CN101077780A - Method for preparing sodium thiocarbonate by phase transfer catalytic method - Google Patents
Method for preparing sodium thiocarbonate by phase transfer catalytic method Download PDFInfo
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- CN101077780A CN101077780A CN 200710078618 CN200710078618A CN101077780A CN 101077780 A CN101077780 A CN 101077780A CN 200710078618 CN200710078618 CN 200710078618 CN 200710078618 A CN200710078618 A CN 200710078618A CN 101077780 A CN101077780 A CN 101077780A
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Abstract
The present invention discloses phase transfer catalysis process of preparing sodium sulfocarbonate. The process is one normal temperature and normal pressure reaction process of sodium sulfide and carbon disulfide in the presence of ionic liquid as the phase transfer catalyst. The process includes the steps of: mixing industrial pure carbon disulfide and sodium sulfide water solution, adding ionic liquid in 5-10 vol% of the carbon disulfide, reacting for 5-10 min, and cooling to separate out sodium sulfocarbonate crystal. The present invention has lowered phase interface between sodium sulfide or sodium hydroxide water solution and carbon disulfide, raised reaction rate at normal temperature and normal pressure, low sodium sulfocarbonate preparing cost.
Description
Technical field
The present invention relates to utilize the method for ionic liquid as the synthetic sodium thiocarbonate of phase-transfer catalyst.
Background technology
Ionic liquid is the material that is made of ion that is in a liquid state under near temperature room temperature or the room temperature, is called ionic liquid at room temperature, room temperature melting salt or organic ion liquid etc. again.Ionic liquid at room temperature is meant the ionic compound that is liquid near the temperature range very big room temperature, and it has well solved the instability problem of material under hot conditions, so ionic liquid at room temperature has very big research and market potential.Mainly concentrate on sign, catalytic synthesis, extracting and separating and the electrochemistry aspect of ion liquid preparation, physics and chemical property both at home and abroad at present about the research of ionic liquid chemistry.
Ionic liquid is of a great variety, changes positively charged ion, anionic various combination, can design to synthesize different ionic liquids.Ion liquid positively charged ion is generally that volume ratio is big, the organic ion of low-symmetry.The most frequently used is imidazol ion, quaternary ammonium ion, pyridinium ion, phosphonium ion, sulfonium ion, pyrroles's ion, thiazole ion, triazolone ion and the pyrazoles ion etc. that have different alkyl substituents.Ionic liquid at room temperature is in water white liquid state, has very big advantage at it aspect the solvent in the organic reaction, and the disclosed CN1361716A of Chinese patent has detailed argumentation to this.Except to the research of ionic liquid as the solvent aspect, people have also done certain research to the catalysis characteristics of ionic liquid, and the functionalized ion liquid of new function specific (task-specific) more and more is subjected to people's attention at present.
Sodium thiocarbonate is important heavy metal containing wastewater treatment agent, also is polysulfide synthetic starting material, and commodity are called Thio-Red
, its preparation sodium sulphite or aqueous sodium hydroxide solution and dithiocarbonic anhydride of adopting react more.Because it is the boiling point low (boiling point is 43.6 ℃ under the normal pressure) of dithiocarbonic anhydride, and inflammable, explosive.Because the dithiocarbonic anhydride and the aqueous solution do not dissolve each other, there is phase interface in reaction, makes combined coefficient lower again.From the CN1837051 of Chinese patent disclosure as can be known, with alcohol as phase-transfer catalyst, and with reaction system put into microwave catalysis synthetic/abstraction instrument reacts.During 30 ℃～40 ℃ of temperature of reaction, reach transformation efficiency reaction times of 98% needs 20min.As can be seen, also there is long reaction time in synthesizing of sodium thiocarbonate, illustrates that alcohol is not high as the efficient of consisting of phase-transferring agent, and the later stage need use condensation reflux unit to separate.
