CN102633703A - Method for synthesizing thiourea dioxide by oxygen process - Google Patents
Method for synthesizing thiourea dioxide by oxygen process Download PDFInfo
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- CN102633703A CN102633703A CN2012100945401A CN201210094540A CN102633703A CN 102633703 A CN102633703 A CN 102633703A CN 2012100945401 A CN2012100945401 A CN 2012100945401A CN 201210094540 A CN201210094540 A CN 201210094540A CN 102633703 A CN102633703 A CN 102633703A
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- oxygen
- peroxide
- thiocarbamide
- thiourea peroxide
- thiourea
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Abstract
The invention belongs to the technical field of fine chemical industry and discloses a method for synthesizing thiourea dioxide by an oxygen process. The method disclosed by the invention is a synthesis method by which thiourea dioxide is prepared in an ether type solvent by taking thiourea and oxygen as basic raw materials and can avoid the problems that a large amount of mother liquor is generated during the synthesis process so that excess waste water is further caused. According to the invention, the used basic raw material oxygen is mild in nature, easy to obtain, economic and environment-friendly; the adjustable range of the reaction temperature of a system is wide; the operation steps are simple, the reaction period is short, and the shortcomings of repeated feeding reaction can be avoided; the solvent in the post-treatment process can be recovered and reutilized, so that circulating utilization is realized and energy consumption is low; and furthermore, a required device is simple, the content and the yield are improved in comparison with the prior art, and the method has great economic value.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to the chemical synthetic technology, particularly the synthetic technology of thiourea peroxide.
Background technology
Thiourea peroxide also is FAS, is white crystalline powder, and pure thiourea peroxide is a kind of not only anaerobic voltinism but also the stable compound that does not have reductibility, and the solubleness in water is 26.7 grams per liters (20 ℃), and the pH value of saturated aqueous solution is 5.0.Highly stable in 20-30 ℃ the aqueous solution, but can decompose the basic soln heating that is dissolved with thiourea peroxide, and dissociating to be the-sulfinic acid of reductibility, embodies stronger reductive action.Thiourea peroxide is the substitute products of vat powder, and it is strong to have reductibility, and Heat stability is good stores characteristics such as convenient transportation.This product is in use pollution-free, is mainly used in the bleaching reductive agent of printing and dyeing industry middle cotton, hair, chemical fibre and the reductive agent of thioxine dyes, the stamp of dispersed dye, and occasions such as loose colour are processed or are removed in stripping of textiles again; Be used for association with pulp bleaching in the paper industry; Make newborn peptizing agent in the shooting industry, can make the printing paper exposed portion show high stability; As the synthetic fiber modification catalyzer, can make differential fiber be no lack of Huang, also can be used as oxidation inhibitor and be used for organic synthesis.
About synthesizing of thiourea peroxide; What most literature was reported is thiocarbamide and the synthetic thiourea peroxide of ydrogen peroxide 50 reaction, is prone in this synthetic route produce a large amount of mother liquors, causes wastewater flow rate excessive aborning; And back several times product gas purity of mother liquid recycle and yield all obvious decline can occur; Have in the production process than limitations, therefore select one relatively cheap, safe novel synthesis technique simple to operate will have very big economic worth.
Summary of the invention
The object of the present invention is to provide a kind of is basic material with thiocarbamide and oxygen, the compound method of preparation thiourea peroxide in ether solvent.Its concrete design route is following:
Concrete steps comprise:
(1) dissolution process: with thiocarbamide, initiator, catalyst dissolution in ether solvent;
(2) building-up process: aerating oxygen reaction in thiourea solution under-5 ℃～85 ℃ gets the thiourea peroxide ethereal solution;
(3) last handling process: with the thiourea peroxide ethereal solution decrease temperature crystalline that obtains, warp filters, alcohol is washed, drying obtains solid thiourea peroxide product, and filtrating processing is applied mechanically.
Wherein, the mass ratio of thiocarbamide and ether solvent is 1:1～10 in step (1) dissolution process, and this is that solid-to-liquid ratio is excessive because when the mass ratio of thiocarbamide and ether solvent is lower than 1:1, and it is big to stir resistance, dissolves inhomogeneous; When the mass ratio of thiocarbamide and ether solvent was higher than 1:10, product all was dissolved in the ether solvent, and product-free is separated out behind the decrease temperature crystalline.
Used ether solvent is rudimentary ether or THF or 1, and 4-dioxane or its mixture, wherein rudimentary ether are that ether, propyl ether etc. contain carbon number and are lower than 8 rudimentary ether.Why select one or more of this three kinds of ether solvents; Be because these several kinds not only can be used as solvent; Can also be the peroxide etherate by dioxygen oxidation, and thiocarbamide has reductibility, and then the peroxide etherate be oxidized to thiourea peroxide as oxygenant with thiocarbamide; The two reaction is quick, and the peroxide etherate can not exist and enrichment in the reaction.And solvent for use is water or alcohols or the mixture of the two in the hydrogen peroxide oxidation thiocarbamide technology of the prior art.
