CN87101820A - A kind of preparation method who is used for the new dolomite inhibitor sulfomethylated derivative of calcium lignosulfonate of phosphate rock floating - Google Patents
A kind of preparation method who is used for the new dolomite inhibitor sulfomethylated derivative of calcium lignosulfonate of phosphate rock floating Download PDFInfo
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- CN87101820A CN87101820A CN87101820.9A CN87101820A CN87101820A CN 87101820 A CN87101820 A CN 87101820A CN 87101820 A CN87101820 A CN 87101820A CN 87101820 A CN87101820 A CN 87101820A
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- calcium lignosulfonate
- sulfomethylation
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Abstract
A kind of novel, preparation method of phosphorus ore flotation depressor sulfomethylated derivative of calcium lignosulfonate (be called for short L-339) efficiently, it is a raw material with needlebush sulphite process papermaking byproduct calcium lignosulfonate, in the presence of sulfuric acid, after the acidifying decalcification, carry out sulfomethylation and make with formaldehyde, S-WAT.This method has adopted the optimum process condition that helps improving product flotation rejection, and the L of gained-339 product is used for phosphate rock floating to be used as inhibitor and can reach good floatation indicators, for the development and use of low-grade phosphate ore provide approach.This method technological process and need are simple with equipment, easy to operate, are suitable for suitability for industrialized production.
Description
The invention relates to the preparation method of a kind of new dolomite inhibitor sulfomethylated derivative of calcium lignosulfonate that phosphate rock floating uses, belong to the chemical industry field.
Sulfomethylated derivative of calcium lignosulfonate is a kind of novel, rhombspar inhibitor efficiently, it not only has the intensive selectivity to suppress ability to rhombspar, and can suppress impurity such as calcite, siliceous and iron aluminium effectively, be specially adapted to the flotation of high magnesium type sedimentary metamorphic rock phosphorite ore.Its application makes the phosphate rock floating product under the prerequisite of higher-grade, high yield, has reduced the content of MgO impurity significantly.Improved the phosphorus concentrate quality, for approach has been opened up in the exploitation utilization of a large amount of low-grade phosphate ores.In being the patent application specification of 86107171 " application of sulfomethylated derivative of calcium lignosulfonate in phosphate rock floating ", application number describes in detail about this point.
The sulfonation of lignin and other derivative be it is found that and are familiar with that And is widely used in producing fields such as dispersion agent and tensio-active agent, and its preparation technology is also had the patent report abroad.A kind of preparation method who is used to strengthen the sulfonated lignin product of dispersion agent and surfactant activity is for example disclosed among the United States Patent (USP) U.S.P4069217, it is to be raw material with the sodium lignosulfonate, through alkaline oxygenated, hydrolysis, part take off sulphur, complicated technology such as sulfonation reaction makes again.So far be not reported as for relating to the preparation method of phosphate rock floating as the lignin sulfonated derivative of rhombspar inhibitor.
The objective of the invention is, provide a kind of technology simple, be applicable to the preparation method of phosphate rock floating as the sulfomethylated derivative of calcium lignosulfonate (being called for short L-339) of rhombspar inhibitor.
Raw material calcium lignosulfonate of the present invention is the byproduct of needlebush timber sulphite process papermaking gained such as pine.The structural unit of needle lignin mainly is a lignum-vitae base propane
With a spot of hydroxy propane
As everyone knows, phenol nuclear can directly be introduced a sulphur methyl with formaldehyde in the presence of S-WAT, the calcium lignosulfonate molecular structure unit has phenol nuclear, therefore can adopt this method to carry out sulfomethylation, be that calcium lignosulfonate carries out sulfomethylation with formaldehyde, S-WAT after the sulfuric acid acidation decalcification,-the OH ortho position is introduced the sulphur methyl, thereby is made the rhombspar inhibitor with expection flotation performance.
The method that the present invention utilizes above-mentioned principle to prepare L-339 is made up of following three reactions:
(1) formaldehyde and S-WAT carry out the hydroxyl addition reaction in the presence of acid, generate S-WAT formaldehyde affixture and sodium sulfate mixture, and it is standby to be sulfomethylation reagent.
