CN103708517B - The method of powdery iron-free poly aluminium chloride prepared by a kind of high whiteness calcium aluminate - Google Patents
The method of powdery iron-free poly aluminium chloride prepared by a kind of high whiteness calcium aluminate Download PDFInfo
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Abstract
The invention discloses a kind of method that powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate.Comprise following raw material and preparation process: aluminium hydroxide and calcite in powder respectively through naturally cooling after comparatively high temps pre-burning and grinds, are obtained aluminum oxide powder and calcium oxide powder by (1); (2) this aluminum oxide powder and calcium oxide powder mixed with high heating value coal dust by a certain percentage make spherule, then after high-temperature calcination naturally cooling grinds, obtain high whiteness calcium aluminate powder; (3) this calcium aluminate powder is added in iron-free liquor alumini chloridi as basicity conditioning agent reacts, and then add rafifinal deironing, obtain iron-free poly aluminium chloride liquid, after spray-dried for this liquid poly aluminium chloride, obtain powdery iron-free poly aluminium chloride of the present invention.Coagulation effect of the present invention is good, heavy metal content is low, the rear water outlet residual aluminum of process is up to standard, production cost is not high, other quality index can meet " Drinking Water poly aluminium chloride " (GB15892-2009) standard-required.
Description
Technical field
The present invention relates to inorganic aluminate water purification agent field, be specifically related to a kind of method that powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate.
Background technology
Poly aluminium chloride has the advantages such as good drug efficacy, dosage is few, easy to use, price is low, has become one of China's most popular Drinking Water process water purification agent.And the Chinese government and the safety of the common people to Drinking Water are also more and more paid attention to, require more and more stricter.Define the control criterion of heavy (class) metal such as arsenic, cadmium, chromium (sexavalence), mercury, lead in country " drinking water sanitary standard " (GB 5749-2006), original standard base has been revised heavy (class) metal index such as arsenic, cadmium, lead.Correspond, " Drinking Water poly aluminium chloride " (GB15892-2009) defines the control criterion of heavy (class) metal such as arsenic, cadmium, chromium (sexavalence), mercury, lead equally.According to the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009) standard, it is qualified that the drinking water poly aluminium chloride product that a lot of enterprise produces at present is difficult to.National correlation department tissue in 2013 is revised to adapt to " drinking water sanitary standard " (GB 5749-2006) to " Drinking Water poly aluminium chloride " (GB15892-2009) standard and is enforced requirement to water quality." Drinking Water poly aluminium chloride " new standard revised will propose stricter requirement to the quality of poly aluminium chloride, makes the production of poly aluminium chloride industry be faced with larger challenge.
China's poly aluminium chloride industry production mainly adopts the production technique such as bauxitic clay (or flyash) acid-soluble two step method, calcium aluminate acid-soluble one-step, aluminium hydroxide acid-soluble one-step and the acid-soluble two step method of aluminium hydroxide.Wherein regulating basicity to carry out producing with calcium aluminate is the poly aluminium chloride production method that China creates, comprise bauxitic clay (or flyash) acid-soluble two step method (main raw material is bauxitic clay or flyash, calcium aluminate and hydrochloric acid), calcium aluminate acid-soluble one-step (main raw material is calcium aluminate and hydrochloric acid) and the acid-soluble two step method of aluminium hydroxide (main raw material is aluminium hydroxide, calcium aluminate and hydrochloric acid), the poly aluminium chloride manufacturing enterprise of China more than 90% adopts above-mentioned processing method.Only aluminium hydroxide acid-soluble one-step (main raw material is aluminium hydroxide and hydrochloric acid) is adopted to produce less than the poly aluminium chloride manufacturing enterprise of 10%.Following problem is mainly there is in these methods in drinking water treatment field:
(1) the acid-soluble two step method coverage rate of bauxitic clay (or flyash) is the widest, and it has, and technique is simple, working condition is gentle, easy to operate, raw material and the low advantage of production cost.But because the impact of impurity in raw material causes product purity not good, heavy metal content is higher, product is yellow, that tawny is even darker color.This series products should not be used for drinking water treatment;
(2) calcium aluminate acid-soluble one-step equally also has the advantages such as technique is simple, working condition is gentle, easy to operate, but calcium aluminate price rises steadily in recent years, this explained hereafter cost constantly raises up, and product heavy metal content is also higher, should not be used for drinking water treatment;
(3) the poly aluminium chloride product that aluminium hydroxide acid-soluble one-step is produced has the advantages such as purity is high, quality better, white color, heavy metal content are low, can be used for the production of drinking water treatment and paper industry.But the condition that cost of material is expensive, production process needs High Temperature High Pressure is harsh, production unit loss is large, and product basicity is low, and coagulation effect is poor, greatly, it is higher to carry out after drinking water treatment residual aluminum in water for the chemical feeding quantity needed in water treatment;
(4) the acid-soluble two step method of aluminium hydroxide have working condition gentleness, product coagulation effect good, for advantages such as Al residual in water after drinking water treatment are low, be at present for the main product of drinking water treatment.But by the impact of calcium aluminate raw material, heavy metal content is unstable in product, often there is the phenomenon that can not reach " Drinking Water poly aluminium chloride " (GB15892-2009) standard-required.
