CN102557093B - Additive applied to process for producing aluminum oxide by bayer method and preparation method of additive - Google Patents
Additive applied to process for producing aluminum oxide by bayer method and preparation method of additive Download PDFInfo
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- CN102557093B CN102557093B CN201210051478.8A CN201210051478A CN102557093B CN 102557093 B CN102557093 B CN 102557093B CN 201210051478 A CN201210051478 A CN 201210051478A CN 102557093 B CN102557093 B CN 102557093B
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Abstract
The invention discloses an additive applied to a process for producing aluminum oxide by a bayer method and a preparation method of the additive. The additive comprises the following components in percentage by mass: 0.1 to 20 percent of polystyrene-acrylamide-crylic acid, 1 to 30 percent of silicon alkyl phenyl carboxylic acid, 1 to 20 percent of alcohol, 0.2 to 5 percent of NaOH and the balance of water. The preparation method comprises the following steps: mixing the polystyrene-acrylamide-crylic acid and water, and stirring and dissolving the mixture in the water bath at the temperature of between 30 and 55 DEG C to form uniform liquid; mixing the silicon alkyl cyclic carboxylic acid and the alcohol, stirring and dissolving into solution; and mixing the liquid and the solution, adding the NaOH with stirring to adjust the pH value to be 8 to 11, and stirring at high speed for 30 minutes to obtain product. The additive is applied to the process of producing the aluminum oxide by the bayer method, so that the strength and the granularity of the aluminum oxide can be improved.
Description
Technical field
The present invention relates to a kind of for additive in producing aluminium oxide by bayer technique and preparation method thereof.
Background technology
Aluminum oxide is the main raw material of Aluminum Electrolysis Production, is also the indispensable important source material of industry such as electronics, chemical industry, refractory materials, pottery simultaneously.In recent years, due to the popularization of electrolytic aluminium factory environmental protection and the automatic point feeding prebaked cell of energy-conservation needs, particularly dry FGD process and large-scale centre, not only to the purity of aluminum oxide, and strict requirement be it is also proposed to the physical properties of aluminum oxide.
It is one of important procedure of alumina producing Bayer process that sodium aluminate solution crystal seed decomposes, China's Bayer process with the diaspore type bauxite of indissoluble for raw material, leaching condition is harsh, the caustic sodium concentration of the molecule of dissolution fluid when solution is higher, obtained aluminum oxide compares with external typical sandy alumina product, main drawback is that product strength is low, can not ensure that fine particle content is in OK range simultaneously.Since " entry to WTO ", external granularity is good, the quality oxide aluminium product that intensity is large, impacts China alumina market, so solve sodium aluminate solution crystal seed to decompose the aluminum oxide producing high-quality, is China's aluminum i ndustry problem in the urgent need to address.
As far back as the eighties in last century, just have the research for three boehmite ore deposits abroad, and have the relevant decomposition additive improved the quality of products, but practice shows, examples of such additives is inapplicable with the technique of diaspore ore alumina producing Bayer process for China.And for the research in this type of ore deposit, be almost blank abroad.
China " eight or five " period, once concentrated the state-run large enterprises of Chalco and the strength of correlative study institute, and tried hard to, with the method by changing production technique, solving the problem that powdery aluminum granularity is poor, intensity is low, but not succeeding.
The domestic and international additive for Bayer process sodium aluminate solution decomposition of crystal seed at present, for water-dispersion additive or oil soluble additive, all belong to the additive improving aluminum oxide grain size, though the granularity of aluminum oxide can be improved after this kind of additive adds, seed precipitation of sodium aluminate rate of decomposition can be reduced or affect the intensity of aluminum oxide.And improve the additive of rate of decomposition, often cause the refinement of product aluminum oxide.In addition, for China's diaspore ore, water-soluble additive and water dispersible additive, often because of its residual generation foam in decomposed solution, and other production workshop section can be affected.