(2) calcium lignosulfonate and sulfuric acid carry out acidifying decalcification reaction, generate C
aSO
4Precipitation.
(3) above-mentioned calcium lignosulfonate decalcification product and sulfomethylation reagent carry out sulfomethylation and obtain the product sulfomethylated derivative of calcium lignosulfonate.
Embodiment of the present invention follow these steps to carry out:
Sulfomethylation reagent is prefabricated-add metering hot water in the reactor, stirring down, the adding solid sodium sulfite makes its dissolving, add formalin then, drip the dilute sulphuric acid of 30% concentration again, the speed that splashes into ℃ is advisable with temperature of charge＜70, finish, in 70～75 ℃ down reaction after 0.5 hour discharging standby, S-WAT, formaldehyde and sulfuric acid all with etc. mole number add.
Add metering hot water in calcium lignosulfonate acidifying decalcification and the sulfomethylation process-reactor, add the stirring of solid calcium lignosulfonate then and make its dissolving, splash into the dilute sulphuric acid of 60% concentration, produce C
aSO
4Precipitation splashes into prefabricated sulfomethylation reagent wherein again, at last the reaction product discharging is weighed, and presses the calcium lignosulfonate charging capacity with 30% concentration measurement, adds to measure to merge behind the water washing reactor to stir evenly, and promptly gets the L-339 product.
Further specify the processing condition and the examination and test of products method of calcium lignosulfonate acidifying decalcification and sulfomethylation process among the preparation method of the present invention below.
One, the reinforced proportioning of reactant
Because calcium lignosulfonate is the mixture of different molecular weight, different structure unit molecule, can't calculate the mole number that it participates in sulfomethylation.The present invention seeks the best proportioning between the reactant by change sulfomethylation reagent and vitriolic consumption.Fig. 1 and Fig. 2 represent respectively when the calcium lignosulfonate charging capacity is 5Kg, the variation of sulfuric acid and sulfomethylation reagent dosage is to the influence of product L-339 rejection (E% is that phosphorus ore is roughly selected sorting index among the figure), as seen from the figure, the vitriolic optimum amount is 1.2Kg, sulfomethylation reagent is 6 moles, be converted into weight ratio, then calcium lignosulfonate: sulfuric acid: sulfomethylation reagent is that 1: 0.24: 0.61 selected scope is 1: 0.23～0.25: 0.56～0.68
Two, temperature of reaction
Reaction mass viscosity of the present invention is bigger, for fear of local superheating or the coking phenomenon occurs.The sulfomethylation temperature is unsuitable too high, and the present invention adopts 85～88 ℃, and the L-339 product floatation indicators that obtains under this temperature is better, and is mobile during discharging.
Three, acidificatoin time
Calcium lignosulfonate adds the rejection that the length of acidificatoin time behind the dilute sulphuric acid also can influence product, and Fig. 3 represents that acidificatoin time and product roughly select the relation of sorting index, and the present invention determines that according to Fig. 3 acidificatoin time is 18～22 minutes, Best Times 20 minutes.
Four, the sulfomethylation time
The time of sulfomethylation is relevant with temperature of reaction and stirring velocity, it is that 43 rev/mins and temperature of reaction are under 85～88 ℃ the condition that Fig. 4 is illustrated in agitator speed, relation between reaction times and the product rejection, among the figure as can be known optimum reacting time be generally to be advisable in 6.5 hours with 6-7 hour.
Five, reaction density
The weight percent that the calcium lignosulfonate charging capacity accounts for the Total Water sum of calcium lignosulfonate and adding is the reaction density of calcium lignosulfonate, this concentration value is 50% among the preparation method of the present invention, under this concentration, material has good mobility and can guarantee that reactor has bigger throughput.The summation of the water yield that water and dissolving added during S-WAT when above-mentioned Total Water was dissolved lignin calcium sulphonate water, dilute sulphuric acid, because both are quantitative for the backs, so this concentration is actual is to be controlled by the dissolving water yield of calcium lignosulfonate, and it is equated with the charging capacity of calcium lignosulfonate with both water yield sums of back.
