CN108017565A - Hydrogenating reduction method prepares DSD acid - Google Patents
Hydrogenating reduction method prepares DSD acid Download PDFInfo
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- CN108017565A CN108017565A CN201711399317.7A CN201711399317A CN108017565A CN 108017565 A CN108017565 A CN 108017565A CN 201711399317 A CN201711399317 A CN 201711399317A CN 108017565 A CN108017565 A CN 108017565A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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Abstract
The invention discloses a kind of hydrogenating reduction method to prepare DSD acid, including 4,4' dinitrostilbene 2, and 2' disulfonic acids sodium, Raney Ni, potassium dihydrogen phosphate, disodium dihydrogen and hydrogen, are specifically divided into following steps：S1 weighs 32g4 in 23 DEG C of room temperatures, 4' dinitrostilbenes 2, 2' disulfonic acid sodium raw materials solution, and to filtering 4, 4' dinitrostilbenes 2, 2' disulfonic acid sodium raw materials solution carries out filtering and impurity removing, 4 after filtering and impurity removing, 4' dinitrostilbenes 2, 2' disulfonic acid sodium raw materials solution is added in reactor, then 3.0g potassium dihydrogen phosphates and 1.5g disodium dihydrogens are weighed and is added after being dissolved in 450ml water in reactor, and rotated clockwise by the agitating device in reactor and the reaction raw materials of inside reactor are stirred, after S2 is by stirring, again to adding the 2.0g raney nickel catalysts after purifying in reactor.The present invention using Raney Ni catalysis transmit reduction 4,4 dinitrostilbenes 2,2' sodium disulfonates (DND) prepare DSD acid, overcome iron powder reducing method labor intensity it is big the problem of.
Description
Technical field
The present invention relates to detergent, textile industry, plastics, photograph and paper industry technical field, is specially a kind of hydrogenation
Reduction method prepares DSD acid.
Background technology
Chemical reaction refers to the cracking of molecules into atom, and atom rearranges the process of combination producing recruit, is known as chemistry
Reaction.The discoloration generation sediment etc. that emits light and heat is often accompanied by the reaction, is often accompanied by shining in the reaction, is generated heat, changes colour, generating
Sediment etc..Judge whether a reaction is that the foundation chemically reacted is to react whether to generate new material.Managed according to chemical bond
By, and can judge whether it is chemical reaction according to the fracture of key and the generation of new keys whether is had been friends in the past in a change procedure.
4,4- diaminobenzil -2,2' sodium disulfonates (DSD acid) are that have among the important dyestuff of difunctional
Body, is widely used in detergent, textile industry, plastics, photograph and paper industry.
Industrial common Pd/C (5%) catalytic hydrogenation catalysts are catalyzed the catalysis for transmitting reducing DNS as sodium formate
Agent, has investigated the influence of dosage and activity to the conversion ratio, selectivity of DNS reduction respectively.Test result indicates that Pd/C (5%)
It is excessive to the catalytic activity of sodium formate transmission reduction, cause a large amount of accessory substances 4,4' diaminourea bibenzyl -2,2' disulfonic acid (DADB)
Generation is domestic general all using iron powder reducing that is ancient and falling behind, but the labor intensity of traditional iron powder reduction method is big, environmental pollution
The problems such as, and external new process all uses catalytic hydrogenation method, though palladium/carbon catalyst is selective good, price is difficult for regeneration.
The content of the invention
（One）The technical problem of solution
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenating reduction method to prepare DSD acid, solves the country and generally all adopts
With iron powder reducing that is ancient and falling behind, and external new process all uses catalytic hydrogenation method, though palladium/carbon catalyst is selective good,
The problem of price is difficult for regeneration.
