed of response is too fast, will make in the DSD acid product benzyl thing content higher, and throughput also reduces greatly simultaneously.
Temperature of reaction is higher than 80 ℃, and the DSD acid solution of preparation is easy to oxidized, makes the DSD acid product colourity of generation defective; When temperature of reaction was lower than 25 ℃, reaction was carried out complete inadequately, and the DSD acid product colourity of generation is defective equally.
When reaction pressure was higher than 2.0MPa, benzyl thing content was higher in the DSD acid product of generation; When reaction pressure was lower than 0.1MPa, reaction was carried out complete inadequately, and the DSD acid product colourity of generation is defective.
When the add-on of reacting middle catalyst was higher than 3.0 grams/100 gram raw materials, benzyl thing content was higher in the DSD acid product of generation; When the add-on of reacting middle catalyst was lower than 0.3 gram/100 gram raw materials, reaction was carried out complete inadequately, and the DSD acid product colourity of generation is defective.
The pH value is higher than 7 or be lower than at 3 o'clock in the reaction, and the DSD acid product colourity of generation exceeds standard; The pH value is higher than at 9 o'clock, and reaction can't be carried out, and only generates jelly shape by product.The pH value of reaction soln is regulated with the lower concentration mineral acid, uses Hydrogen chloride or dilute sulphuric acid usually.
Therefore, further preferred reaction conditions is: raw material mass concentration in solvent is 10-20%, temperature 30-50 ℃, and pressure 0.5-1.5MPa, pH value 3.5-6, the catalyzer add-on is 0.3-1.0 gram/100 gram raw materials.
According to preparation method of the present invention, reaction finish, leach obtain behind the catalyzer 4,4 '-diaminobenzil-2,2 '-sodium disulfonate salts solution adds acid for adjusting pH value, separates out DSD acid, filters to obtain solid phase prod.Filtrating (being the waste water of generation) water white transparency, COD is not higher than 100mg/L.Also can with obtain 4,4 '-diaminobenzil-2,2 '-sodium disulfonate salts solution are without acid out, directly be used for synthetic diphenyl ethylene fluorescent bleaches; So both save acid out with used alkali in acid and the synthetic white dyes process, also thoroughly eliminated the spent process water that DSD acid is produced.
Compared with prior art, the method for preparing DSD acid provided by the invention, it is simple to have technology, operational condition is gentle, be easy to control, pollute little, the reaction catalyst system therefor active high, selectivity is high, cost is low, the life-span is long, advantages such as good product quality.Be embodied in following three aspects:
1. because suppressor factor and Primary Catalysts are carried on the identical carrier; The fixed ratio of suppressor factor and Primary Catalysts; Avoid catalyzer is applied mechanically in the process needs corresponding adjusting suppressor factor add-on because of the loss of Primary Catalysts problem, can save the operation that needs to handle suppressor factor in the DSD acid last handling process simultaneously.
2. preparation method of the present invention, 4,4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid transformation efficiency can reach 100%, and product yield is greater than 98%, and the product chromatographic purity is greater than 95%, and benzyl thing content is less than 0.3% in the product, and colourity is less than 0.2.
3. the waste water water white transparency that produces when preparation solid DSD is sour, COD value are below 100mg/L, well below iron powder technology (COD value of waste water 1000mg/L) and existing hydrogenation technique (COD value of waste water 2000mg/L); When using DSD acid sodium-salt solution directly to synthesize diphenyl ethylene fluorescent bleaches, it is particularly outstanding with advantage of no DSD acid producing waste water discharging that it saves soda acid materials.
Embodiment
Following specific embodiment is used to further specify the present invention.But the present invention only limits to these instances absolutely not, can carry out various conversion according to claim institute restricted portion.Raw materials used and reagent all has commercially available in the instance.