Six, the examination and test of products
The L-339 product is that 53～55% o'clock separating effects are best at transmittance, therefore with the transmittance of measuring the product aqueous solution as the indirect Quality Control Analysis method of product of the present invention, the product transmittance was qualified at 50～60% o'clock.
The content of reduzate is better in 9-11% person's effect in the raw material calcium lignosulfonate of the present invention.
Adopt preparation method of the present invention, its technological process and required equipment are simple, easy to operate, because the present invention has adopted the optimum process condition that helps improving the product rejection, therefore the L-339 product that makes is used for phosphate rock floating and can reaches good floatation indicators as the rhombspar inhibitor, is a kind of phosphorus ore flotation depressor of excellence.
Among above-mentioned Fig. 1～Fig. 4, ordinate zou E% is the phosphate rock floating sorting index, and it is the index of reflection flotation effect.
Further specify preparation method of the present invention below by embodiment.
Add 4Kg cold water in 20 liters of acidproof enamel reactors, adding 3.8Kg industry S-WAT is carefully brilliant under stirring, and adding 2.55Kg37% formalin splashes into 30% dilute sulphuric acid (1.53Kg98%H then after the dissolving
2SO
4Be dissolved in 3.65Kg water, rate of addition is advisable less than 70 ℃ with temperature of charge, finishes, and in 70-75 ℃ of reaction 0.5 hour, gets brown solution and is sulfomethylation reagent, and discharging is standby.
Add 2.7Kg hot water in 20 liters of acidproof enamel reactors, stir adding 5Kg powdery or granule shape calcium lignosulfonate down, stir evenly the dilute sulphuric acid (1.2K that the back drips 60% concentration
g98%H
2SO
4Be dissolved in 0.8K
gCold water), dripped off in about 10 minutes, be warming up to 70 ℃, drip 3.05K after 20 minutes
gAbove-mentioned prefabricated sulfomethylation reagent dripped off in 10 minutes, was warming up to 85～88 ℃, start at reaction 6.5 hours when adding acid, discharging is weighed, and presses the calcium lignosulfonate charging capacity and calculates with 30% concentration, add metering water, merging stirs evenly behind the washing reaction still, promptly makes the L-339 product of 30% concentration.
The L-339 product is the black viscous liquid, has calcium sulfate precipitation to separate out after leaving standstill for a long time, needn't remove, and is made into 2% aqueous solution after shaking up and uses.
Raw materials used being described as follows in the foregoing description:
1, calcium lignosulfonate
Cut into a mountain and collect the outlet of man-made fiber slurry factory, tawny solid or dry powder, moisture 9% lignosulfonic acid calcium contents 55-60%, reduzate content 12%, C in Jilin Province
aO content 7.87%, when feeding intake by 100%.
2, formaldehyde
Industrial goods, content 37%.
3, S-WAT
Industrial goods, content 96%, when feeding intake by 100%.
4, sulfuric acid
Industrial goods, content 98%.
Claims (5)
1, the preparation method of a kind of phosphate rock floating rhombspar inhibitor sulfomethylated derivative of calcium lignosulfonate (L-339), it is characterized in that, this inhibitor is to be raw material with the calcium lignosulfonate, in the presence of sulfuric acid, carry out sulfomethylation with formaldehyde, S-WAT and make after the acidifying decalcification, preparation process is as follows:
(1), sulfomethylation trial-production preparation--S-WAT is dissolved in water in the reactor, moles of formaldehyde such as addings are mixed, and stir the dilute sulphuric acid that drips equimolar 30% concentration down, 70～75 ℃ were reacted 0.5 hour down, it is standby that resultant of reaction is sulfomethylation reagent.
(2), calcium lignosulfonate acidifying decalcification--input calcium lignosulfonate and hot water are mixed in the reactor.Stir down and drip 60% dilute sulphuric acid, be warming up to 70 ℃ of reactions 18～20 minutes, produce C
aSO
4Precipitation.
(3), drip sulfomethylation reagent in the reactant of above-mentioned (2) by (1) preparation, be warming up to 85～88 ℃, in step (2), add the discharging in 6～7 hours that reacts in the acid.
