CN101921293A - Method for preparing dialkyl dithiophosphate - Google Patents
Method for preparing dialkyl dithiophosphate Download PDFInfo
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- CN101921293A CN101921293A CN 201010238038 CN201010238038A CN101921293A CN 101921293 A CN101921293 A CN 101921293A CN 201010238038 CN201010238038 CN 201010238038 CN 201010238038 A CN201010238038 A CN 201010238038A CN 101921293 A CN101921293 A CN 101921293A
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Abstract
The invention discloses a method for preparing dialkyl dithiophosphate, comprising the following steps: (1) continuously adding phosphorus pentasulfide in an alcohol solution under stirring when the pressure is minus 0.01-0.05MPa and the temperature is 30-100 DEG C, and preserving the temperature and reacting for 2-5h to obtain dialkyl phosphorodithioicacid, wherein the weight ratio of the added phosphorus pentasulfide to the alcohol solution is 1: 4.0-4.8; and (2) under the temperature of 20-60 DEG C, adding a sodium hydroxide solution with the concentration of 15-25wt% in the dialkyl phosphorodithioicacid based on the weight ratio of 1: 1.0-1.1, and performing neutralization reaction to obtain the dialkyl dithiophosphate. In the invention, the reaction of the phosphorus pentasulfide and the alcohol solution has good effect, short reaction time, short production cycle and high product yield, and the waste gas generated by the reaction can be recycled, thus the invention is an environment-friendly and efficient production process.
Description
Technical field
The present invention relates to the collecting agent preparing technical field, relate in particular to a kind of preparation method of dialkyl dithiophosphate.
Background technology
Dialkyl dithiophosphate is a kind of sulfide mineral collector commonly used, be commonly called as black powder, compare with another kind of collecting agent xanthate commonly used, the flotation nature of black powder has two principal features: (1) collecting power is lower, selectivity is higher, and is particularly less to sulfurous iron ore collecting power, so be used as the differential flotation collecting agent in high copper of Containing Sulfur iron and lead zinc sulphur ore flotation, can obtain the concentrate than good quality, while many kinds of black powder are to the collecting better performances of gold; (2) good stability can use unlikely quilt to decompose rapidly under low pH value.
The preparation method of dialkyl dithiophosphate is for adopting thiophosphoric anhydride and the different corresponding black powder acid of alcohols reaction generation, place sedimentation then, be generally 3 to 5 days, and filtered then and remove the impurity that reaction generates, again black powder acid is obtained corresponding black powder with the sodium hydroxide neutralization.The deficiency that prior art exists is: the production cycle is long, and production efficiency is low, and impurity is many in the product, and exhaust emission is serious.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiency that prior art exists, provide a kind of and react uniform and stable, product impurity is few, with short production cycle, production cost is low and the preparation method of the dialkyl dithiophosphate of environmental pollution difference.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of preparation method of dialkyl dithiophosphate may further comprise the steps:
(1) under the whipped state, be-0.01～0.05MPa at pressure, when temperature is 30～100 ℃, join thiophosphoric anhydride in the alcoholic solution continuously, the adding weight ratio of described thiophosphoric anhydride and alcoholic solution is 1: 4.0～4.8, and insulation reaction 2～5 hours obtains dialkyl dithiophosphoric acid.
(2) when temperature is 20～60 ℃, with concentration is that the sodium hydroxide solution of 15～25wt% joins in the dialkyl dithiophosphoric acid, the adding weight ratio of described sodium hydroxide solution and dialkyl dithiophosphoric acid is 1: 1.0～1.1, carries out neutralization reaction and obtains dialkyl dithiophosphate.
In the step (1), when joining thiophosphoric anhydride in the alcoholic solution continuously, the employing automatic feeding device adds, described automatic feeding device comprises the feeding device that is communicated with the reaction vessel of alcoholic solution with thiophosphoric anhydride, be located at temperature measuring equipment in the described reaction vessel and the discharging control device that is communicated with temperature measuring equipment and feeding device respectively, temperature of reaction in the reaction vessel that described discharging control device measures according to temperature measuring equipment, the adding speed of regulating thiophosphoric anhydride in the feeding device automatically.
