CN101234765A - Method of reutilization of waste lye in producing zirconium oxychloride from alkali fusion zircon - Google Patents
Method of reutilization of waste lye in producing zirconium oxychloride from alkali fusion zircon Download PDFInfo
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- CN101234765A CN101234765A CNA2007100634401A CN200710063440A CN101234765A CN 101234765 A CN101234765 A CN 101234765A CN A2007100634401 A CNA2007100634401 A CN A2007100634401A CN 200710063440 A CN200710063440 A CN 200710063440A CN 101234765 A CN101234765 A CN 101234765A
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- zircon
- waste lye
- zirconium oxychloride
- lye
- alkali
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Abstract
The invention relates to a method for recycling and reusing waste alkali solution in the production of zirconium oxychloride by using alkali fusion zircon in which precipitant is added to the waste alkali solution in the production of the zirconium oxychloride by using the alkali zircon; then, the obtained solution is heated, stirred, filtered and concentrated to obtain alkali solution and solid alkali directly used for sintering the zircon. The added precipitant refers to lime milk and quick lime; silicate ions in the waste alkali solution can be precipitated in a form of hydrated calcium silicon residue through heating and stirring to achieve the recycling and reusing of the waste alkali solution. The method for recycling and reusing the waste alkali solution has the advantages of no required special equipment, simple operation, remarkable economic and social benefits as well as easy implementation and promotion and at the same time solves the problem of recycling and reusing of a great amount of waste alkali solution produced in production process of the zirconium oxychloride; therefore, the production cost is reduced and consumption of soda resource in zirconium oxychloride industry is decreased.
Description
Technical field
The invention belongs to the recoverying and utilizing method of waste lye in a kind of producing zirconium oxychloride from alkali fusion zircon, relate to the processing that contains the silicate ion waste lye, be specially adapted to the recycling of waste lye in the producing zirconium oxychloride from alkali fusion zircon.
Background technology
According to relevant, 2004 and 2005, China's producing zirconium oxychloride from alkali fusion zircon output surpassed 100,000 tons/year, and the annual industrial alkali waste liquid that produces just reaches more than 250,000 tons.The waste lye of producing zirconium oxychloride from alkali fusion zircon is created in the water washing process of sintered material, mainly contains Na
2SiO
3With, wherein contain 5 weight %～12 weight %NaOH and 2 weight %～6 weight %SiO
2, at present, most zirconium chemicals manufacturer does not fully recycle waste lye, but sell at a bargain as industrial effluent, be used for the production of paper industry and water glass (being commonly called as sodium silicate), both wasted a large amount of caustic soda resources, the economic interests of having lost enterprise again.
Summary of the invention
The object of the present invention is to provide the recoverying and utilizing method of waste lye in a kind of producing zirconium oxychloride from alkali fusion zircon, be by in the producing zirconium oxychloride from alkali fusion zircon the recycling of a large amount of waste lyes of generation, a kind of cost-effective spent lye treatment method is provided.
For achieving the above object, the present invention takes following technical scheme:
The recoverying and utilizing method of waste lye in a kind of producing zirconium oxychloride from alkali fusion zircon.This method is: add precipitation agent in the waste lye that produces in the producing zirconium oxychloride from alkali fusion zircon flow process, after heating, stirring fully reaction, obtain alkali lye and throw out, then after filtration or leave standstill clarification, separate alkali lye and throw out, separate the industrial raw material that the throw out that obtains can be used as products such as producing cement, slag powders after treatment, the alkali lye that obtains is after concentrating, obtain the liquid caustic soda of NaOH content 28～35 weight % or the liquid caustic soda of greater concn, can substitute the sintering that caustic soda directly applies to zircon.
Waste lye used in the present invention is the waste lye (hereinafter also being called for short waste lye) that obtains in the water washing process with the sintered material in the producing zirconium oxychloride from alkali fusion zircon technology, mainly contains Na
2SiO
3With, wherein contain 5 weight %～12 weight %NaOH and 2 weight %～6 weight %SiO
2The present invention is to be raw material with this waste lye, separates the purification waste lye by milk of lime or unslaked lime precipitated silicate radical ion, and the alkali lye after concentrated can directly apply to the sintering of zircon.
In the recoverying and utilizing method of waste lye, described precipitation agent is milk of lime suspension liquid or unslaked lime in producing zirconium oxychloride from alkali fusion zircon of the present invention.Milk of lime suspension liquid precipitation agent compound method: the milk of lime suspension liquid that certain mass unslaked lime is mixed with suitable concn, the solvent that uses can be water or waste lye, the concentration of milk of lime (CaO content) is according to easy to operate and definite, and wherein said waste lye is the waste lye in the producing zirconium oxychloride from alkali fusion zircon.Also can directly select for use unslaked lime as precipitation agent without the preparing lime milk suspension liquid.
