CN106831497B - A kind of method of coproduction biruea and hydroxyl sulfate - Google Patents
A kind of method of coproduction biruea and hydroxyl sulfate Download PDFInfo
- Publication number
- CN106831497B CN106831497B CN201710019799.2A CN201710019799A CN106831497B CN 106831497 B CN106831497 B CN 106831497B CN 201710019799 A CN201710019799 A CN 201710019799A CN 106831497 B CN106831497 B CN 106831497B
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- Prior art keywords
- biruea
- reaction
- catalyst
- cyanate
- coproduction
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1454—Preparation of hydroxylamine salts by processes not covered by one or more of groups C01B21/1418 - C01B21/1445, e.g. by conversion of one salt into another
Abstract
The invention discloses a kind of methods of coproduction biruea and hydroxyl sulfate, nitrourea is added in hydrogenation reaction kettle, sulfuric acid and catalyst, control material ratio, reaction temperature and reaction pressure, after hydroxylamine salt to be generated and semicarbazides salt, centrifuge out catalyst, it is neutralized to system acidity and is more than cyanic acid, the solution containing cyanate is slowly added dropwise, semicarbazides salt directly generates solid biruea with cyanate under acid system, and hydroxylamine salt is converted to hydroxyl sulfate in the presence of sulphuric acid, biruea can be used for producing ADC foaming agents, and hydroxyl sulfate is used as analytical reagent, reducing agent, it is also used for organic synthesis.Beneficial effects of the present invention are：Cyanate is directly added into without being detached to intermediate products using nitrourea hydrogenation synthesis hydroxylamine salt and semicarbazides salt, you can coproduction solid biruea and hydroxyl sulfate realize the maximization of benefit.
Description
Technical field
The present invention relates to the production field of biruea, mainly a kind of method of coproduction biruea and hydroxyl sulfate.
Background technology
Biruea is a kind of important fine-chemical intermediate, mainly for the production of ADC foaming agents (azodicarbonamide),
Also it is anti-molten etc. that fire-proof smoke suppressor, antilubricant, the fire prevention of high degree cable be can be used as.
The method of production biruea is mainly that hydrazine hydrate and urea are condensed in the case where having acid or acid-free condition at present, patent
(application number：201510149075.0) a kind of new process synthesizing biruea using semicarbazides is described, by semicarbazides and cyanic acid
Salt solid is added to the water, and controls temperature, is then slowly added into acid, you can obtain biruea solid.The technique can be in normal temperature and pressure
Lower operation, yield reaches 100%, while by-product is sodium salt, environmentally safe.
One of primary raw material is semicarbazides in above-mentioned technique, and semicarbazides reported in the literature has many synthetic methods.The U.S.
Using carbon monoxide and hydrazine hydrate as raw material in patent (US24526), semicarbazides is obtained by the reaction under high pressure and metal carbonyl catalysis,
It is acidified again up to semicarbazide hydrochloride with hydrochloric acid later.United States Patent (USP) (US2749217) describes a kind of nitrourea and adds hydrogen coproduction hydroxyl
The technique of amine salt and semicarbazides salt uses inorganic acid and atent solvent for reaction solution, under hydrogenation catalyst effect, has investigated not
Influence with process conditions to hydroxylamine salt and semicarbazides salt selectivity.Reaction equation is as follows：
Process conditions are mild compared to US24526 in the technique, but nitrourea is hydrogenated to hydroxylamine salt and semicarbazides salt
Reaction be competitive reaction, it is both soluble easily in water, and azanol is easy to be thermally decomposed, and causes later separation difficult, it is difficult to comprehensive
It utilizes.
Invention content
It is an object of the invention to overcome the shortcomings of the prior art, and provide a kind of coproduction biruea and hydroxyl sulfate
Method, nitrourea, sulfuric acid and catalyst, control material ratio, reaction temperature and reaction pressure are added in hydrogenation reaction kettle,
After hydroxylamine salt to be generated and semicarbazides salt, catalyst is centrifuged out, the solution containing cyanate, semicarbazides salt and cyanogen is slowly added dropwise
Hydrochlorate directly generates biruea under acid system, and hydroxylamine salt is converted to hydroxyl sulfate in the presence of sulphuric acid, and biruea is available
In production ADC foaming agents, and hydroxyl sulfate is used as analytical reagent, reducing agent, is also used for organic synthesis, benefit may be implemented most
Bigization.