In the step (2), react with sodium hydroxide solution after the tail gas recycle that described neutralization reaction produces, convert Sodium sulfhydrate to and recycle.
In the step (2), carry out in absorbing converter when the tail gas of recovery and sodium hydroxide reaction, the pressure in the absorption tower is-0.01～0.05MPa, and described absorption progression is 2～8 grades, and the described Sodium sulfhydrate concentration that converts to is 18～25wt%.
Described alcoholic solution is the alcoholic solution of concentration 〉=99.5wt%; The alcoholic solution of described concentration 〉=99.5wt% is the solution of ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol or primary isoamyl alcohol.
In the step (1), the concentration of the dialkyl dithiophosphoric acid that reaction obtains is 82～88wt%.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, thiophosphoric anhydride of the present invention and alcoholic solution reaction effect are good, and the reaction times is short, and is with short production cycle, and the product yield height, so the production efficiency height, and production cost is low.
2, the present invention adopts automatic feeding device when thiophosphoric anhydride is reinforced, automatically regulate the adding speed of thiophosphoric anhydride according to the temperature of reaction of thiophosphoric anhydride and alcoholic solution, therefore steadily, byproduct of reaction is few continuously in reaction, and product impurity is few, the feed stock conversion height, the product yield height, and, saved placement precipitation step of the prior art because by product is few, therefore simplify technical process, shortened the production cycle.
3, the present invention is converted to Sodium sulfhydrate with the tail gas that neutralization reaction produces, Sodium sulfhydrate can be used as byproduct and takes out, not only having increased productivity effect, and avoided in the prior art because of the exhaust emissions pollution on the environment, is a kind of environmental protection, production technique efficiently.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
(1) automatic feeding device is being housed, electric mixer and condenser, described condenser connects in the 1000ml closed reaction vessel of 4 grades of absorption converters, adding concentration is the isobutanol solution of 99.5wt%, start stirring, keep system pressure to be-0.01MPa, when the controlled temperature of automatic feeding device is set at 50 ℃, use automatic feeding device to join in the isobutanol solution uniformly thiophosphoric anhydride continuously, the adding weight ratio of described thiophosphoric anhydride and isobutanol solution is 1: 4.2, add follow-up continuation of insurance temperature reaction 5 hours, obtaining concentration is the diisobutyl phosphorodithioic acid of 83wt%.
(2) when temperature is 30 ℃, with concentration is that the sodium hydroxide solution of 20wt% slowly joins in the reaction vessel, the adding weight ratio of described sodium hydroxide and diisobutyl phosphorodithioic acid is 1: 1, carry out neutralization reaction, start the tail gas that absorbs the generation of converter absorption reaction simultaneously, obtain product diisobutyl phosphorodithioic acid sodium.
(3) keeping absorbing the converter internal pressure is 0.01MPa, and the tail gas of recovery and the sodium hydroxide solution of 20wt% are carried out 4 grades of absorption conversion reactions, is converted to the sodium hydrosulfide of 20wt%.
Embodiment 2
(1) automatic feeding device is being housed, electric mixer and condenser, described condenser connects in the 1000ml closed reaction vessel of 6 grades of absorption converters, adding concentration is the ethanolic soln of 99.5wt%, start stirring, the maintenance system pressure is 0.02MPa, when the controlled temperature of automatic feeding device is set at 70 ℃, use automatic feeding device to join in the ethanolic soln uniformly thiophosphoric anhydride continuously, the adding weight ratio of described thiophosphoric anhydride and ethanolic soln is 1: 4.5, add follow-up continuation of insurance temperature reaction 4 hours, obtain the diethyldithiophosphoric acid that concentration is 84wt%.