（Two）Technical solution
To achieve the above object, the present invention provides following technical solution：A kind of hydrogenating reduction method prepares DSD acid, including 4,4'- bis-
Nitro diphenyl ethylene -2,2'- disulfonic acid sodium, Raney Ni, potassium dihydrogen phosphate, disodium dihydrogen and hydrogen, are specifically divided into following
Step：
S1 weighs 32g4 in 23 DEG C of room temperatures, 4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution, and to filtering 4,
4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution carries out filtering and impurity removing, 4, the 4'- dinitros two after filtering and impurity removing
Styrene -2,2'- disulfonic acid sodium raw materials solution is added in reactor, then weighs 3.0g potassium dihydrogen phosphates and 1.5g biphosphates
Disodium is added in reactor after being dissolved in 450ml water, and is rotated clockwise by the agitating device in reactor to inside reactor
Reaction raw materials be stirred.
After S2 is by stirring, then to adding the 2.0g raney nickel catalysts after purifying in reactor, in order to ensure safe need
Tighten the autoclave leak test in reactor.
S3 test do not leak after, in order to ensure that hydrogen gas explosion does not occur, into generator from air condition be filled with hydrogen or
When switching to transport under air condition state load number and specified cooling condition from hydrogen state row's hydrogen, it is necessary to avoid hydrogen and air
Contact, and the displacement that intermediate medium carries out should be passed through, intermediate medium is generally the inert gases such as carbon dioxide or nitrogen, uses hydrogen
Displacement 6-7 times,.
Hydrogen is poured after S4 leak tests 3min and then in reactor to 2.0Mpa, 5min need to be in reactor after hydrogenation
Portion carries out heating question response device and is warming up to 140 DEG C and starts fully reaction.
S5 is considered as reaction when pressure does not decline in 30min post-reactors and terminates, and opens reactor, pours out reaction solution,
Raney nickel catalyst is filtered by filter, then the reaction solution after filtering is heated, after 120 DEG C of heating,
Under acid condition, Cucumber can be converted into suspended state by solubilised state or colloidal attitude, and obtain product by acid out.
Preferably, this described technique optimum operation condition is 4,4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials
Mass concentration is 60~75g/L.
Preferably, this described technique optimum operation condition be raney nickel catalyst be material quality 4%~7%.
Preferably, this described technique optimum operation condition is that reaction temperature is 140~160 DEG C.
Preferably, this described technique optimum operation condition is that reaction pressure is 2.0~2.5Mpa.
（Three）Beneficial effect
The present invention provides a kind of hydrogenating reduction method to prepare DSD acid, possesses following beneficial effect：
（1）The present invention effectively reduces the cost of catalyst using raney nickel catalyst, and systematically have studied buffer solution
Middle catalytic hydrogenation prepares the process conditions of DSD acid, optimal formula rate is drawn by multiple experimental formula so that in this technique
Under the conditions of reduce yield up to 96.1%, material concentration influences reaction yield little, but has a great influence to by-product benzyl thing, when dense
When spending relatively low, benzyl thing yield improves, and product quality is unqualified, and after concentration is more than 80g/L, coloring thing increase is therefore, former
This is preferred material concentration range in 60~75 g/L, and as temperature improves, yield also increases, but when temperature is more than more than 160 DEG C, holds
Coloring thing is also easy to produce, therefore, temperature range is controlled at 140~160 DEG C, and low pressure is unfavorable for reacting, and production by-product is more, and pressure is high
When improve requirement to equipment, therefore, suitable pressure limit is 2.0~2.5MPa, makes the preparation of DSD acid have in high yield
With the effect of high quality.
（2）The present invention transmits reduction 4,4- dinitrostilbene -2,2' sodium disulfonates (DND) system using Raney Ni catalysis
The characteristics of standby DSD acid new methods is the catalytic hydrogenating reduction that can realize DNS under normal pressure, low for equipment requirements, and is overcome
The problems such as labor intensity of traditional iron powder reduction method is big, environmental pollution.
Embodiment
Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, belongs to the scope of protection of the invention.