Summary of the invention
the technical problem to be solved in the present invention is: the additive Problems existing solving above-mentioned middle Bayer process sodium aluminate solution decomposition of crystal seed, the emulsion-type that the invention provides a kind of improved product strength of using in bayer's process aluminum oxide production process and granularity decomposes additive and preparation method thereof.
the technical solution used in the present invention:
Of the present invention a kind of for the additive in producing aluminium oxide by bayer technique, its formula composition massfraction is:
Polystyrene-acrylamide-vinylformic acid 0.1 ~ 20%
Silylation benzene carboxylic acid 1 ~ 30%
Alcohol 1 ~ 20%
NaOH 0.2～5%
Water surplus,
Wherein, polystyrene-acrylamide-acrylic acid molecular weight is 500 ~ 1,600 ten thousand, and molecular formula is:
Number fraction shared by X, Y, Z is: X is 10 ~ 50%; Z is 1 ~ 20%; All the other are Y.
Described is a kind of for the additive in producing aluminium oxide by bayer technique, polystyrene-acrylamide-synthesis of conjugated carboxylic alkeneacid is: be dissolved in water by 20 g acrylamides, add 0.005 ~ 0.01g chainextender MPMD 2-methyl isophthalic acid, 5-pentamethylene diamine, slowly pour in four-hole boiling flask, 1.2g ST-80 emulsifying agent is slowly poured in four-hole boiling flask, again vinylbenzene is joined in reaction system, pass into nitrogen, add 0.010g Diisopropyl azodicarboxylate initiator, at 15 ~ 35 DEG C, under 300r/min stirs, react 1 h, again under 100r/min stirs, within 3 ~ 5 hours, complete polyreaction,
40%NaOH slowly to entering in above-mentioned solution, at 60 DEG C, hydrolysis reaction 1 hour; After reaction terminates, the hydrochloric acid adjustment pH adding 10% is 4 ~ 5, add methyl alcohol to product precipitation completely and be separated, then by the toluene soak of products therefrom with 3 times amount, removing styrol copolymer, dryly obtains polystyrene-acrylamide-vinylformic acid;
Above-mentioned ST-80 emulsifying agent by Span-80 and Tween-80 compound, HLB=10;
Vinylbenzene and the concrete consumption of 40%NaOH, the percentage composition according to X, Y and Z in molecule calculates:
Vinylbenzene consumption=acrylamide quality × Z ÷ (100-Z) × 1.1;
40%NaOH consumption=acrylamide quality × X ÷ (100-Z) ÷ acrylic molecules amount × NaOH molecular weight ÷ 40%.
Described is a kind of for the additive in producing aluminium oxide by bayer technique, silylation phenyl carboxylic acid: with the C-Si type tensio-active agent of 1 Siliciumatom, and containing 1 benzene ring texture in molecule, side chain carbon number is: 1 ~ 8 carboxylic acid, and molecular formula is:
Wherein: n=1 ~ 7.
Described is a kind of for the additive in producing aluminium oxide by bayer technique, alcohol: carbon number is the alcohol of 3 ~ 9.
Described is a kind of for the additive in producing aluminium oxide by bayer technique, alcohol: propyl alcohol, Virahol, propyl carbinol, n-Octanol, isooctyl alcohol, n-Heptyl alcohol.
Described a kind of preparation method for the additive in producing aluminium oxide by bayer technique, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 30 ~ 55 DEG C;
(2) mixed with alcohol by silane basic ring carboxylic acid, stirring and dissolving becomes solution;
(3) mix 1 with 2 gains, under agitation, add NaOH and adjust pH to 7 ~ 11, high-speed stirring obtained product after 30 minutes.
the beneficial effect that the present invention reaches: the technology utilizes the polyacrylamide polymeric surface active agent and silane basic ring carboxylic-acid surfactant blend that contain phenyl ring, can when not changing decomposition technique condition.In the decomposition starting stage, when interpolation concentration is 10 ~ 25ppm, can when ensureing product aluminum oxide grain size, improve intensity and the granularity of product aluminum oxide, and improve Bayer process sodium aluminate solution corrosion, concrete manifestation is as follows:
(1) prepare in the process of aluminum oxide in Bayer process, do not change seed precipitation of sodium aluminate decomposition technique condition, utilize containing compound when the polyacrylamide polymeric surface active agent of phenyl ring and silylation carboxylic-acid (as: 4-[4-(trimethyl silicane methyl) phenyl] butyric acid), use at decomposition Different periods, intensity and granularity that Bayer process sodium aluminate solution decomposition of crystal seed prepares aluminum oxide can be improved, be of value to the raising of Bayer process sodium aluminate solution corrosion.