The purpose of the present invention is by following technical solution to complete.The side of this coproduction biruea and hydroxyl sulfate
Method, this method several steps under including：
A. a certain amount of nitrourea, sulfuric acid and catalyst are added into hydrogenation reaction kettle, wherein sulfuric acid and nitrourea rubs
You are than being 0.5~32:1, wherein catalyst amount is the 0.5%~3% of nitrourea quality, opens stirring；
B. it is passed through hydrogen, rises to reaction temperature and reaction pressure, and control the reaction time.Wherein reaction temperature is 0~50
DEG C, reaction pressure is in 0.10~10Mpa；
C. after reaction, reaction Mother liquor is centrifuged, isolates catalyst, be neutralized to sulfuric acid concentration 5%~
50%, guarantee system acidity is more than cyanic acid acidity, and the solution containing cyanate is slowly slowly added dropwise into system, that is, has white precipitate
It generates, filters up to biruea product.Wherein the molar ratio of cyanate and nitrourea is 0.8~2:1.
D. filtrate is subjected to condensing crystallizing, you can obtain hydroxyl sulfate product, the reaction was continued for unreacted raw material, and cycle makes
With raising total recovery.
In the present invention, catalyst is noble metal catalyst, one kind or several in active component Pd, Pt, Au, Ag etc.
Kind, carrier is one or more of activated carbon, alundum (Al2O3), silica etc., the load capacity of active component is 1%~
10%.
In the present invention, step b is realized under pressurized condition, and the conversion of nitrourea is conducive to, and step c is normal in room temperature
Pressure is realized, is conducive to cost-effective.
In the present invention, cyanate is one or more of Zassol, potassium cyanate, calcium cyanate, cyanic acid magnesium in step c.
Beneficial effects of the present invention are：Using nitrourea hydrogenation synthesis hydroxylamine salt and semicarbazides salt, without being carried out to product
Separation, can be directly added into cyanate, you can coproduction biruea and hydroxyl sulfate realize the maximization of benefit.
Specific implementation mode
Detailed introduction is done to the present invention below in conjunction with embodiment：
The method of this coproduction biruea and hydroxyl sulfate of the present invention, this method several steps under including：
A. a certain amount of nitrourea, sulfuric acid and catalyst are added into hydrogenation reaction kettle, wherein sulfuric acid and nitrourea rubs
You are than being 0.5~32:1, wherein catalyst amount is the 0.5%~3% of nitrourea quality, opens stirring；Your gold catalyst is
Metal catalyst, one or more of active component Pd, Pt, Au, Ag etc., carrier are activated carbon, alundum (Al2O3), dioxy
The load capacity of one or more of SiClx etc., active component is 1%~10%.
B. it is passed through hydrogen, rises to reaction temperature and reaction pressure, and control the reaction time.Wherein reaction temperature is 0~50
DEG C, reaction pressure is in 0.10~10Mpa；
C. after reaction, reaction Mother liquor is centrifuged, isolates catalyst, be neutralized to sulfuric acid concentration 5%~
50%, guarantee system acidity is more than cyanic acid acidity, and the solution containing cyanate is slowly slowly added dropwise into system, that is, has white precipitate
It generates, filters up to biruea product.Wherein the molar ratio of cyanate and nitrourea is 0.8~2:1, cyanate be Zassol,
One or more of potassium cyanate, calcium cyanate, cyanic acid magnesium.
D. filtrate is subjected to condensing crystallizing, you can obtain hydroxyl sulfate product, the reaction was continued for unreacted raw material, and cycle makes
With raising total recovery.
In the present invention, step b is realized under pressurized condition, and the conversion of nitrourea is conducive to, and step c is normal in room temperature
Pressure is realized, is conducive to cost-effective.
Embodiment 1
It is negative that 10.5g nitroureas, 20mL water, the sulfuric acid of 10mL a concentration of 60% and 0.1g is added into hydrogenation reaction kettle successively
The Pt/C catalyst that carrying capacity is 5% opens stirring.Reaction temperature is increased to 20 DEG C, keeps pressure 0.5Mpa, to the end of reaction
Afterwards, pressure is laid down, catalyst is centrifuged out, it is 10% to be neutralized to sulfuric acid concentration, and cyanic acid sodium solution is then slowly added dropwise, wherein
The content of Zassol is 6.6g, and the white precipitate of generation is filtered, washed, dries and weighs.Filtrate is subjected to condensing crystallizing, it is raw
At white crystalline material, be filtered, washed, dry and weigh.