According to the development trend of current inorganic aluminate water purification agent, developing efficient, that residual aluminum is low, heavy metal content the is low poly aluminium chloride product being suitable for the use of Drinking Water treatment industry will be the focus studied at present and in the future.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that coagulation effect is good, heavy metal content is low, powdery iron-free poly aluminium chloride prepared by the rear high whiteness calcium aluminate that water outlet residual aluminum is up to standard, production cost is not high, other quality index can meet " Drinking Water poly aluminium chloride " (GB15892-2009) standard-required of process.
In order to solve the problems of the technologies described above, the method for powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate provided by the invention, comprises following raw material and preparation process:
(1) be, that the aluminium hydroxide of 64% ~ 65% and calcium carbonate mass content is greater than 98%, whiteness is greater than 90% calcite in powder pre-burning at 850 DEG C ~ 950 DEG C temperature naturally cool to normal temperature after 3 hours ~ 5 hours by quality of alumina content, then worn into 80 order ~ 120 order powders respectively, obtained the activated aluminum oxide powder of tool and calcium oxide powder;
(2) be, the coal dust of more than 7000kcal/kg by the aluminum oxide powder of step (1) gained, calcium oxide powder and calorific value be 55% ~ 60%, 30% ~ 35% and 10% to mix by massfraction respectively, add appropriate clear water stirring and make spherule, again through the temperature calcination 4 hours ~ 6 hours of 1200 DEG C ~ 1300 DEG C, wear into 100 order ~ 180 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder that quality of alumina content is 60% ~ 65%;
(3), be in the iron-free aluminum chloride liquid of 5.0% ~ 10.0% at quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 120 revs/min ~ 200 revs/min conditions, then react 60 minutes ~ 90 minutes at temperature is 25 DEG C ~ 100 DEG C, the rafifinal deironing 30 minutes ~ 60 minutes of 1.0% ~ 3.0% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 280 DEG C ~ 300 DEG C by this poly aluminium chloride liquid at hot blast temperature, tail air temperature is carry out spraying dry at 100 DEG C ~ 110 DEG C, obtain the powdery iron-free poly aluminium chloride that quality of alumina content is 29% ~ 33%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
Adopt the high whiteness calcium aluminate of technique scheme to prepare the method for powdery iron-free poly aluminium chloride, there is following features:
1, the preparation of high whiteness calcium aluminate with aluminium hydroxide and calcite for raw material, through the calcining of secondary differing temps, first by aluminium hydroxide and calcite in powder respectively at 850 DEG C ~ 950 DEG C temperature pre-burning within 2 hours ~ 5 hours, activate, and then by the aluminum oxide powder of gained, calcium oxide powder and calorific value are the coal dust of 7000kcal/kg is 55% ~ 60% by massfraction respectively, 30% ~ 35% and 10% mixing again through the temperature calcination 4 hours ~ 6 hours of 1200 ~ 1300 DEG C, obtain the high whiteness calcium aluminate powder that quality of alumina content is 60 % ~ 65%, this technical characterstic can ensure that calcining temperature is lower than 1300 DEG C, existing calcium aluminate rotary kiln production equipment can be adapted to, do not need to build special Sweet natural gas or the high temperature resistant calciner of heavy oil,
2, gained high whiteness calcium aluminate powder activity is high, poly aluminium chloride liquid can be produced under quality of alumina mark is the iron-free concentration of aluminum chloride of 5.0 % ~ 10.0% and temperature is 30 DEG C ~ 100 DEG C conditions, through the rafifinal deironing 30 minutes ~ 60 minutes of calcium aluminate massfraction 1.0 % ~ 3.0%, after filtering, gained is iron-free poly aluminium chloride liquid, be 280 DEG C ~ 300 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 100 DEG C ~ 110 DEG C, obtain the powdery iron-free poly aluminium chloride that quality of alumina content is 29% ~ 31%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).This technical characterstic makes gained high whiteness calcium aluminate powder not only can be used for existing poly aluminium chloride manufacturing enterprise, also can meet Running-water Company and make the poly aluminium chloride that be up to state standards " Drinking Water poly aluminium chloride " (GB15892-2009) require by oneself when there is no heating unit, for drink water purifying process;
3, no matter gained powdery iron-free poly aluminium chloride is that coagulation effect or whiteness are all better than similar products at home and abroad level, can meet the needs of domestic and international market to high-quality poly aluminium chloride product, and production process meets cleaner production and environmental requirement.