Summary of the invention
At above shortcomings in the prior art, the purpose of this invention is to provide a kind of utilization efficiently phase-transfer catalyst prepare the method for sodium thiocarbonate.
The object of the present invention is achieved like this: a kind of method of preparing sodium thiocarbonate by phase transfer catalytic method, it is characterized in that, and as phase-transfer catalyst, make sodium sulphite and dithiocarbonic anhydride under normal pressure and temperature, finish reaction with ionic liquid; Concrete steps are as follows:
A, commercially pure dithiocarbonic anhydride and sodium sulfide solution are mixed, the ratio of the amount of substance of dithiocarbonic anhydride and sodium sulphite (mole) is about 1～1.2: 1; Add ionic liquid under mechanical stirring, ion liquid consumption is 5%～10% of a dithiocarbonic anhydride volume, preferred 8%.
B, under normal pressure, room temperature, react 5min～10min;
After c, reaction finished, cooling reaction system allowed the sodium thiocarbonate crystallization separate out, and carries out the solid-liquid filtering separation;
It is sodium thiocarbonate that d, separation obtain crystal; Contain ionic liquid and water in the mother liquor, recyclable utilization again.
Described sodium sulphite gets final product with water dissolution, be the aqueous solution of 10%～80% (mass percent) or saturated solution all can, more suitable as 30%～60% the aqueous solution.
Used ionic liquid is pyrrole miaow chlorine, pyrrole miaow boron fluorine four or pyrrole miaow boron fluorine six.
Wherein the reaction process of step b is carried out under microwave radiation, and the microwave frequency of employing is that 2450MHz, power are 600W～1000W; Under microwave heating condition, controlling reaction time is 1min-3min, preferred 2min.
Compared to existing technology, the present invention has following beneficial effect:
(1) select for use ionic liquid as phase-transfer catalyst, reduced the phase interface between sodium sulphite or aqueous sodium hydroxide solution and the dithiocarbonic anhydride, improve reaction efficiency, reaction can be carried out at normal temperatures and pressures quickly, and in reaction process, do not needed heating and reflux.
(2) method that adopts ionic liquid and microwave to combine is utilized the non-thermal effect of microwave heating, and reaction system is at room temperature reacted, and shortens the reaction times when reducing the ionic liquid consumption; Improve reaction efficiency greatly, reduced the preparation cost of sodium thiocarbonate.
(3) utilize ionic liquid to be easy to the characteristics of Separation and Recovery, can reuse, reach and economize on resources the purpose that reduces cost.
In a word, the present invention is the preparation rapidly and efficiently of sodium thiocarbonate, and ionic liquid provides a new approach as the synthetic trithiocarbonate of phase-transfer catalyst.
Embodiment
Embodiment 1: with 24gNa
2S9H
2The O solid is dissolved in the 50mL distilled water, and the sodium sulfide solution of preparation is contained in the three-necked flask; Add 25mL CS
2With 1.25mL pyrrole miaow boron fluorine four ionic liquids.Reaction system is behind reaction 10min under the room temperature normal pressure, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 95.8%.
Embodiment 2: with 24gNa
2S9H
2The O solid is dissolved in the 50mL distilled water, and sodium sulfide solution is contained in the three-necked flask; Add 25mL CS
2With 2.5mL pyrrole miaow boron fluorine four ionic liquids.Reaction system is behind reaction 5min under the room temperature normal pressure, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 94.7%.
Embodiment 3: with 30gNa
2S9H
2The O solid is dissolved in the 50mL distilled water, and sodium sulfide solution is contained in the three-necked flask, adds 30mL CS
2With 2.4ml pyrrole miaow chlorion liquid.Reaction system is radiation 1min under microwave power 1000W, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 99.5%.
Embodiment 4: with 24gNa
2S9H
2The O solid is dissolved in the 50mL distilled water, and sodium sulfide solution is contained in the three-necked flask, adds 30mL CS
2With 3.0mL pyrrole miaow boron fluorine four ionic liquids.Reaction system is radiation 2min under microwave power 800W, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 99.2%.
