CN1169625C - Chelating maromolecular inhibitor for bauxite anti-flotation and its preparation method - Google Patents
Chelating maromolecular inhibitor for bauxite anti-flotation and its preparation method Download PDFInfo
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- CN1169625C CN1169625C CNB011372281A CN01137228A CN1169625C CN 1169625 C CN1169625 C CN 1169625C CN B011372281 A CNB011372281 A CN B011372281A CN 01137228 A CN01137228 A CN 01137228A CN 1169625 C CN1169625 C CN 1169625C
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- starch
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- bauxite
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Abstract
The present invention relates to a water soluble polymer compound-hydroxamic acid starch which uses starch, alpha-halogenated acetic acid and hydroxylamine as raw material and is made by a nucleophilic substitution reaction and nucleophilic addition-elimination reaction. The molecular structure of the present invention comprises a plurality of-OH and-C (OH) NOH groups. The present invention sufficiently displays favorable inhibition capability for diaspore in an alumyte reverse flotation process, and does not influence the floatability of aluminosilicate minerals, such as kaolinite, illite, pyrophyllite, etc. The present invention is a chelating type inhibitor with high selectivity.
Description
Technical field:
The present invention relates to a kind of is raw material with starch, alpha-halogen acetic acid esters and azanol, make water-soluble high-molecular compound---hydroxamic acid starch by nucleophilic substitution and nucleophilic addition-elimination reaction, this water-soluble high-molecular compound is a kind of chelating type highly selective inhibitor, can effectively suppress the flotation of diaspore, suitable inhibitor as the diaspore type bauxite Counterfloatating desiliconization.
Background technology:
China's diaspore type bauxite reserves are abundant, have the resources characteristic of the high silicon of high alumina, high aluminium silicon ratio, and main gangue mineral is aluminosilicates such as kaolinite, illite and pyrophillite.For a long time, China's aluminum oxide industry circle employing is expensive, the sintering process or the producing alumina by mixed combined process of high energy consumption, and product lacks competitiveness in the international market.The enforcement period of the ninth five-year plan, successfully developed suitable China bauxite resource characteristics bauxite direct-flotation desiliconisation---aluminium concentrate Bayer process new technology makes the low-cost production aluminium oxide become possibility.But the froth pulp float-amount of direct-flotation desiliconisation technology is big, mechanical entrainment is serious, causes collecting agent medicine consumption big on the one hand, and the surface-active collecting agent that has that concentrate carries on the other hand influences follow-up Bayer process flow process.On the contrary, reverse floatation process has that the froth pulp float-amount is few, collecting agent consumption is few, and particularly concentrate does not carry collecting agent.Yet, the collecting agent existence has good floatability to diaspore, the inhibitor of the diaspore of the inverse floatation of bauxite of bibliographical information is starch or tannin at present, its shortcoming is a little less than the inhibition ability to diaspore, and suppress to lack selectivity, promptly aluminosilicates such as kaolinite, illite and pyrophillite are all had inhibitory action.
Summary of the invention:
The objective of the invention is deficiency at the existing medicament of inverse floatation of bauxite, providing a kind of is raw material with starch, alpha-halogen acetic acid esters and azanol, obtaining a kind ofly has good inhibition to diaspore, and high selectivity chelating type water-soluble macromolecule inhibitor that aluminium silicate mineral floatabilities such as kaolinite, illite and pyrophillite are not exerted an influence and preparation method thereof.
The objective of the invention is to reach by following proposal:
At first by starch and alpha-halogen acetic acid esters when the alkali as a catalyst, make O-acetate groups starch by nucleophilic substitution, add azanol then, make hydroxamic acid starch by nucleophilic addition-elimination reaction.Concrete preparation process (referring to accompanying drawing) is:
In the reactor that agitator, reflux condensing tube and dropping funel are housed, starch is scattered in 85% proper amount of solvent, under agitation adds catalyst, at room temperature activate certain hour after, add the alpha-halogen acetic acid esters, stirring reaction is to complete under uniform temperature.With the product suction filtration, then filter cake is scattered in the ethanol water, splash into the aqueous hydroxylamine solution for preparing in advance simultaneously, continue stirring reaction at a certain temperature to complete, with watery hydrochloric acid neutralization, suction filtration, after filter cake repeatedly washs with 85% ethanol water, in 40 ℃ of freeze-day with constant temperature, obtain hydroxamic acid starch.