Instance 1: Preparation of Catalyst
1.33 gram Platinic chloride (H
2PtCl
66H
2O) be dissolved in 2 milliliter of 10% hydrochloric acid 0.16 gram venus crystals (Cu (CH
3COO)
2H
2O) and 0.17 gram zinc acetate (Zn (CH
3COO)
22H
2O) be dissolved in 10 ml waters, two solution mix for use.Add in 250 milliliters of four-hole bottles (having whisking appliance, TM, condensing surface and tap funnel) with 120 ml waters with through activated carbon 9.4 grams that nitric acid treatment is crossed; Drip the mixing solutions of ready made platinum, copper and zinc salt down in 50 ℃ of stirrings; About 1 hour of the dropping time of control, drip the continuation stirring and it was permeated on activated carbon fully in 30 minutes.Between 7-8, add 2.5 milliliter of 85% Hydrazine Hydrate 80 with saturated sodium carbonate solution adjusting pH value, be warming up to 90 ℃, be incubated 1 hour, afterwards, be cooled to 25 ℃, filter, washing is to neutral, till suction filtration does not extremely drip.The catalyzer that obtains (in dry product platiniferous 5%, copper 0.5%, zinc 0.5%) sealing is for use.
Use same quadrat method, the add-on of adjustment platinum and copper, zinc can obtain the catalyzer of desired content (for example platinum 1-10%, copper 0.1-1% zinc 0.1-1%).
Instance 2:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 15 grams are dissolved in 100 ml waters, regulate the pH value and (use 1% hydrochloric acid; Together following) be 5.5, Pt-Cu-Zn/C catalyzer (Pt 5%, Cu 0.5%, Zn 0.5%) 0.1 gram adds in 250 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.0MPa, start stirring; Heat temperature raising, 50 ℃ of control reaction temperature are carried out hydrogenation reaction.React after 60 minutes, pressure no longer descends; Insulated and stirred is after 30 minutes again, and reaction finishes.Be cooled to 25 ℃, with nitrogen replacement twice, discharging filters out catalyst recirculation and applies mechanically, and obtains 4 after the pressure release, 4 '-diaminobenzil-2,2 '-sodium disulfonate solution.With 4,4 '-diaminobenzil-2, adding 30% sulfuric acid is acidified to pH less than 1 to 2 '-sodium disulfonate solution in stirring down, filters, and obtains off-white color filter cake (the wet article of DSD acid) 26.5 grams, gets 11.88 grams after the oven dry.The total amino value 97.5% of the DSD acid of testing product, colourity 0.15,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.2%, product yield 99%.Filtrating water white transparency shape, COD is 37mg/L.
Above-mentioned catalyst recirculation is used 8 times, and the quality product that obtains all can reach industry standard, and yield is more than 98%, and wherein 2～6 secondary response speed are suitable with for the first time, and the 7th～8 secondary response speed reduces, and the reaction times prolongs about 30 minutes.
In kind, add the above-mentioned catalyzer that has recycled 8 times and also replenish raw catalyst used in the instance 2 0.01 gram.React after 60 minutes, pressure no longer descends; Insulated and stirred is after 30 minutes again, and reaction finishes, and post-treating method is the same, obtains 12 gram DSD acid, total amino value 96%, colourity 0.18, benzyl thing content 0.21%, product yield 98.5%.The filtrating water white transparency, COD 48mg/L.
Instance 3:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 30 grams are dissolved in 200 ml waters; Regulating the pH value is 5.5, and Pt-Cu-Zn/C catalyzer (Pt 3%, Cu 0.3%, Zn 0.3%) 0.3 gram adds in 500 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.0MPa, start stirring; Heat temperature raising, 50 ℃ of control reaction temperature are carried out hydrogenation reaction.React after 60 minutes, pressure no longer descends; Insulated and stirred is after 30 minutes again, and reaction finishes.The operation of cooling back leaches catalyzer with instance 2, obtains 4,4 '-diaminobenzil-2, and 210 milliliters of 2 '-sodium disulfonate solution are divided equally two parts and are carried out the further synthetic white dyes APC application experiment of different processing modes.
With above-mentioned 105 milliliter 4,4 '-diaminobenzil-2,2 '-sodium disulfonate solution is handled according to the same procedure of instance 2; Obtain off-white color DSD acidleach cake 26.5 grams, oven dry back 11.9 grams, total amino value 97.5%; Colourity 0.1, benzyl thing content 0.1%, yield 99.2%.Use it for synthetic white dyes APC (synthesizing), products obtained therefrom yield 92.8% with known in those skilled in the art three methods that contract; Compare intensity 9.55 minutes, whiteness-0.1 with the fluorescent whitening agent VBL standard.