Embodiment 2
It is negative that 10.5g nitroureas, 20mL water, the sulfuric acid of 10mL a concentration of 80% and 0.1g is added into hydrogenation reaction kettle successively
The Pd/C catalyst that carrying capacity is 5% opens stirring.Reaction temperature is increased to 50 DEG C, keeps pressure 0.5Mpa, to the end of reaction
Afterwards, pressure is laid down, catalyst is centrifuged out, it is 10% to be neutralized to sulfuric acid concentration, and cyanic acid sodium solution is then slowly added dropwise, wherein
The content of Zassol is 7.92g, and the white precipitate of generation is filtered, washed, dries and weighs.Filtrate is subjected to condensing crystallizing, it is raw
At white crystalline material, be filtered, washed, dry and weigh.
Embodiment 3
It is negative that 10.5g nitroureas, 20mL water, the sulfuric acid of 20mL a concentration of 80% and 0.1g is added into hydrogenation reaction kettle successively
The Pd/Al that carrying capacity is 10%2O3Catalyst opens stirring.Reaction temperature is increased to 50 DEG C, keeps pressure 1.0Mpa, waits for reaction knot
Shu Hou lays down pressure, centrifuges out catalyst, and it is 10% to be neutralized to sulfuric acid concentration, and cyanic acid sodium solution is then slowly added dropwise,
The content of middle Zassol is 7.92g, and the white precipitate of generation is filtered, washed, dries, and measures fusing point and weighs.Filtrate is carried out
Condensing crystallizing, the white crystalline material of generation are filtered, washed, dry, and measure fusing point and weigh.
Embodiment result is as follows：
Wherein, white precipitate fusing point is 242~248 DEG C, and white crystals fusing point is 170~172 DEG C
It is understood that the above-mentioned specific implementation mode technical solution that the invention is not limited in any way, every to adopt
The technical solution obtained with the mode of equivalent replacement or equivalent exchange all belongs to the scope of protection of the present invention.
Claims (4)
1. a kind of method of coproduction biruea and hydroxyl sulfate, which is characterized in that this method includes following steps：
A. a certain amount of nitrourea, sulfuric acid and catalyst, the wherein molar ratio of sulfuric acid and nitrourea are added into hydrogenation reaction kettle
It is 0.5~32:1, wherein catalyst amount is the 0.5%~3% of nitrourea quality, opens stirring；
B. it is passed through hydrogen, rises to reaction temperature and reaction pressure, and control the reaction time, wherein reaction temperature is at 0~50 DEG C, instead
Answer pressure in 0.10~10Mpa；
C. after reaction, reaction Mother liquor is centrifuged, isolates catalyst, reused；It is acid big to be neutralized to system
After cyanic acid acidity, the solution containing cyanate is slowly slowly added dropwise into system, that is, has white precipitate generation, filters up to union II
Urea product；Wherein the molar ratio of cyanate and nitrourea is 0.8~2:1；
D. filtrate is subjected to condensing crystallizing, you can obtain hydroxyl sulfate product, the reaction was continued for unreacted raw material, recycles.
2. the method for coproduction biruea and hydroxyl sulfate according to claim 1, it is characterised in that：Catalyst in step a
For noble metal catalyst, one or more of active component Pd, Pt, Au or Ag, carrier is activated carbon, alundum (Al2O3)
Or one or more of silica.
3. the method for coproduction biruea and hydroxyl sulfate according to claim 1, it is characterised in that：Cyanate in step c
For one or more of Zassol, potassium cyanate, calcium cyanate, cyanic acid magnesium.
4. the method for coproduction biruea and hydroxyl sulfate according to claim 2, it is characterised in that：Activearm in catalyst
The load capacity divided is 1%~10%.
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| CN201710019799.2A CN106831497B (en) | 2017-01-11 | 2017-01-11 | A kind of method of coproduction biruea and hydroxyl sulfate |
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| CN201710019799.2A CN106831497B (en) | 2017-01-11 | 2017-01-11 | A kind of method of coproduction biruea and hydroxyl sulfate |
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| CN106831497B true CN106831497B (en) | 2018-10-02 |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2749217A (en) * | 1953-10-12 | 1956-06-05 | Spencer Chem Co | Production of hydroxylamine and semicarbazide salts |
| US3238226A (en) * | 1962-02-19 | 1966-03-01 | Nat Polychemicals Inc | Synthesis of hydrazine, semi-carbazide, and hydrazinedicarbonamide |
| US4482738A (en) * | 1983-08-01 | 1984-11-13 | Olin Corporation | Process for preparing semicarbazide hydrochloride |
| CN104844481A (en) * | 2015-03-31 | 2015-08-19 | 杭州海虹精细化工有限公司 | Process for synthesizing biurea by adopting semicarbazide |
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