In sum, the present invention is a kind of method that coagulation effect is good, heavy metal content is low, powdery iron-free poly aluminium chloride prepared by the rear high whiteness calcium aluminate that water outlet residual aluminum is up to standard, production cost is not high, other quality index can meet " Drinking Water poly aluminium chloride " (GB15892-2009) standard-required of process, for domestic aluminium salt industry provides a kind of high-quality poly aluminium chloride product of reaching advanced world standards, and production cost is lower than international like product, production technology is simple, production process environmental protection.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
embodiment 1:
The method of powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, comprises following raw material and preparation process:
(1), by 1000g quality of alumina content be 64% aluminium hydroxide and 1000g calcium carbonate mass content 98.5%, calcite in powder pre-burning at 850 DEG C of temperature of whiteness 91% naturally cooled to normal temperature after 5 hours, then worn into 80 order powders respectively, obtained the activated aluminum oxide 630g of tool and 550g calcium oxide powder;
(2), getting the aluminum oxide powder 550g of step (1) gained, calcium oxide powder 350g and calorific value is that the coal dust 100g of 7100kcal/kg mixes, add appropriate clear water stirring and make spherule, again through the temperature calcination 6 hours of 1200 DEG C, wear into 100 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder 900g that quality of alumina content is 60%;
(3), be in the iron-free aluminum chloride liquid of 5.0% at 10000g quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 120 revs/min of conditions, then react 90 minutes at temperature is 25 DEG C, the rafifinal deironing 60 minutes of 1.5% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 280 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 105 DEG C, obtain the powdery iron-free poly aluminium chloride that 3460g quality of alumina content is 30%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
embodiment 2:
The method of powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, comprises following raw material and preparation process:
(1), by 1000g quality of alumina content be 64.5% aluminium hydroxide and 1000g calcium carbonate mass content 99%, calcite in powder pre-burning at 900 DEG C of temperature of whiteness 92% naturally cooled to normal temperature after 4 hours, then worn into 100 order powders respectively, obtained the activated aluminum oxide 645g of tool and 550g calcium oxide powder;
(2), getting the aluminum oxide powder 600g of step (1) gained, calcium oxide powder 300g and calorific value is that the coal dust 100g of 7100kcal/kg mixes, add appropriate clear water stirring and make spherule, again through the temperature calcination 5 hours of 1250 DEG C, wear into 120 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder 920g that quality of alumina content is 65%;
(3), be in the iron-free aluminum chloride liquid of 10.0% at 6000g quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 150 revs/min of conditions, then react 70 minutes at temperature is 50 DEG C, the rafifinal deironing 30 minutes of 2.5% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 300 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 110 DEG C, obtain the powdery iron-free poly aluminium chloride that 3620g quality of alumina content is 33%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
embodiment 3:
The method of powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, comprises following raw material and preparation process:
(1), by 1000g quality of alumina content be 65% aluminium hydroxide and calcium carbonate mass content 99%, calcite in powder pre-burning at 950 DEG C of temperature of whiteness 91% naturally cooled to normal temperature after 3 hours, then worn into 120 order powders respectively, obtained the activated aluminum oxide 650g of tool and 550g calcium oxide powder;
(2), getting the aluminum oxide powder 580g of step (1) gained, calcium oxide powder 320g and calorific value is that the coal dust 100g of 7100kcal/kg mixes, add appropriate clear water stirring and make spherule, again through the temperature calcination 4 hours of 1300 DEG C, wear into 180 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder 900g that quality of alumina content is 64.5%;
(3), be in the iron-free aluminum chloride liquid of 8.0% at 7300g quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 200 revs/min of conditions, then react 60 minutes at temperature is 100 DEG C, the rafifinal deironing 30 minutes of 3.0% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 290 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 105 DEG C, obtain the powdery iron-free poly aluminium chloride that 3750g quality of alumina content is 31%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
embodiment 4:
The method of powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, comprises following raw material and preparation process:
(1), by 1000g quality of alumina content be 64.5% aluminium hydroxide and 1000g calcium carbonate mass content 98.5%, calcite in powder pre-burning at 900 DEG C of temperature of whiteness 91% naturally cooled to normal temperature after 4 hours, then worn into 120 order powders respectively, obtained the activated aluminum oxide 645g of tool and 550g calcium oxide powder;
(2), getting the aluminum oxide powder 560g of step (1) gained, calcium oxide powder 340g and calorific value is that the coal dust 100g of 7100kcal/kg mixes, add appropriate clear water stirring and make spherule, again through the temperature calcination 5 hours of 1250 DEG C, wear into 150 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder 900g that quality of alumina content is 62%;
(3), be in the iron-free aluminum chloride liquid of 7.0% at 8000g quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 180 revs/min of conditions, then react 80 minutes at temperature is 80 DEG C, the rafifinal deironing 45 minutes of 2.0% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 280 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 100 DEG C, obtain the powdery iron-free poly aluminium chloride that 3880g quality of alumina content is 29%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
embodiment 5:
The method of powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, comprises following raw material and preparation process:
(1), by 10t quality of alumina content be 64.5% aluminium hydroxide and 10t calcium carbonate mass content 98.5%, calcite in powder pre-burning at 900 DEG C of temperature of whiteness 91% naturally cooled to normal temperature after 4 hours, then worn into 120 order powders respectively, obtained the activated aluminum oxide 6.45t of tool and 5.5t calcium oxide powder;
(2), getting the aluminum oxide powder 5.6t of step (1) gained, calcium oxide powder 3.4t and calorific value is that the coal dust 1t of 7100kcal/kg mixes, add appropriate clear water stirring and make spherule, again through the temperature calcination 5 hours of 1250 DEG C, wear into 150 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder 9t that quality of alumina content is 62%;
(3), be in the iron-free aluminum chloride liquid of 7.0% at 80t quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 180 revs/min of conditions, then react 80 minutes at temperature is 80 DEG C, the rafifinal deironing 45 minutes of 1.0 % of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 280 DEG C by this liquid poly aluminium chloride at hot blast temperature, tail air temperature is carry out spraying dry at 105 DEG C, obtain the powdery iron-free poly aluminium chloride that 38.0t quality of alumina content is 30%, other quality index of this product are up to state standards the requirement of " Drinking Water poly aluminium chloride " (GB15892-2009).
Claims (1)
1. a method for powdery iron-free poly aluminium chloride prepared by high whiteness calcium aluminate, it is characterized in that: comprise following raw material and preparation process:
(1) be, that the aluminium hydroxide of 64% ~ 65% and calcium carbonate mass content is greater than 98%, whiteness is greater than 90% calcite in powder pre-burning at 850 DEG C ~ 950 DEG C temperature naturally cool to normal temperature after 3 hours ~ 5 hours by quality of alumina content, then worn into 80 order ~ 120 order powders respectively, obtained the activated aluminum oxide powder of tool and calcium oxide powder;
(2) be, the coal dust of more than 7000kcal/kg by the aluminum oxide powder of step (1) gained, calcium oxide powder and calorific value be 55% ~ 60%, 30% ~ 35% and 10% to mix by massfraction respectively, add appropriate clear water stirring and make spherule, again through the temperature calcination 4 hours ~ 6 hours of 1200 DEG C ~ 1300 DEG C, wear into 100 order ~ 180 order powders after naturally cooling to normal temperature, obtain the high whiteness calcium aluminate powder that quality of alumina content is 60% ~ 65%;
(3), be in the iron-free aluminum chloride liquid of 5.0% ~ 10.0% at quality of alumina mark, low whipping speed is the calcium aluminate powder adding step (2) gained under 120 revs/min ~ 200 revs/min conditions, then react 60 minutes ~ 90 minutes at temperature is 25 DEG C ~ 100 DEG C, the rafifinal deironing 30 minutes ~ 60 minutes of 1.0% ~ 3.0% of calcium aluminate massfraction is added again after reaction, iron-free poly aluminium chloride liquid is obtained after filtration, be 280 DEG C ~ 300 DEG C by this poly aluminium chloride liquid at hot blast temperature, tail air temperature is carry out spraying dry at 100 DEG C ~ 110 DEG C, obtain the powdery iron-free poly aluminium chloride that quality of alumina content is 29% ~ 33%.
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| CN104828849B (en) * | 2015-04-24 | 2016-08-24 | 长沙理工大学 | A kind of by the method for duralumin standby high-whiteness polyaluminium chloride made of stones |
| CN113461349A (en) * | 2021-07-23 | 2021-10-01 | 深圳市市政工程总公司 | Preparation method of sludge dewatering curing agent |
| CN116040670B (en) * | 2023-03-31 | 2023-08-08 | 内蒙古蒙泰集团有限公司 | Method for producing polyaluminum chloride in process of preparing aluminum silicon oxide from fly ash |
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| CN101928135A (en) * | 2010-09-01 | 2010-12-29 | 中国地质大学（北京） | Calcium hexaluminate lightweight refractory brick and preparation method thereof |
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