In the recoverying and utilizing method of waste lye, described precipitation agent is a unslaked lime in producing zirconium oxychloride from alkali fusion zircon of the present invention.The content of the content of active calcium oxide and waste lye mesosilicic acid radical ion is relevant in the consumption of unslaked lime and the unslaked lime, active CaO and SiO
2The theoretical molar ratio is 1: 1, but in practice, in order to obtain treatment effect preferably, all can be higher than this ratio generally speaking.The present invention recommends in the unslaked lime SiO in the active CaO and waste lye
2Mol ratio is 1.0-1.8: 1.
In the recoverying and utilizing method of waste lye, described precipitation agent is the milk of lime suspension liquid in producing zirconium oxychloride from alkali fusion zircon of the present invention.Described milk of lime suspension liquid is that unslaked lime and solvent are mixed with, employed solvent is water or waste lye, wherein, described waste lye is the waste lye in the producing zirconium oxychloride from alkali fusion zircon, and the proportioning of unslaked lime and solvent is controlled at 0.2-0.5 kilogram lime/rise solvent.SiO in active CaO and the waste lye in the milk of lime suspension liquid
2Mol ratio is 1.0-1.8: 1.
In the recoverying and utilizing method of waste lye, the employed solvent of preparing lime milk suspension liquid precipitation agent is preferably waste lye in producing zirconium oxychloride from alkali fusion zircon of the present invention, and this waste lye is the waste lye in the producing zirconium oxychloride from alkali fusion zircon.When solvent is waste lye, SiO in active CaO and the waste lye in the described milk of lime suspension liquid
2Waste lye in the mol ratio also comprises the waste lye as solvent.
In the recoverying and utilizing method of waste lye, in described heated and stirred process, temperature is 30-95 ℃ in producing zirconium oxychloride from alkali fusion zircon of the present invention, and churning time is 30-120 minute.Concrete Heating temperature and churning time are determined according to treatment effect, production efficiency and handled easily.
In producing zirconium oxychloride from alkali fusion zircon of the present invention in the recoverying and utilizing method of waste lye, in described filtration procedure, can with after the heated and stirred and the suspension liquid that fully reacts of waste lye and precipitation agent directly will send into pressure filter, through direct press filtration, separate hydrated calcium white residue and alkali lye in the suspension liquid, also can separate the hydrated calcium white residue of upper strata alkali lye and lower sediment with after also fully the suspension liquid of reaction process leaves standstill clarification after the heated and stirred.Alkali lye is descended concentrating of step, can be used as the industrial raw material of products such as producing cement, slag powders after the hydrated calcium white residue is handled through dewatered drying.
In producing zirconium oxychloride from alkali fusion zircon of the present invention in the recoverying and utilizing method of waste lye, in described concentration process, can take multiple concentrated mode, the condition that retort internal heating and add heating for example, concrete type of heating possess according to factory and determining.Alkali lye after the processing can be concentrated into the liquid caustic soda of NaOH content 28～35 weight % or greater concn, and this liquid caustic soda can directly apply to the sintering of zircon.
Steps in sequence in producing zirconium oxychloride from alkali fusion zircon of the present invention in the waste lye recoverying and utilizing method is:
(1) preparing lime milk suspension liquid can directly be precipitation agent with unslaked lime without the preparing lime milk suspension liquid also;
(2) milk of lime suspension liquid or unslaked lime in waste lye and the step (1) are joined in the retort with certain proportion, heated and stirred is fully reacted then, and Heating temperature is 30-95 ℃, and churning time is 30-120 minute;
(3) reacted suspension liquid is sent into pressure filter, directly separate hydrated calcium white residue and alkali lye; Perhaps reacted suspension liquid is left standstill clarification, separate the hydrated calcium white residue of upper strata alkali lye and lower sediment then;
(4) mode with retort internal heating or outer heating concentrates alkali lye, is concentrated into the liquid caustic soda of NaOH content 28～35 weight % or greater concn, and this liquid caustic soda can directly apply to the sintering of zircon.