(2) when temperature is 40 ℃, with concentration is that the sodium hydroxide solution of 19wt% slowly joins in the reaction vessel, the adding weight ratio of described sodium hydroxide and diethyldithiophosphoric acid is 1: 1.05, carry out neutralization reaction, start the tail gas that absorbs the generation of converter absorption reaction simultaneously, obtain product diethyldithiophosphoric acid sodium.
(3) keeping absorbing the converter internal pressure is 0.02MPa, and the tail gas of recovery and the sodium hydroxide solution of 19wt% are carried out level Four absorption conversion reaction, is converted to the sodium hydrosulfide of 21wt%.
Embodiment 3
(1) automatic feeding device is being housed, electric mixer and condenser, described condenser connects in the 1000ml closed reaction vessel of 7 grades of absorption converters, adding concentration is the aqueous isopropanol of 99.5wt%, start stirring, the maintenance system pressure is 0.03MPa, when the controlled temperature of automatic feeding device is set at 85 ℃, use automatic feeding device to join in the aqueous isopropanol uniformly thiophosphoric anhydride continuously, the adding weight ratio of described thiophosphoric anhydride and aqueous isopropanol is 1: 4.6, add follow-up continuation of insurance temperature reaction 3 hours, the diisopropyl disulfide that obtains concentration and be 85wt% is for phosphoric acid.
(2) when temperature is 50 ℃, with concentration is that the sodium hydroxide solution of 18wt% slowly joins in the reaction vessel, the adding weight ratio of described sodium hydroxide and dipropyl butyl phosphorodithioic acid is 1: 1.1, carry out neutralization reaction, start the tail gas that absorbs the generation of converter absorption reaction simultaneously, obtain the product diisopropyl disulfide for sodium phosphate.
(3) keeping absorbing the converter internal pressure is 0.03MPa, and the tail gas of recovery and the sodium hydroxide solution of 18wt% are carried out level Four absorption conversion reaction, is converted to the sodium hydrosulfide of 20wt%.
Claims (6)
1. the preparation method of a dialkyl dithiophosphate is characterized in that may further comprise the steps:
(1) under the whipped state, be-0.01～0.05MPa at pressure, when temperature is 30～100 ℃, join thiophosphoric anhydride in the alcoholic solution continuously, the adding weight ratio of described thiophosphoric anhydride and alcoholic solution is 1: 4.0～4.8, and insulation reaction 2～5 hours obtains dialkyl dithiophosphoric acid;
(2) when temperature is 20～60 ℃, with concentration is that the sodium hydroxide solution of 15～25wt% joins in the dialkyl dithiophosphoric acid, the adding weight ratio of described sodium hydroxide solution and dialkyl dithiophosphoric acid is 1: 1.0～1.1, carries out neutralization reaction and obtains dialkyl dithiophosphate.
2. the preparation method of dialkyl dithiophosphate as claimed in claim 1, it is characterized in that: in the step (1), when joining thiophosphoric anhydride in the alcoholic solution continuously, the employing automatic feeding device adds, described automatic feeding device comprises the feeding device that is communicated with the reaction vessel of alcoholic solution with thiophosphoric anhydride, be located at temperature measuring equipment in the described reaction vessel and the discharging control device that is communicated with temperature measuring equipment and feeding device respectively, temperature of reaction in the reaction vessel that described discharging control device measures according to temperature measuring equipment, the adding speed of regulating thiophosphoric anhydride in the feeding device automatically.
3. the preparation method of dialkyl dithiophosphate as claimed in claim 2 is characterized in that: in the step (2), react with sodium hydroxide solution after the tail gas recycle that described neutralization reaction produces, convert Sodium sulfhydrate to and recycle.
4. the preparation method of dialkyl dithiophosphate as claimed in claim 3, it is characterized in that: in the step (2), carry out in absorbing converter when tail gas that reclaims and sodium hydroxide reaction, described absorption progression is 2～8 grades, and the described Sodium sulfhydrate concentration that converts to is 18～25wt%.