Because initiator plays the effect of catalyst in reaction, can carry out smoothly and cause the dioxygen oxidation ethers becoming superoxide in order to guarantee a series of oxidizing reactions, so the initiator of selecting for use in the present invention is a strong oxidizer; Be preferably ydrogen peroxide 50 or concentrated nitric acid; Utilize its strong oxidizing property, the recurring of initiator system oxidizing reaction, the dioxygen oxidation ether solvent generates peroxo-ether; Adopt catalyzer to carry out catalysis simultaneously, and then peroxo-ether aminoiminomethanesulfonic acid generate thiourea peroxide.Be converted into thiourea peroxide with ydrogen peroxide 50 direct oxidation thiocarbamide in the prior art and compare, except difference on the principle, ydrogen peroxide 50 or concentrated nitric acid are as initiator among the present invention; Institute's consumption has seldom been avoided the big problem of sewage load, and the present invention has simultaneously changed solvent; Quality product is better than prior art, and solvent is recyclable in the last handling process utilizes again, has realized recycle; Compare with existing technology and also to have simplified operation steps, the drawback of the reaction of having avoided feeding intake repeatedly.For from impurity enriched and color aspect, guarantee the convenience of post-reaction treatment and the raising of product quality, be preferably ydrogen peroxide 50 or concentrated nitric acid.The molar weight of used initiator is 0.01～0.1 times of thiocarbamide molar weight, because used initiator is strong oxidizer, if initiator is very few, does not have initiation, can't the initiator system oxidizing reaction recur; If initiator is too much,, cause reaction process out of control with the direct oxidation thiocarbamide.
Catalyst system therefor is NH
4VO
3Or V
2O
5, be preferably NH
4VO
3, NH
4VO
3And V
2O
5Being vanadium sub-group compound, is the catalyzer of dioxygen oxidation ethers in the present invention, can improve the oxidisability of oxygen, does not see the report of the synthetic thiourea peroxide of relevant oxygen method now in the document.Because V
2O
5Solubleness less than NH
4VO
3, and certain toxicity is arranged, so preferred catalyst is NH
4VO
3The molar weight of catalyst system therefor is 0.0001～0.01 times of thiocarbamide molar weight, if the molar weight of catalyzer is lower than 0.0001 times thiocarbamide molar weight, the katalysis that does not have can not guarantee to react and carry out smoothly; If the molar weight of catalyzer is higher than 0.01 times thiocarbamide molar weight, cause waste, make troubles to last handling process simultaneously.The molar weight of selecting catalyst is 0.0001～0.01 times of thiocarbamide molar weight, can guarantee that reaction carries out consumption that again can save catalyst, isolating difficulty when further having reduced aftertreatment smoothly.
The used oxygen of said step (2) building-up process is pure oxygen or air, is preferably pure oxygen, can reduce aeration time, and then shortens the reaction times; The system temperature of reaction is-5 ℃～85 ℃, and adjustable extent is wide, comes pilot-gas feeding amount through attemperation; Temperature is high, and then gas feeding amount is big, and temperature is low; Then gas feeding amount is little, comes controls reaction speed with this, if temperature of reaction is lower than-5 ℃; Reaction institute energy requirement is not enough, and the reaction times prolongs; If be higher than 85 ℃, the thiocarbamide self stability reduces, and by product increases, and is unfavorable for obtaining the finished product, also is unfavorable for the aftertreatment of reacting.The pH value of system is 4.5～5.5, in this scope, can guarantee the stability of product, can guarantee that again activity of such catalysts does not receive the interference of system, if the pH value is lower than 4.5, activity of such catalysts reduces; If be higher than 5.5, the stability of product thiourea peroxide reduces and is prone to decompose.
Decrease temperature crystalline, filtration, alcohol in said step (3) last handling process is washed and drying all is a known technology; The product that finally obtains is the solid thiourea peroxide; Contain catalyzer, a small amount of thiocarbamide and trace impurity in the filtrating; Wherein trace impurity does not have influence to building-up process, uses so gained filtrating can directly be made solvent, thereby has practiced thrift solvent and catalyst consumption.The temperature of decrease temperature crystalline is 0 ℃～25 ℃ in the last handling process, in this scope, can guarantee the yield of product, can guarantee that again product quality is unaffected, simultaneously energy efficient; The temperature of decrease temperature crystalline is lower than 0 ℃, if solvent comprises water then has icing possibility, simultaneous temperature is crossed the low energy consumption that increased, if be higher than 25 ℃, crystal is not also separated out fully, does not even separate out, and product yield is lost.