105 milliliter 4 of another part, 4 '-diaminobenzil-2,2 '-sodium disulfonate solution directly are used for synthetic white dyes APC (compound method is the same, just economizes the step of alkali dissolution DSD acid slightly), products obtained therefrom yield 93%; Compare intensity 9.85 minutes, whiteness+0.1 with the fluorescent whitening agent VBL standard.
Above experimental result shows; Adopt that preparation method of the present invention obtains 4; 4 '-diaminobenzil-2; 2 '-sodium disulfonate solution substitutes DSD acid solid and makes raw material, directly is used to prepare white dyes, and the product of preparation product with the DSD acid solids of equimolar amount on yield, intensity, whiteness index is suitable.
Instance 4:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 15 grams are dissolved in 80 ml waters; Regulating the pH value is 5.5, and Pt-Cu-Zn/C catalyzer (Pt 3%, Cu 0.3%, Zn 0.3%) 0.15 gram adds in 250 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.5MPa, start stirring; Heat temperature raising, 40 ℃ of control reaction temperature are carried out hydrogenation reaction.React after 65 minutes, pressure no longer descends; Insulated and stirred is after 30 minutes again, and reaction finishes.Aftertreatment is with instance 2.Get off-white color filter cake 26 grams, get 11.9 grams after the oven dry.The total amino value 97% of DSD acid, colourity 0.18,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.15%, product yield 98.65%.The filtrating water white transparency, COD 40mg/L.
Instance 5:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 150 grams are dissolved in 1000 ml waters; Regulating the pH value is 4, and Pt-Cu-Zn/C catalyzer (Pt 5%, Cu 0.5%, Zn 0.5%) 1.0 grams add in 3000 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 0.6MPa, start stirring; Heat temperature raising, 50 ℃ of control reaction temperature are carried out hydrogenation reaction.Reaction times and post-processing operation get off-white color filter cake 280 grams with instance 2, get 119 grams after the oven dry.The total amino value 97.0% of DSD acid, colourity 0.18,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.2%, product yield 98.6%.The filtrating water white transparency, COD 58mg/L.
Instance 6:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 150 grams are dissolved in 1200 ml waters; Regulating the pH value is 6.0, and Pt-Cu-Zn/C catalyzer (Pt 4%, Cu 0.4%, Zn 0.2%) 1.2 grams add in 3000 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.5MPa, start stirring; Heat temperature raising, 50 ℃ of control reaction temperature are carried out hydrogenation reaction.React after 55 minutes, pressure no longer descends; Insulated and stirred is after 30 minutes again, and reaction finishes.Aftertreatment gets off-white color filter cake 275 grams with instance 2, gets 120 grams after the oven dry.The total amino value 95.8% of DSD acid, colourity 0.17,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.2%, product yield 98.25%.The filtrating water white transparency, COD 38mg/L.
Instance 7:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 150 grams are dissolved in 1000 ml waters; Regulating the pH value is 5, and Pt-Cu-Zn/C catalyzer (Pt 8%, Cu 0.6%, Zn 0.8%) 0.6 gram adds in 3000 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.0MPa, start stirring; Heat temperature raising, 45 ℃ of control reaction temperature are carried out hydrogenation reaction.Reaction times and post-processing operation get off-white color filter cake 282 grams with instance 2, get 119.8 grams after the oven dry.The total amino value 96.0% of DSD acid, colourity 0.20,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.2%, product yield 98.3%.The filtrating water white transparency, COD 27mg/L.