Employed catalyst is alkali metal or alkaline-earth metal, also can be oxide or the hydroxide or the carbonate of alkali or alkaline-earth metal.
Aqueous hydroxylamine solution is at room temperature mixed with alkali metal hydroxide or alkali metal carbonate solution by hydroxylamine hydrochloride or sulfate liquor and gets, and material mole proportioning is 0.5～1: 1～0.5.
The mass ratio that feeds intake of starch, alpha-halogen acetic acid esters and azanol is 10～3.57: 6～3: 1.Employed solvent is fatty alcohol or the alkyl ketone that contains 1～6 carbon number.
The priming reaction temperature is 28～32 ℃ of room temperatures; The nucleophilic substitution temperature is not higher than the gelatinization point of material, is 40～60 ℃; The temperature of nucleophilic addition-elimination reaction is not higher than the decomposition temperature of azanol, is 30～60 ℃.
The chelating maromolecular inhibitor that is used for inverse floatation of bauxite, employed starch, chemical formula is:
——(C
6H
10O
5)
n——
In the formula: n is the glucose unit number.
Employed alpha-halogen acetic acid esters general formula is:
X-CH
2COOR
In the formula: X is Cl or Br, I
R contains straight, the branched alkyl of 1～20 carbon atom or cycloalkyl, aryl, aralkyl.
The above-mentioned synthetic product for preparing is a kind of water-soluble macromolecule compound, contain in its molecular structure a plurality of-OH and-C (OH) NOH group, the technology that it is used for inverse floatation of bauxite has fully shown it is a kind of function groups chelating type inhibitor that diaspore is had good rejection.
Description of drawings:
Accompanying drawing 1: the inhibitor synthetic schemes that is used for inverse floatation of bauxite.
The specific embodiment:
Embodiment 1
In the 250ml three-necked bottle of agitator, reflux condensing tube and dropping funel is housed, 25g starch is scattered in the 100ml isopropyl alcohol, under agitation adds 30%KOH solution 20ml, behind 30 ℃ of activation 30min, add the 28g methyl chloroacetate, in 40 ℃ of following stirring reaction 5h.With the product suction filtration, filter cake is scattered in the 100ml85% ethanol, splash into the hydroxylamine chloride 7g and the potassium hydroxide 4g that are dissolved in 60ml water in advance respectively simultaneously, stop heating behind the continuation stirring reaction 2h down at 60 ℃, neutralize with watery hydrochloric acid, after suction filtration, filter cake repeatedly wash with 85% ethanol water, in 40 ℃ of freeze-day with constant temperature.Promptly get hydroxamic acid starch.
Lauryl amine with 40mg/l is a collecting agent, with hydroxamic acid starch is inhibitor, carry out the float test of diaspore, kaolinite, pyrophillite, illite mineral, this product has obvious inhibitory action in the floatability of pH1～6 pair diaspore, as about pH4, the come-up rate of diaspore can be reduced to 18% from 66.3%, and kaolinite, pyrophillite, three kinds of mineral of illite are not produced inhibitory action.When lauryl amine and this product consumption were 40mg/l, this product was as shown in table 1 to the influence of four kinds of mineral floatabilities under different pH condition.About pH4, when collecting agent lauryl amine consumption was 40mg/l, this product consumption was as shown in table 2 to the influence of diaspore, kaolinite, illite and four kinds of mineral come-ups of pyrophillite rate.