The present invention is brand-new technology, and the basic material oxygen of the aminoiminomethanesulfonic acid that is used for is gentleer than the ydrogen peroxide 50 character in the existing technology, more is easy to get, and is more economical, more environmental protection; The temperature of reaction adjustable extent of system is wide, comes pilot-gas feeding amount through attemperation, and temperature is high, and then gas feeding amount is big, and temperature is low, and then gas feeding amount is little, comes controls reaction speed with this; Operation steps of the present invention is simple simultaneously, and reaction time is short, and energy consumption is low; Avoid in building-up process, producing a large amount of mother liquors and caused the excessive problem of wastewater flow rate; And required device is simple, and content is compared with existing technology with yield and increased, and has very big economic worth.
Embodiment
Below in conjunction with specific embodiment invention is described further, but not as to the restriction of summary of the invention, all based on purification principle according to the invention technology all belong to integral part of the present invention.The raw materials used commercially available prod that is among the present invention.
Embodiment one
The thiocarbamide that in the four-hole boiling flask of 250ml, adds 16g massfraction 99%, 0.002gNH
4VO
3With 15.32ml 1, the 4-dioxane is controlled under-5 ℃ in flask at the uniform velocity aerating oxygen gas, begins to drip the nitric acid 0.02g of massfraction 68% simultaneously; After dropwising, be 4.5 at pH, temperature is under-5 ℃ the condition, and the content of thiocarbamide is followed the tracks of in isothermal reaction sampling in 6 hours; If the content of thiocarbamide is less than 1%, then stopped reaction is higher than 1% as if content; Then continue reaction 1 hour, be cooled to 5 ℃ of filtrations then, the gained filter cake is with 30ml washing with alcohol after drying; Obtain the 17.3g thiourea peroxide, the product of content 99.6%, yield 79.8%.
Embodiment two
The thiocarbamide that in the four-hole boiling flask of 250ml, adds 17g massfraction 98.7%, 0.04g V
2O
5With the 94.26ml THF, be controlled under 40 ℃ in flask in aerating oxygen gas at the uniform velocity, begin to drip the ydrogen peroxide 50 1.25g of massfraction 30% simultaneously, after dropwising; At pH is 5,, temperature is the content that thiocarbamide is followed the tracks of in 40 ℃ of following isothermal reactions sampling in 6 hours; If the content of thiocarbamide is less than 1%, then stopped reaction is higher than 1% as if content; Then continue reaction 1 hour, be cooled to 5 ℃ of filtrations then, the gained filter cake is with 30ml washing with alcohol after drying; Obtain the 16.3g thiourea peroxide, the product of content 98.6%, yield 75.4%.
Embodiment three
The thiocarbamide that in the four-hole boiling flask of 250ml, adds 17g massfraction 98.7%, 0.26gNH
4VO
3With the 235ml ether, be controlled under 85 ℃ in flask in aerating oxygen gas at the uniform velocity, begin to drip the ydrogen peroxide 50 2.5g of massfraction 30% simultaneously; After dropwising, be 5.5 at pH, temperature is the content that thiocarbamide is followed the tracks of in 85 ℃ of following isothermal reactions sampling in 6 hours; If the content of thiocarbamide is less than 1%, then stopped reaction is higher than 1% as if content; Then continue reaction 1 hour, be cooled to 5 ℃ of filtrations then, the gained filter cake is with 30ml washing with alcohol after drying; Obtain the 18.1g thiourea peroxide, the product of content 99.1%, yield 83.0%.
Embodiment four
The thiocarbamide that in the four-hole boiling flask of 250ml, adds 16g massfraction 99%, 0.19g V
2O
5With 30ml ether and 30ml THF, be controlled under 20 ℃ in flask in aerating oxygen gas at the uniform velocity, begin to drip the concentrated nitric acid 0.39g of massfraction 68% simultaneously, after dropwising; At pH is 4.8, and temperature is the content that thiocarbamide is followed the tracks of in 20 ℃ of following isothermal reactions sampling in 6 hours, if the content of thiocarbamide is less than 1%; Then stopped reaction if content is higher than 1%, then continues reaction 1 hour; Be lower than 1% up to thiocarbamide content, be cooled to 5 ℃ of filtrations then, the gained filter cake is with 30ml washing with alcohol after drying; Obtain the 18.6g thiourea peroxide, the product of content 99.4%, yield 82.1%.