Advantage of the present invention is: the present invention mainly solves the recycling problem of a large amount of waste lyes that produced in the zirconium oxychloride production technique, can reduce its production cost, has also reduced the consumption of zirconium oxychloride industry to the caustic soda resource simultaneously.It is raw material that the present invention is to use the waste lye in the producing zirconium oxychloride from alkali fusion zircon, removes silicate ion in the waste lye by milk of lime or unslaked lime precipitation, is the silicate ion in the waste lye is precipitated out in the mode of hydrated calcium white residue; By filtering, separate hydrated calcium white residue and alkali lye; Alkali lye is through concentrating the liquid caustic soda that just can obtain NaOH content 28～35 weight % or greater concn, and this liquid caustic soda can directly apply to the sintering of zircon, reaches the purpose that waste lye is recycled.The present invention does not need specific installation, and is simple to operate, and economic and social benefit is obvious, easy to implement to promote, recycles for waste lye and opens up a new outlet.
Embodiment
The preparing lime milk suspension liquid, also can be without the preparing lime milk suspension liquid, it directly is precipitation agent with unslaked lime, waste lye and milk of lime suspension liquid or unslaked lime join in the retort with certain proportion then, heated and stirred is fully reacted then, Heating temperature is 30-95 ℃, and churning time is 30-120 minute.Reacted suspension liquid is sent into pressure filter, directly separate hydrated calcium white residue and alkali lye; Perhaps reacted suspension liquid is left standstill clarification, separate the hydrated calcium white residue of upper strata alkali lye and lower sediment then.Mode with retort internal heating or outer heating concentrates alkali lye, is concentrated into the liquid caustic soda of NaOH content 28～35 weight % or greater concn, and this liquid caustic soda can directly apply to the sintering of zircon.
Embodiment 1: be the embodiment of precipitation agent with unslaked lime
Use the waste lye in the producing zirconium oxychloride from alkali fusion zircon, contain 10.2 weight %NaOH, 5.29 weight %SiO in this waste lye
2The mass percentage content of active CaO is 90% in the unslaked lime that uses.
70 kilogram of raw lime and 1000L waste lye are joined in the retort, wherein, SiO in active CaO and the waste lye in the unslaked lime
2About 1.06: 1 of mol ratio, heated and stirred is fully reacted then, 30 ℃ of Heating temperatures, churning time 30 minutes; Reacted suspension liquid is sent into pressure filter, separate hydrated calcium white residue and alkali lye; Utilize water vapor internal heating vaporizer with the alkali liquor concentration that press filtration goes out, make out and contain 29.2 weight %NaOH, 0.42 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.Made drawing contains 29.2 weight %NaOH, 0.42 weight %SiO
2Alkali lye also can further concentrate, again through after further concentrating, can draw and contain 48.2 weight %NaOH, 0.69 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.
Embodiment 2: be the embodiment of precipitation agent with unslaked lime
Use the waste lye in the producing zirconium oxychloride from alkali fusion zircon, contain 10.2 weight %NaOH, 5.29 weight %SiO in this waste lye
2The mass percentage content of active CaO is 90% in the unslaked lime that uses.
120 kilogram of raw lime and 1000L waste lye are joined in the retort, wherein, SiO in active CaO and the waste lye in the unslaked lime
2About 1.8: 1 of mol ratio, heated and stirred is fully reacted then, 95 ℃ of Heating temperatures, churning time 120 minutes; The suspension liquid process of also fully reacting after the heated and stirred is left standstill clarification, separate the hydrated calcium white residue of upper strata alkali lye and lower sediment; Utilize water vapor internal heating vaporizer with isolated alkali liquor concentration, make out and contain 33.2 weight %NaOH, 0.10 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.Made drawing contains 33.2 weight %NaOH, 0.10 weight %SiO
2Alkali lye also can further concentrate, again through after further concentrating, can draw and contain 48.6 weight %NaOH, 0.15 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.
Embodiment 3: be the embodiment of precipitation agent with milk of lime
Use the waste lye in the producing zirconium oxychloride from alkali fusion zircon, contain 10.2 weight %NaOH, 5.29 weight %SiO in this waste lye
2The mass percentage content of active CaO is 90% in the unslaked lime that uses.
70 kilogram of raw lime are mixed with 350 liters of waste lyes, preparation milk of lime suspension liquid, wherein, the proportioning of unslaked lime and solvent is about 0.2 kilogram of lime/rise solvent.650L waste lye and the aforementioned milk of lime suspension liquid that makes are joined in the retort, wherein, SiO in active CaO and the waste lye in the unslaked lime
2About 1.06: 1 of total mol ratio, heated and stirred is fully reacted then, 30 ℃ of Heating temperatures, churning time 30 minutes; Reacted suspension liquid is sent into pressure filter, separate hydrated calcium white residue and alkali lye; Utilize water vapor internal heating vaporizer with the alkali liquor concentration that press filtration goes out, make out and contain 31.2 weight %NaOH, 0.22 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.Made drawing contains 31.2 weight %NaOH, 0.22 weight %SiO
2Alkali lye also can further concentrate, again through after further concentrating, can draw and contain 48.5 weight %NaOH, 0.34 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.