(2) the hydro-polyacrylamide macromolecular compound containing benzene ring structure, there is amphiphilic structure, for water soluble surfactant active, in group water solution, can with silylation phenyl carboxylic acid tensio-active agent mixture, form stable emulsification system, make this type of macromolecule emulsion type additive, namely there is the improved product alumina intensity of oil soluble additive and the advantage of granularity, also there is the advantage that water-soluble additive can improve rate of decomposition.Meanwhile, utilize the hydrophobicity of phenyl ring in this macromolecular compound, make decomposition additive easily be adsorbed onto the surface of aluminium hydroxide, depart from decomposing solution after filtration, not easily enter into decomposing solution, thus ensure that additive can not affect follow-up workshop section and produce.
(3) silylation phenyl carboxylic acid class tensio-active agent, not only surface tension can be reduced, also there is the effect suppressing foam to produce simultaneously, granularity and the intensity of product aluminum oxide can be improved after composite, and can eliminate or reduce the foam of tensio-active agent generation, thus ensure that additive can not affect follow-up workshop section and produce.
Accompanying drawing explanation
Product A l (OH) when Fig. 1 is embodiment 2 empty sample 60h
3sEM photo.
Fig. 2 is product A l (OH) when adding additives decompose 60h in embodiment 2
3sEM photo.
embodiment:
embodiment 1polystyrene-acrylamide-synthesis of conjugated carboxylic alkeneacid
20g acrylamide is dissolved in 40 mL water, add 0.008g chainextender MPMD(2-methyl isophthalic acid, 5-pentamethylene diamine), slowly pour in four-hole boiling flask, 1.2g ST-80 emulsifying agent is slowly poured in four-hole boiling flask, again vinylbenzene is joined in reaction system, pass into nitrogen 20min, add 0.010g Diisopropyl azodicarboxylate initiator, under 30 DEG C of temperature, 300r/min stir, react 1 hour, then under 100r/min stirs, within 4 hours, complete polyreaction;
40%NaOH slowly to entering in above-mentioned solution, at 60 DEG C, hydrolysis reaction 1 hour; After reaction terminates, the hydrochloric acid adjustment pH adding 10% is 4.5, adds methyl alcohol to product and precipitates completely and be separated; Again by the toluene soak of products therefrom by 3 times amount, removing styrol copolymer, dry polystyrene-acrylamide-vinylformic acid;
Above-mentioned ST-80 emulsifying agent by Span-80 and Tween-80 compound, HLB=10;
Vinylbenzene and the concrete consumption of 40%NaOH, the percentage composition according to X, Y and Z in molecule calculates:
Vinylbenzene consumption=acrylamide quality × Z ÷ (100-Z) × 1.1;
40%NaOH consumption=acrylamide quality × X ÷ (100-Z) ÷ acrylic molecules amount × NaOH molecular weight ÷ 40%.
embodiment 2preferred additive formulations and preparation method thereof
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 45 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 2.
As can be seen from the test-results of table 2, compared with blank, additive can increase the median size of product, reduces the fine particle content being less than 45 μm and reduces, improve product granularity; The abrasion index adding the aluminum oxide of additive reduces about about 28% than blank, and improve product strength, rate of decomposition slightly improves simultaneously.
Why additive can improve product A l
2o
3intensity, mainly because the additive product A l (OH) that makes sodium aluminate solution crystal seed decompose
3present ball shape structure (see Fig. 1 and 2), thus enhance roasting after product Al
2o
3intensity.
embodiment 3
Preferred additive formulations is in table 3, and experimental result is in table 4
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 45 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 4.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 50 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 6.
embodiment 5
Preferred additive formulations is in table 7, and experimental result is in table 8.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 8.
embodiment 6
Preferred additive formulations is in table 9, and experimental result is in table 10.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 45 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 10.
embodiment 7
Preferred additive formulations is in table 11, and experimental result is in table 12.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 12.
embodiment 8
Preferred additive formulations is in table 13, and experimental result is in table 14.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 14.
The preferred additive of table 14 is to product A l
2o
3the impact of intensity and granularity
embodiment 9
Preferred additive formulations is in table 15, and experimental result is in table 16.
The preferred additive formulations of table 15
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 16.
embodiment 10
Preferred additive formulations is in table 17, and experimental result is in table 18.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 18.
embodiment 11
Preferred additive formulations is in table 19, and experimental result is in table 20.