Embodiment five
The thiocarbamide that in the four-hole boiling flask of 250ml, adds 17g massfraction 98.7%, 0.21gNH
4VO
3With 75ml 1, the ether of 4-dioxane and 80ml, be controlled under 60 ℃ in flask in aerating oxygen gas at the uniform velocity, begin to drip the ydrogen peroxide 50 2g of massfraction 30% simultaneously; After dropwising, be 5.2 at pH, temperature is the content that thiocarbamide is followed the tracks of in the sampling in 6 hours of 60 ℃ of following constant temperature insulation reaction, if the content of thiocarbamide is less than 1%; Then stopped reaction if content is higher than 1%, then continues reaction 1 hour; Be lower than 1% up to thiocarbamide content, be cooled to 5 ℃ of filtrations then, the gained filter cake is with 30ml washing with alcohol after drying; Obtain the 17.9g thiourea peroxide, the product of content 99.0%, yield 78.7%.
Utilize institute of the present invention synthetic thiourea peroxide; Content is compared all with existing technology with yield and is increased; In building-up process, avoided producing a large amount of mother liquors and caused the excessive problem of wastewater flow rate, and operation steps and required device are simple, the temperature of reaction adjustable extent of system is wide; Reaction time is short, has avoided the drawback that feeds intake repeatedly and react; Solvent is recyclable in the last handling process utilizes again, has realized recycle, and energy consumption is low, has very big economic worth.
Claims (9)
1. the method for the synthetic thiourea peroxide of an oxygen method, it is characterized in that: with thiocarbamide and oxygen is basic material, in ether solvent, prepares thiourea peroxide.
2. the method for the synthetic thiourea peroxide of oxygen method according to claim 1 is characterized in that: concrete design route is following:
Concrete steps comprise:
(1) dissolution process: with thiocarbamide, initiator, catalyst dissolution in ether solvent;
(2) building-up process: aerating oxygen reaction in thiourea solution under-5 ℃～85 ℃ gets the thiourea peroxide ethereal solution;
(3) last handling process: with the thiourea peroxide ethereal solution decrease temperature crystalline that obtains, warp filters, alcohol is washed, drying obtains solid thiourea peroxide product, and filtrating processing is applied mechanically.
3. the method for the synthetic thiourea peroxide of oxygen method according to claim 2 is characterized in that: the mass ratio of thiocarbamide and ether solvent is 1:1～10 in the said step (1).
4. the method for the synthetic thiourea peroxide of oxygen method according to claim 2, it is characterized in that: the ether solvent in the said step (1) is rudimentary ether or THF or 1,4-dioxane or its mixture.
5. the method for the synthetic thiourea peroxide of oxygen method according to claim 2, it is characterized in that: the initiator in the said step (1) is a strong oxidizer.
6. according to the method for claim 2 or the synthetic thiourea peroxide of 5 described oxygen methods, it is characterized in that: described initiator is preferably ydrogen peroxide 50 or concentrated nitric acid, and used molar weight is 0.01～0.1 times of thiocarbamide molar weight.
7. the method for the synthetic thiourea peroxide of oxygen method according to claim 2, it is characterized in that: the catalyzer in the said step (1) is NH
4VO
3Or V
2O
5, used molar weight is 0.0001～0.01 times of thiocarbamide molar weight.
8. according to the method for claim 2 or the synthetic thiourea peroxide of 7 described oxygen methods, it is characterized in that: said catalyzer is preferably NH
4VO
3
9. the method for the synthetic thiourea peroxide of oxygen method according to claim 2 is characterized in that: the pH value of system is 4.5～5.5 in the said step (2).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030956A (en) * | 2013-03-06 | 2014-09-10 | 济南大学 | Composite catalyst for synthesis of thiourea dioxide and application thereof |
Citations (3)
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|---|---|---|---|---|
| JPS49100072A (en) * | 1973-01-31 | 1974-09-20 | ||
| JPH09100072A (en) * | 1995-10-05 | 1997-04-15 | Alps Electric Co Ltd | Printer |
| CN101372150A (en) * | 2007-08-22 | 2009-02-25 | 和成欣业股份有限公司 | Apparatus for forming composite panel |
-
2012
- 2012-04-01 CN CN201210094540.1A patent/CN102633703B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49100072A (en) * | 1973-01-31 | 1974-09-20 | ||
| JPH09100072A (en) * | 1995-10-05 | 1997-04-15 | Alps Electric Co Ltd | Printer |
| CN101372150A (en) * | 2007-08-22 | 2009-02-25 | 和成欣业股份有限公司 | Apparatus for forming composite panel |
Non-Patent Citations (4)
| Title |
|---|
| GEORGE CRANK 等: "oxidations of thioureas with photochemically generated singlet oxygen", 《J.PHOTOCHEM.PHOTOBIOL.A:CHEM.》 * |
| 崔建华: "过氧化氢合成二氧化硫脲研究进展", 《化学推进剂与高分子材料》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030956A (en) * | 2013-03-06 | 2014-09-10 | 济南大学 | Composite catalyst for synthesis of thiourea dioxide and application thereof |
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