As the described method of above-mentioned claim 1, it is characterized in that 2, the vitriolic rate of addition is advisable for 70 ℃ with temperature of charge in the step (1).
As above-mentioned claim 1 or 2 described methods, it is characterized in that 3, the used sulfuric acid amount (calculating by clean sulfuric acid amount) and the ratio of sulfomethylation reagent dosage of calcium lignosulfonate charging capacity and acidifying is 1: 0.23～0.25: 0.56～0.68(weight ratio).The optimum proportion ratio is 1: 0.24: 0.61.
4, as the described method of above-mentioned claim 3, it is characterized in that, the reaction density of calcium lignosulfonate is 50%, under the situation that the water consumption and the used water yield of dilute sulphuric acid of dissolving S-WAT are determined, and hot water amount's control that this concentration is added by the dissolved lignin calcium sulphonate.
5, as above-mentioned claim 1 or 2 or 4 described methods, it is characterized in that, weigh after the product discharging, press the calcium lignosulfonate charging capacity, add to merge behind the metering water washing reactor and stir evenly with 30% concentration measurement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101820.9A CN1005258B (en) | 1987-03-07 | 1987-03-07 | Preparation method of sulfomethylated derivative of lignin calcium sulfonate, a new dolomite deressant for phosphorus mineral floatation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101820.9A CN1005258B (en) | 1987-03-07 | 1987-03-07 | Preparation method of sulfomethylated derivative of lignin calcium sulfonate, a new dolomite deressant for phosphorus mineral floatation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101820A true CN87101820A (en) | 1988-09-21 |
| CN1005258B CN1005258B (en) | 1989-09-27 |
Family
ID=4813640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101820.9A Expired CN1005258B (en) | 1987-03-07 | 1987-03-07 | Preparation method of sulfomethylated derivative of lignin calcium sulfonate, a new dolomite deressant for phosphorus mineral floatation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005258B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691574A (en) * | 2013-12-17 | 2014-04-02 | 广西大学 | Preparation method and application of dolomite inhibitor |
| CN105195334A (en) * | 2015-10-30 | 2015-12-30 | 中国地质科学院矿产综合利用研究所 | Magnesium-rich silicate mineral flotation inhibitor and preparation method and application thereof |
| CN106238223A (en) * | 2016-10-27 | 2016-12-21 | 武汉工程大学 | Melamine derivative Compositional type phosphate rock floating calcium and magnesium inhibitor and preparation, using method |
| CN111036411A (en) * | 2019-11-27 | 2020-04-21 | 东北大学 | Application of inhibitor acrylic acid maleic acid copolymer sodium salt in flotation and demagging of phosphate ore |
-
1987
- 1987-03-07 CN CN87101820.9A patent/CN1005258B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691574A (en) * | 2013-12-17 | 2014-04-02 | 广西大学 | Preparation method and application of dolomite inhibitor |
| CN105195334A (en) * | 2015-10-30 | 2015-12-30 | 中国地质科学院矿产综合利用研究所 | Magnesium-rich silicate mineral flotation inhibitor and preparation method and application thereof |
| CN105195334B (en) * | 2015-10-30 | 2017-09-12 | 中国地质科学院矿产综合利用研究所 | Magnesium-rich silicate mineral flotation inhibitor and preparation method and application thereof |
| CN106238223A (en) * | 2016-10-27 | 2016-12-21 | 武汉工程大学 | Melamine derivative Compositional type phosphate rock floating calcium and magnesium inhibitor and preparation, using method |
| CN106238223B (en) * | 2016-10-27 | 2018-08-24 | 武汉工程大学 | Melamine derivative Compositional type phosphate rock floating calcium and magnesium inhibitor and its preparation, application method |
| CN111036411A (en) * | 2019-11-27 | 2020-04-21 | 东北大学 | Application of inhibitor acrylic acid maleic acid copolymer sodium salt in flotation and demagging of phosphate ore |
| CN111036411B (en) * | 2019-11-27 | 2021-01-01 | 东北大学 | Application of inhibitor acrylic acid maleic acid copolymer sodium salt in flotation and demagging of phosphate ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005258B (en) | 1989-09-27 |
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