Hydroxamic acid starch is to the influence of mineral come-up rate under the different pH of table 1
| Diaspore | pH | 3.0 | 4.2 | 5.1 | 6.6 | 7.4 | 9.1 | 11.3 |
| The come-up rate, % | 13.3 | 17.6 | 25.3 | 47.3 | 60.3 | 58.0 | 34.0 | |
| Kaolinite | pH | 2.8 | 4.7 | 5.8 | 7.2 | 8.5 | 9.8 | 10.9 |
| The come-up rate, % | 73.7 | 54.0 | 35.0 | 27.7 | 26.7 | 18.7 | 18.7 | |
| Pyrophillite | pH | 2.8 | 3.8 | 4.3 | 6.7 | 7.3 | 8.6 | 9.8 |
| The come-up rate, % | 70.7 | 71.7 | 67.3 | 51.0 | 46.0 | 42.7 | 24.3 | |
| Illite | pH | 2.9 | 3.4 | 4.1 | 5.8 | 7.1 | 8.3 | 9.6 |
| The come-up rate, % | 47.0 | 46.7 | 30.3 | 8.3 | 5.0 | 4.7 | 4.3 |
Table 2 pH4 left and right sides hydroxamic acid starch consumption is to the influence of mineral floatability
Embodiment 2 is in being equipped with the 250ml three-necked bottle of agitator, reflux condensing tube and dropping funel, 25g starch is scattered in the 100ml isopropyl alcohol, under agitation adds 30%NaOH solution 20ml, behind 30 ℃ of activation 30min, add the 14g methyl chloroacetate, in 40 ℃ of following stirring reaction 5h.With the product suction filtration, filter cake is scattered in the 100ml85% ethanol, splash into the hydroxylamine chloride 3.5g and the sodium carbonate 4g that are dissolved in 30ml water in advance respectively simultaneously, stop heating behind the continuation stirring reaction 2h down at 50 ℃, neutralize with watery hydrochloric acid, suction filtration, filter cake obtain hydroxamic acid starch in 40 ℃ of freeze-day with constant temperature after repeatedly washing with 85% ethanol water.
Lauryl amine with 40mg/l is a collecting agent, with hydroxamic acid starch is inhibitor, carry out the float test of diaspore, kaolinite, pyrophillite, illite mineral, this product has obvious inhibitory action in the floatability of pH1～6 pair diaspore, as about pH4, the come-up rate of diaspore can be reduced to 23.7% from 66.3%, and kaolinite, pyrophillite, three kinds of mineral of illite are not produced inhibition.
Embodiment 3 is scattered in 25g starch in the 100ml n-butanol in the 250ml three-necked bottle of agitator, reflux condensing tube and dropping funel is housed, and under agitation adds 30%Na
2CO
3Solution 20ml behind 30 ℃ of activation 30min, adds the 18g bromoacetate, in 40 ℃ of following stirring reaction 5h.With the product suction filtration, filter cake is scattered in the 100ml85% ethanol, splash into the hydroxylamine chloride 3.5g and the sodium carbonate 4g that are dissolved in 30ml water in advance respectively simultaneously, stop heating behind the continuation stirring reaction 2h down at 40 ℃, with watery hydrochloric acid neutralization, suction filtration, after filter cake repeatedly washs with 85% ethanol water, in 40 ℃ of freeze-day with constant temperature, promptly get hydroxamic acid starch.
Lauryl amine with 40mg/l is a collecting agent, with hydroxamic acid starch is inhibitor, carry out the float test of diaspore, kaolinite, pyrophillite, illite mineral, this product has obvious inhibitory action in the floatability of pH1～6 pair diaspore, as about pH4, the come-up rate of diaspore can be reduced to 29.7% from 66.3%, and kaolinite, pyrophillite, three kinds of mineral floatabilities of illite are had no adverse effects.
Embodiment 4 contrast properties test: under similarity condition, compare the flotation experiment with ative starch, table 3 is respectively with table 4 that (dosing is identical under different pH values, lauryl amine, ative starch consumption are 40mg/l) with the ative starch different amounts under (flotation pH value is identical, pH=4) the come-up rate of diaspore, kaolinite, illite and pyrophillite.
Table 3 ative starch under different pH condition to the influence of mineral come-up rate
| Diaspore | pH | 3.1 | 4.2 | 5.5 | 7.1 | 7.9 | 9. | 10.6 |
| The come-up rate, % | 60.0 | 64.3 | 70.0 | 76.0 | 67.0 | 36.7 | 39.3 | |
| Kaolinite | pH | 2.8 | 4.9 | 6.0 | 7.0 | 8.4 | 9.6 | 10.9 |
| The come-up rate, % | 67.0 | 45.7 | 36.3 | 29.0 | 25.3 | 16.7 | 11.3 | |
| Pyrophillite | pH | 2.7 | 3.9 | 4.9 | 6.1 | 7.4 | 8.3 | 9.6 |
| The come-up rate, % | 60.0 | 68.3 | 60.0 | 52.3 | 34.7 | 39.7 | 28.3 | |
| Illite | pH | 3.07 | 3.3 | 4.2 | 5.7 | 7.2 | 8.3 | 9.9 |
| The come-up rate, % | 45.0 | 48.0 | 31.3 | 17.7 | 9.7 | 4.0 | 5.7 |
Table 4 ative starch different amounts is to the influence of mineral come-up rate
Claims (6)
1. the preparation method who is used for the big molecule inhibitor of chelating of inverse floatation of bauxite, it is characterized in that: at first by starch and alpha-halogen acetic acid esters when the alkali as a catalyst, make O-acetate groups starch by nucleophilic substitution, add azanol then, make hydroxamic acid starch by nucleophilic addition-elimination reaction, concrete preparation process is:
In the reactor that agitator, reflux condensing tube and dropping funel are housed, starch is scattered in the solvent, under agitation add catalyst, at room temperature activate 30min after, add the alpha-halogen acetic acid esters, in 40 ℃ of left and right sides stirring reactions to fully; With the product suction filtration, filter cake is scattered in 85% ethanol water then, splash into the aqueous hydroxylamine solution for preparing in advance simultaneously, continue stirring reaction down to complete at 40～60 ℃, with watery hydrochloric acid neutralization, suction filtration, after filter cake repeatedly washs with 85% ethanol water, in 40 ℃ of freeze-day with constant temperature, obtain hydroxamic acid starch.