The present invention provides a kind of technical solution：Hydrogenating reduction method prepares DSD acid, including 4,4'- dinitrostilbene -2,
2'- disulfonic acids sodium, Raney Ni, potassium dihydrogen phosphate, disodium dihydrogen and hydrogen, are specifically divided into following steps：
S1 weighs 32g4 in 23 DEG C of room temperatures, 4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution, and to filtering 4,
4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution carries out filtering and impurity removing, 4, the 4'- dinitros two after filtering and impurity removing
Styrene -2,2'- disulfonic acid sodium raw materials solution is added in reactor, then weighs 3.0g potassium dihydrogen phosphates and 1.5g biphosphates
Disodium is added in reactor after being dissolved in 450ml water, and is rotated clockwise by the agitating device in reactor to inside reactor
Reaction raw materials be stirred, potassium dihydrogen phosphate（Chemical formula：KH2PO4）It is sealed, stablizes in air, lost at 400 DEG C
Water, becomes metaphosphate, and for preparing buffer solution, measure arsenic, antimony, phosphorus, aluminium and iron, prepare phosphorus titer, prepare culture medium, survey
Determine Phos in serum, alkaline phosphatase activity, the physicochemical property of disodium dihydrogen is white crystalline powder, relative density
1.862, it is heated to more than 220 DEG C and resolves into sodium metaphosphate.It is soluble easily in water, chelate, aqueous solution can be formed with Cu2+, Fe2+
Phosphoric acid is hydrolyzed into the heating of dilute sulfuric acid diluted mineral acid, and source and preparation method are that sodium dihydrogen phosphate is heated to 200 DEG C of dehydrations and is made；Or
Sodium carbonate is added in phosphoric acid, 200 DEG C is heated to and is made by dehydration, this technique optimum operation condition is 4,4'- dinitros two
Styrene -2,2'- disulfonic acid sodium raw materials mass concentration is 60~75g/L, and material concentration influences less, but to pair reaction yield
Production benzyl thing has a great influence.When concentration is relatively low, benzyl thing yield improves, and product quality is unqualified;When concentration more than 80g/L with
Afterwards, colour thing increase, therefore, material concentration scope this be preferred in 60~75 g/L.
After S2 is by stirring, then to adding the 2.0g raney nickel catalysts after purifying in reactor, in order to ensure safe need
The autoclave leak test in reactor is tightened, Raney Ni is that a kind of small grains by the nickel alumin(i)um alloy with loose structure form
Solid-state different-phase catalyst, it is earliest by American engineer Mo Lilanni in the hydrogenation process of vegetable oil, as catalyst
And use.Since " blue Buddhist nun " is the registration mark of Grace chemical company, so strictly speaking, only have this company wears dimension
The product of gloomy Division of Chemistry pupil production could be referred to as " Raney Ni ", its preparation process is at nickel alumin(i)um alloy strong caustic
Reason, in this course, most aluminium can be reacted and dissolved with sodium hydroxide, leave many micropores not of uniform size.
It is so tiny grey powder on Raney Ni surface, but from microcosmic angle, each molecule in powder is one
Three-dimensional porous structure, this loose structure cause its surface area to greatly increase, and what great surface area was brought is very high urge
Change activity, this allows for Raney Ni and is widely used in organic synthesis and industrial hydrogenation as a kind of different-phase catalyst
In.And " metallic framework catalyst " or " sponge-metallic catalyst " is used for address has a microcellular structure, and physics and chemistry
Property is similar to the catalyst of Raney Ni, and the increase of catalyst amount, benzyl thing and DSD acid yield all increase.To ensure benzyl
Thing content is less than 1.5%, and what catalytic amount accounted for raw material DND mass 4%~7% is advisable, and is effectively reduced and urged using raney nickel catalyst
The cost of agent, and the process conditions that catalytic hydrogenation in buffer solution prepares DSD acid are systematically have studied, by being repeatedly formulated
Experiment draws optimal formula rate so that yield is reduced under this process conditions up to 96.1%, makes the preparation of DSD acid have height
The effect of yield and high quality, is catalyzed using Raney Ni and transmits reduction 4,4- dinitrostilbenes -2,2' sodium disulfonate (DND)
The characteristics of preparing DSD acid new methods is the catalytic hydrogenating reduction that can realize DNS under normal pressure, low for equipment requirements, and is overcome
The problems such as labor intensity of traditional iron powder reduction method is big, environmental pollution, this technique optimum operation condition is raney nickel catalyst
For the 4%~7% of material quality, as temperature improves, yield also increases, but when temperature is more than more than 160 DEG C, easily produces coloring
Thing, therefore, temperature range are controlled at 140~160 DEG C, this technique optimum operation condition is that reaction temperature is 140~160 DEG C.