Embodiment 5: with 30gNa
2S9H
2The O solid is dissolved in the 60mL distilled water, and sodium sulfide solution is contained in the three-necked flask, adds 30mL CS
2With 2.0mL pyrrole miaow boron fluorine four ionic liquids.Reaction system is radiation 2min under microwave power 600W, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 98.6%.
Embodiment 6: with 30gNa
2S9H
2The O solid is dissolved in the 60mL distilled water, and sodium sulfide solution is contained in the three-necked flask, adds 40mL CS
2With 2mL pyrrole miaow boron fluorine six ionic liquids.Reaction system is radiation 3min under microwave power 1000W, and solution changes separating funnel over to, leaves standstill separatory.Then, obtain the trithiocarbonic acid sodium crystal behind the low temperature crystallization.Show that with spectrophotometric analysis the transformation efficiency of sodium sulphite is 99.4%.
According to the inventive method, it is imidazol ion, quaternary ammonium ion, pyridinium ion, phosphonium ion, sulfonium ion, pyrroles's ion, thiazole ion, three oxazolinium ions or pyrazoles ion etc. that one of ordinary skill in the art also can select positively charged ion for use; Negatively charged ion is BF
4 -, PF
6 -, CF
3SO
3 -, CF
3CO
2 -, SbF
6 -, AlCl
4 -, CuCl
2 -, HSO
4 -Or NO
3 -Ionic liquid, can reach essentially identical effect.
Claims (4)
1, the method for preparing sodium thiocarbonate by phase transfer catalytic method is characterized in that, as phase-transfer catalyst, makes sodium sulphite and dithiocarbonic anhydride finish reaction with ionic liquid under normal pressure and temperature; Concrete steps are as follows:
A, commercially pure dithiocarbonic anhydride and sodium sulfide solution are mixed, the ratio of the amount of substance of dithiocarbonic anhydride and sodium sulphite is 1～1.2: 1; Add ionic liquid under mechanical stirring, ion liquid consumption is 5%～10% of a dithiocarbonic anhydride volume;
B, under normal pressure, room temperature, react 5min～10min;
After c, reaction finished, cooling reaction system allowed the sodium thiocarbonate crystallization separate out, and carries out the solid-liquid filtering separation;
It is sodium thiocarbonate that d, separation obtain crystal; Contain ionic liquid and water in the mother liquor, recycling.
2, the method for preparing sodium thiocarbonate by phase transfer catalytic method according to claim 1, it is characterized in that, the reaction process of step b is carried out under microwave radiation, and the microwave frequency of employing is that 2450MHz, power are 600W～1000W, and controlling reaction time is 1min～3min.
3, the method for preparing sodium thiocarbonate by phase transfer catalytic method according to claim 1 is characterized in that, described sodium sulphite gets final product with water dissolution, is 10%～80% the aqueous solution or saturated solution.
4, the method for preparing sodium thiocarbonate by phase transfer catalytic method according to claim 1 is characterized in that used ionic liquid is pyrrole miaow chlorine, pyrrole miaow boron fluorine four or pyrrole miaow boron fluorine six.
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| CN200710078618A CN101077780B (en) | 2007-06-14 | 2007-06-14 | Method for preparing sodium thiocarbonate by phase transfer catalytic method |
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| CN200710078618A CN101077780B (en) | 2007-06-14 | 2007-06-14 | Method for preparing sodium thiocarbonate by phase transfer catalytic method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926703A (en) * | 2015-04-30 | 2015-09-23 | 广西华锡集团股份有限公司 | Synthetic method and application for sodium carboxymethyl sodium trithiocarbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335412C (en) * | 2006-04-07 | 2007-09-05 | 重庆大学 | Process for preparing sodium sulfocarbonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926703A (en) * | 2015-04-30 | 2015-09-23 | 广西华锡集团股份有限公司 | Synthetic method and application for sodium carboxymethyl sodium trithiocarbonate |
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