5. the preparation method of dialkyl dithiophosphate as claimed in claim 2, it is characterized in that: described alcoholic solution is the alcoholic solution of concentration 〉=99.5wt%; The alcoholic solution of described concentration 〉=99.5wt% is the solution of ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol or primary isoamyl alcohol.
6. the preparation method of dialkyl dithiophosphate as claimed in claim 2 is characterized in that: in the step (1), the concentration of the dialkyl dithiophosphoric acid that reaction obtains is 82～88wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201010238038 CN101921293A (en) | 2010-07-28 | 2010-07-28 | Method for preparing dialkyl dithiophosphate |
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| CN 201010238038 CN101921293A (en) | 2010-07-28 | 2010-07-28 | Method for preparing dialkyl dithiophosphate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017310A (en) * | 2015-07-01 | 2015-11-04 | 辽宁石油化工大学 | Method for catalytic preparation of solvent-free thio-phosphoric acid |
| CN105601667A (en) * | 2015-11-28 | 2016-05-25 | 辽宁石油化工大学 | Production method for oil-containing thiophosphoric acid |
| CN107312031A (en) * | 2017-06-22 | 2017-11-03 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of di-isooctyl dithio zinc phosphate salt |
| CN108892686A (en) * | 2018-06-13 | 2018-11-27 | 烟台恒邦化工助剂有限公司 | A kind of production technology of butyl ammonium aerofloat |
| CN113680535A (en) * | 2021-08-24 | 2021-11-23 | 中南大学 | Alkyl ether group dithiophosphate collecting agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625191A (en) * | 1979-08-09 | 1981-03-10 | Nippon Chem Ind Co Ltd:The | Preparation of high-purity water-soluble o,o-dialkyl dithiophosphate |
| US20040176629A1 (en) * | 2003-03-07 | 2004-09-09 | Prasad Vidyanatha A. | Method for preparing O,O-dialkyl S-[2-(alkylthio)alkyl] phosphorodithioates |
| CN201441905U (en) * | 2009-05-30 | 2010-04-28 | 潍坊世华化工有限公司 | Automatic alkyl phosphorothioate feeding device |
-
2010
- 2010-07-28 CN CN 201010238038 patent/CN101921293A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625191A (en) * | 1979-08-09 | 1981-03-10 | Nippon Chem Ind Co Ltd:The | Preparation of high-purity water-soluble o,o-dialkyl dithiophosphate |
| US20040176629A1 (en) * | 2003-03-07 | 2004-09-09 | Prasad Vidyanatha A. | Method for preparing O,O-dialkyl S-[2-(alkylthio)alkyl] phosphorodithioates |
| CN201441905U (en) * | 2009-05-30 | 2010-04-28 | 潍坊世华化工有限公司 | Automatic alkyl phosphorothioate feeding device |
Non-Patent Citations (1)
| Title |
|---|
| 《陕西化工》 19971231 张长荣等 O, O'-二异丙基二硫代磷酸钠的合成及其应用研究 21-25 1-6 , * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017310A (en) * | 2015-07-01 | 2015-11-04 | 辽宁石油化工大学 | Method for catalytic preparation of solvent-free thio-phosphoric acid |
| CN105601667A (en) * | 2015-11-28 | 2016-05-25 | 辽宁石油化工大学 | Production method for oil-containing thiophosphoric acid |
| CN107312031A (en) * | 2017-06-22 | 2017-11-03 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of di-isooctyl dithio zinc phosphate salt |
| CN108892686A (en) * | 2018-06-13 | 2018-11-27 | 烟台恒邦化工助剂有限公司 | A kind of production technology of butyl ammonium aerofloat |
| CN113680535A (en) * | 2021-08-24 | 2021-11-23 | 中南大学 | Alkyl ether group dithiophosphate collecting agent and preparation method and application thereof |
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Application publication date: 20101222 |