S3 test do not leak after, in order to ensure that hydrogen gas explosion does not occur, into generator from air condition be filled with hydrogen or
When switching to transport under air condition state load number and specified cooling condition from hydrogen state row's hydrogen, it is necessary to avoid hydrogen and air
Contact, and the displacement that intermediate medium carries out should be passed through, intermediate medium is generally the inert gases such as carbon dioxide or nitrogen, uses hydrogen
Displacement 6-7 times.
Hydrogen is poured after S4 leak tests 3min and then in reactor to 2.0Mpa, 5min need to be in reactor after hydrogenation
Portion carries out heating question response device and is warming up to 140 DEG C and starts fully to react, and low pressure is unfavorable for reacting, and production by-product is more, pressure
The requirement to equipment is improved when high.Therefore, suitable pressure limit is 2.0~2.5MPa, this technique optimum operation condition is
Reaction pressure is 2.0~2.5MPa.
S5 is considered as reaction when pressure does not decline in 30min post-reactors and terminates, and opens reactor, pours out reaction solution,
Raney nickel catalyst is filtered by filter, then the reaction solution after filtering is heated, after 120 DEG C of heating,
Under acid condition, Cucumber can be converted into suspended state by solubilised state or colloidal attitude, and draw product, acid out by acid out：
Under acid condition, Cucumber can be converted into suspended state by solubilised state or colloidal attitude, and the methods of recycling flocculation sediment, air supporting will
It is separated from solution, and this method can effectively remove the content of lignin in black liquid, purified cotton black liquor, removes part
COD。
In conclusion invention effectively reduces the cost of catalyst, and system using raney nickel catalyst
Ground have studied the process conditions that catalytic hydrogenation in buffer solution prepares DSD acid, and optimal formula is drawn by multiple experimental formula
Ratio so that yield is reduced under this process conditions up to 96.1%, material concentration influences less, but to by-product benzyl reaction yield
Substratess have a great influence, and when concentration is relatively low, benzyl thing yield improves, and product quality is unqualified, after concentration is more than 80g/L,
Thing increase is coloured, therefore, this is preferred material concentration scope in 60~75 g/L, and as temperature improves, yield also increases, but temperature
During more than more than 160 DEG C, coloring thing is easily produced, therefore, temperature range is controlled at 140~160 DEG C, and low pressure is unfavorable for reacting,
It is more to produce by-product, the requirement to equipment is improved when pressure is high, therefore, suitable pressure limit is 2.0~2.5MPa, is made
The preparation of DSD acid has the effect with high quality in high yield, be catalyzed using Raney Ni transmit 4,4- of reduction dinitrostilbenes-
It is the catalytic hydrogenating reduction that can realize DNS under normal pressure that 2,2' sodium disulfonates (DND), which prepare the characteristics of DSD acid new methods, right
The problems such as equipment requirement is low, and the labor intensity for overcoming traditional iron powder reduction method is big, environmental pollution.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of changes, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of hydrogenating reduction method prepares DSD acid, it is characterised in that：Including 4,4'- dinitrostilbene -2,2'- disulfonic acids
Sodium, Raney Ni, potassium dihydrogen phosphate, disodium dihydrogen and hydrogen, are specifically divided into following steps：
S1 weighs 32g4 in 23 DEG C of room temperatures, 4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution, and to filtering 4,
4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials solution carries out filtering and impurity removing, 4, the 4'- dinitros two after filtering and impurity removing
Styrene -2,2'- disulfonic acid sodium raw materials solution is added in reactor, then weighs 3.0g potassium dihydrogen phosphates and 1.5g biphosphates
Disodium is added in reactor after being dissolved in 450ml water, and is rotated clockwise by the agitating device in reactor to inside reactor
Reaction raw materials be stirred.