2. the preparation method who is used for the big molecule inhibitor of chelating of inverse floatation of bauxite according to claim 1 is characterized in that: employed catalyst is alkali metal or alkaline-earth metal, also can be oxide or the hydroxide or the carbonate of alkali or alkaline-earth metal.
3. the preparation method who is used for the big molecule inhibitor of chelating of inverse floatation of bauxite according to claim 1 and 2, it is characterized in that: aqueous hydroxylamine solution is at room temperature mixed with alkali metal hydroxide or alkali metal carbonate solution by hydroxylamine hydrochloride or sulfate liquor and gets, and the mol ratio of material proportion is 0.5～1: 1～0.5.
4. the preparation method who is used for the big molecule inhibitor of chelating of inverse floatation of bauxite according to claim 1 and 2 is characterized in that: the mass ratio that feeds intake of starch, alpha-halogen acetic acid esters and azanol is 10～3.57: 6～3: 1; Employed solvent is fatty alcohol or the alkyl ketone that contains 1～6 carbon number.
5. the preparation method who is used for the big molecule inhibitor of chelating of inverse floatation of bauxite according to claim 1 and 2 is characterized in that: the priming reaction temperature is 28～32 ℃ of room temperatures, and the nucleophilic substitution temperature is not higher than the gelatinization point of material, at 40～60 ℃; The temperature of nucleophilic addition-elimination reaction is not higher than the decomposition temperature of azanol, is 30～60 ℃.
6. adopt the big molecule inhibitor of chelating that bauxite returns flotation that is used for of claim 1 or 2 described preparation method's preparations, it is characterized in that:
Employed starch, chemical formula is:
——(C
6H
10O
5)
n——
In the formula: n is the glucose unit number;
Employed alpha-halogen acetic acid esters general formula is:
X-CH
2COOR
In the formula: X be Cl or Br, I,
R contains straight, the branched alkyl of 1～20 carbon atom or cycloalkyl, aryl, aralkyl;
The synthetic chelating maromolecular inhibitor that is used for inverse floatation of bauxite for preparing of said method is a kind of water-soluble macromolecule compound, contain in its molecular structure a plurality of-OH and-C (OH) NOH group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011372281A CN1169625C (en) | 2001-10-23 | 2001-10-23 | Chelating maromolecular inhibitor for bauxite anti-flotation and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011372281A CN1169625C (en) | 2001-10-23 | 2001-10-23 | Chelating maromolecular inhibitor for bauxite anti-flotation and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1413773A CN1413773A (en) | 2003-04-30 |
| CN1169625C true CN1169625C (en) | 2004-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011372281A Expired - Fee Related CN1169625C (en) | 2001-10-23 | 2001-10-23 | Chelating maromolecular inhibitor for bauxite anti-flotation and its preparation method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393422C (en) * | 2006-11-03 | 2008-06-11 | 北京矿冶研究总院 | Use method of selective flocculant for reverse flotation of bauxite |
| US9139456B2 (en) | 2008-04-16 | 2015-09-22 | The Curators Of The University Of Missouri | Chelating compounds and immobilized tethered chelators |
| US7932326B2 (en) | 2008-04-16 | 2011-04-26 | The University Of Kentucky Research Foundation | Chelating compounds and immobilized tethered chelators |
| US9259670B2 (en) | 2008-04-16 | 2016-02-16 | The University Of Kentucky Research Foundation | Flow-through filter to remove aluminum from medical solutions |
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