Instance 8:
4,4 '-dinitrobenzene toluylene-2,2 '-sodium disulfonate, 150 grams are dissolved in 1000 ml waters; Regulating the pH value is 3.5, and Pt-Cu-Zn/C catalyzer (Pt 1%, Cu 0.1%, Zn 0.1%) 4.0 grams add in 3000 milliliters of autoclaves of band stirring and built-in prolong; Use nitrogen and hydrogen exchange gas reactor respectively each three times, then hydrogen pressure in the still is transferred to 1.0MPa, start stirring; Heat temperature raising, 60 ℃ of control reaction temperature are carried out hydrogenation reaction.Reaction times and post-processing operation get off-white color filter cake 278 grams with instance 2, get 120 grams after the oven dry.The total amino value 96.0% of DSD acid, colourity 0.19,4,4 '-diamino-connects benzyl-2,2 '-disulfonic acid (being called for short the benzyl thing) content 0.15%, product yield 98.46%.The filtrating water white transparency, COD 50mg/L.
Claims (4)
1. one kind prepares the sour method of DSD, with 4, and 4 '-dinitrobenzene toluylene-2; 2 '-disulfonic acid is that raw material, water are solvent, in the presence of platinum, zinc, copper catalyst, carries out hydrogenating reduction, reaction conditions: 4; 4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid initial mass concentration in solvent is 1-30%, temperature 25-80 ℃; Pressure 0.1-2.0MPa, pH value 3-7, the catalyzer add-on is 0.3-3.0 gram/100 gram raw materials.
2. according to the described method of claim 1, it is characterized in that: described catalyzer with activated carbon as carrier, simultaneously platinum, copper, three kinds of components of zinc on carrier, the charge capacity of each component is respectively 0.1-10% in mass.
3. according to the described method of claim 2, it is characterized in that: the charge capacity of each component is respectively platinum consumption 1-10% on the activity carbon carrier, copper consumption 0.1-1.0%, zinc consumption 0.1-1.0%.
4. according to claim 1 or 3 described methods, it is characterized in that: raw material initial mass concentration in solvent is 10-20%, temperature 30-50 ℃, and pressure 0.5-1.5MPa, pH value 3.5-6, the catalyzer add-on is 0.3-1.0 gram/100 gram raw materials.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842063B1 (en) * | 1970-12-12 | 1973-12-10 | ||
| PL144803B1 (en) * | 1986-03-03 | 1988-07-30 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid | |
| DE3916360A1 (en) * | 1989-05-19 | 1990-11-22 | Ciba Geigy Ag | 4,4-di:amino-stilbene-2,2-di:sulphonic acid - by redn. of corresp. di:nitro cpd. in aq. medium presence of hydrogenation catalyst with forming acid or salt as reducing agent |
| JPH0680622A (en) * | 1992-09-03 | 1994-03-22 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
| CN1121706A (en) * | 1993-04-26 | 1996-05-01 | 孟山都公司 | Process for preparing substituted aromatic amines |
| EP0825979B1 (en) * | 1995-05-19 | 2001-01-03 | Novartis AG | Process for the catalytic hydrogenation of aromatic nitro compounds |
| CN1785969A (en) * | 2005-12-20 | 2006-06-14 | 天津大学 | Semicontinuous method of preparing DSD acid by iron powder reducing DNS sodium salt |
-
2011
- 2011-03-10 CN CN201110057455.3A patent/CN102675161B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842063B1 (en) * | 1970-12-12 | 1973-12-10 | ||
| PL144803B1 (en) * | 1986-03-03 | 1988-07-30 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid | |
| DE3916360A1 (en) * | 1989-05-19 | 1990-11-22 | Ciba Geigy Ag | 4,4-di:amino-stilbene-2,2-di:sulphonic acid - by redn. of corresp. di:nitro cpd. in aq. medium presence of hydrogenation catalyst with forming acid or salt as reducing agent |
| JPH0680622A (en) * | 1992-09-03 | 1994-03-22 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
| CN1121706A (en) * | 1993-04-26 | 1996-05-01 | 孟山都公司 | Process for preparing substituted aromatic amines |
| EP0825979B1 (en) * | 1995-05-19 | 2001-01-03 | Novartis AG | Process for the catalytic hydrogenation of aromatic nitro compounds |
| CN1785969A (en) * | 2005-12-20 | 2006-06-14 | 天津大学 | Semicontinuous method of preparing DSD acid by iron powder reducing DNS sodium salt |
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| CN102675161B (en) | 2014-09-03 |
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