After 2.S2 is by stirring, then to adding the 2.0g raney nickel catalysts after purifying in reactor, in order to ensure security needs
Tighten the autoclave leak test in reactor.
3.S3 test do not leak after, in order to ensure that hydrogen gas explosion does not occur, into generator from air condition be filled with hydrogen or from
When hydrogen state row's hydrogen switchs to transport under air condition state load number and specified cooling condition, it is necessary to avoid hydrogen and air from connecing
Touch, and the displacement that intermediate medium carries out should be passed through, intermediate medium is generally the inert gases such as carbon dioxide or nitrogen, is put with hydrogen
Change 6-7 times.
Hydrogen is poured after 4.S4 leak tests 3min and then in reactor to 2.0Mpa, 5min need to be to the inside of reactor after hydrogenation
Heating question response device is carried out to be warming up to 140 DEG C and start fully reaction.
5.S5 is considered as reaction when pressure subordinate drops in 30min post-reactors and terminates, and opens reactor, pours out reaction solution, leads to
Cross filter to filter raney nickel catalyst, then the reaction solution after filtering is heated, after 120 DEG C of heating, in acid
Under the conditions of property, Cucumber can be converted into suspended state by solubilised state or colloidal attitude, and obtain product by acid out.
6. hydrogenating reduction method according to claim 1 prepares DSD acid, it is characterised in that：This described technique optimum operation bar
Part is that 4,4'- dinitrostilbene -2,2'- disulfonic acid sodium raw materials mass concentrations are 60~75g/L.
7. hydrogenating reduction method according to claim 1 prepares DSD acid, it is characterised in that：This described technique optimum operation bar
Part is 4%~7% that raney nickel catalyst is material quality.
8. hydrogenating reduction method according to claim 1 prepares DSD acid, it is characterised in that：This described technique optimum operation bar
Part is that reaction temperature is 140~160 DEG C.
9. hydrogenating reduction method according to claim 1 prepares DSD acid, it is characterised in that：This described technique optimum operation bar
Part is that reaction pressure is 2.0~2.5Mpa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070395A (en) * | 1975-08-13 | 1978-01-24 | Nippon Kayaku Kabushiki Kaisha | Process for the preparation of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salts |
| JPH04321661A (en) * | 1991-04-19 | 1992-11-11 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostylbene-2,2'-disulfonic acid or salt thereof |
| CN102500395A (en) * | 2011-10-31 | 2012-06-20 | 天津大学 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
| 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) |
-
2017
- 2017-12-22 CN CN201711399317.7A patent/CN108017565A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070395A (en) * | 1975-08-13 | 1978-01-24 | Nippon Kayaku Kabushiki Kaisha | Process for the preparation of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salts |
| JPH04321661A (en) * | 1991-04-19 | 1992-11-11 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostylbene-2,2'-disulfonic acid or salt thereof |
| CN102500395A (en) * | 2011-10-31 | 2012-06-20 | 天津大学 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
| 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) |
Non-Patent Citations (3)
| Title |
|---|
| BAZANOVA, I. N. ET AL: "Reduction of 4,4"-dinitrostilbene-2,2"-disulfonic acid with hydrogen on Raney nickel", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY (TRANSLATION OF ZHURNAL PRIKLADNOI KHIMII)》 * |
| 李斌栋等: "催化氢化法合成DSD酸进展", 《染料工业》 * |
| 王珏等: "DNS加氢还原制备DSD酸", 《化学工业与工程》 * |
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Application publication date: 20180511 |