The above-mentioned macromolecule emulsion type used in bayer's process aluminum oxide production process decomposes the preparation method of additive, comprises the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 35 DEG C;
(2) silane basic ring carboxylic acid is mixed with alcohol, after stirring and dissolving becomes solution;
(3) step (1) mixed with (2) gains, under agitation, add NaOH and adjust pH, high-speed stirring obtained product after 30 minutes.
In Bayer process sodium aluminate solution initial decomposition, disposable add-on 25mg/L, laboratory result is in table 20.
As can be seen from table 3 ~ table 20, compared with blank, additive can increase the median size of product, reduces the fine particle content being less than 45 μm and reduces, improve product granularity; The abrasion index of low about aluminum oxide, improves product strength, and rate of decomposition slightly improves simultaneously.
Claims (4)
1. for the additive in producing aluminium oxide by bayer technique, it is characterized in that: its formula composition massfraction is:
Polystyrene-acrylamide-vinylformic acid 0.1 ~ 20%
Silylation benzene carboxylic acid 1 ~ 30%
Alcohol 1 ~ 20%
NaOH 0.2～5%
Water surplus,
Wherein, polystyrene-acrylamide-acrylic acid molecular weight is 500 ~ 1,600 ten thousand, and molecular formula is:
Number fraction shared by X, Y, Z is: X is 10 ~ 50%; Z is 1 ~ 20%; All the other are Y;
Silylation phenyl carboxylic acid: with the C-Si type tensio-active agent of 1 Siliciumatom, containing 1 benzene ring texture in molecule, side chain carbon number is: 1 ~ 8 carboxylic acid, and molecular formula is:
Wherein: n=1 ~ 7.
2. according to claim 1 a kind of for the additive in producing aluminium oxide by bayer technique, it is characterized in that: alcohol: carbon number is the alcohol of 3 ~ 9.
3. according to claim 1 a kind of for the additive in producing aluminium oxide by bayer technique, it is characterized in that: alcohol: propyl alcohol, Virahol, propyl carbinol, n-Octanol, isooctyl alcohol, n-Heptyl alcohol.
4. a kind of preparation method for the additive in producing aluminium oxide by bayer technique as claimed in claim 1, is characterized in that: comprise the following steps:
(1) polystyrene-acrylamide-vinylformic acid is mixed with water, stirring and dissolving uniformly liquid at water-bath 30 ~ 55 DEG C;
(2) mixed with alcohol by silane basic ring carboxylic acid, stirring and dissolving becomes solution;
(3) mix 1 with 2 gains, under agitation, add NaOH and adjust pH to 7 ~ 11, high-speed stirring obtained product after 30 minutes.
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| CN103342722B (en) * | 2013-07-26 | 2014-04-02 | 台山市新宁制药有限公司 | Preparation method of alkaline bismuth gallate |
| CN111153423A (en) * | 2020-01-03 | 2020-05-15 | 江西理工大学 | Composite inhibitor containing PAH (polycyclic aromatic Hydroquinone) and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327660A1 (en) * | 1988-02-11 | 1989-08-16 | VAW Aluminium AG | Process for the production of fillers and fire-preventing materials based on hydrargillite-type aluminium hydroxide |
| CN1888096A (en) * | 2006-07-18 | 2007-01-03 | 中国铝业股份有限公司 | Prepn process of Bayer process leaching additive |
| CN1911808A (en) * | 2006-09-14 | 2007-02-14 | 中国铝业股份有限公司 | Method for decomposing ultrahigh concentration sodium aluminate solution |
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| US7955589B2 (en) * | 2005-06-23 | 2011-06-07 | Nalco Company | Composition and method for improved aluminum hydroxide production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327660A1 (en) * | 1988-02-11 | 1989-08-16 | VAW Aluminium AG | Process for the production of fillers and fire-preventing materials based on hydrargillite-type aluminium hydroxide |
| CN1888096A (en) * | 2006-07-18 | 2007-01-03 | 中国铝业股份有限公司 | Prepn process of Bayer process leaching additive |
| CN1911808A (en) * | 2006-09-14 | 2007-02-14 | 中国铝业股份有限公司 | Method for decomposing ultrahigh concentration sodium aluminate solution |
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