Embodiment 4: be the embodiment of precipitation agent with milk of lime
Use the waste lye in the producing zirconium oxychloride from alkali fusion zircon, contain 10.2 weight %NaOH, 5.29 weight %SiO in this waste lye
2The mass percentage content of active CaO is 90% in the unslaked lime that uses.
120 kilogram of raw lime are mixed with 240 liters of waste lyes, preparation milk of lime suspension liquid, wherein, the proportioning of unslaked lime and solvent is about 0.5 kilogram of lime/rise solvent.760L waste lye and the aforementioned milk of lime suspension liquid that makes are joined in the retort, wherein, SiO in active CaO and the waste lye in the unslaked lime
2About 1.8: 1 of total mol ratio, heated and stirred is fully reacted then, 95 ℃ of Heating temperatures, churning time 120 minutes; The suspension liquid process of also fully reacting after the heated and stirred is left standstill clarification, separate the hydrated calcium white residue of upper strata alkali lye and lower sediment; Utilize water vapor internal heating vaporizer with isolated alkali liquor concentration, make out and contain 34.1 weight %NaOH, 0.08 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.Made drawing contains 34.1 weight %NaOH, 0.08 weight %SiO
2Alkali lye also can further concentrate, again through after further concentrating, can draw and contain 48.8 weight %NaOH, 0.11 weight %SiO
2Alkali lye, be raw material with this liquid caustic soda, carry out the SINTERING PRODUCTION of zircon, successfully give birth to the qualified zirconium oxychloride of preparation.
Claims (9)
1. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon, it is characterized in that: this method is that the waste lye in producing zirconium oxychloride from alkali fusion zircon adds precipitation agent, through heated and stirred, filter or leave standstill clarification and concentrate, obtain the liquid caustic soda of NaOH content 28～35 weight % or the liquid caustic soda of greater concn, the liquid caustic soda that obtains can directly apply to the sintering of zircon.
2. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 1 is characterized in that: described precipitation agent is a unslaked lime.
3. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 2 is characterized in that: SiO in active CaO and the waste lye in the unslaked lime
2Mol ratio is 1.0-1.8: 1.
4. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 1 is characterized in that: described precipitation agent is the milk of lime suspension liquid.
5. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 4, it is characterized in that: described milk of lime suspension liquid is that unslaked lime and solvent are mixed with, employed solvent is water or waste lye, wherein, described waste lye is the waste lye in the producing zirconium oxychloride from alkali fusion zircon, the proportioning of unslaked lime and solvent is controlled at 0.2-0.5 kilogram lime/rise solvent, SiO in active CaO and the waste lye in the milk of lime suspension liquid
2Mol ratio is 1.0-1.8: 1.
6. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 5 is characterized in that: described solvent is a waste lye.
7. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 1 is characterized in that: in described heated and stirred process, temperature is 30-95 ℃, and churning time is 30-120 minute.
8. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 1, it is characterized in that: in described filtration procedure, be the suspension liquid that obtains after waste lye and precipitation agent are fully reacted through direct press filtration, separate hydrated calcium white residue and alkali lye in the suspension liquid.
9. the recoverying and utilizing method of waste lye in the producing zirconium oxychloride from alkali fusion zircon according to claim 1, it is characterized in that: leave standstill in the clarifying process described, be that the suspension liquid process that will also fully react after the heated and stirred leaves standstill clarification, separate the hydrated calcium white residue of upper strata alkali lye and lower sediment.
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| CNA2007100634401A CN101234765A (en) | 2007-01-31 | 2007-01-31 | Method of reutilization of waste lye in producing zirconium oxychloride from alkali fusion zircon |
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| CNA2007100634401A CN101234765A (en) | 2007-01-31 | 2007-01-31 | Method of reutilization of waste lye in producing zirconium oxychloride from alkali fusion zircon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011463A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Method for removing zirconium in sewage |
| CN110713193A (en) * | 2019-11-18 | 2020-01-21 | 中国科学院过程工程研究所 | Method for recycling zirconium resource from waste silicon slag discharged in zirconium oxychloride production |
-
2007
- 2007-01-31 CN CNA2007100634401A patent/CN101234765A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011463A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Method for removing zirconium in sewage |
| CN110713193A (en) * | 2019-11-18 | 2020-01-21 | 中国科学院过程工程研究所 | Method for recycling zirconium resource from waste silicon slag discharged in zirconium oxychloride production |
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Open date: 20080806 |