CN105753278A - Method for purification and reduction of fluorine-containing sludge in solar cell or glass reduction industry - Google Patents
Method for purification and reduction of fluorine-containing sludge in solar cell or glass reduction industry Download PDFInfo
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- CN105753278A CN105753278A CN201610217738.2A CN201610217738A CN105753278A CN 105753278 A CN105753278 A CN 105753278A CN 201610217738 A CN201610217738 A CN 201610217738A CN 105753278 A CN105753278 A CN 105753278A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a method for purification and reduction of fluorine-containing sludge in the solar cell or glass reduction industry and belongs to the technical field of environmental protection. The method comprises the following steps: successively carrying out primary washing on the fluorine-containing sludge discharged by a waste water treatment station in a certain solid-to-liquid ratio, acid pickling, secondary washing and waste water treatment. By adopting the method disclosed by the invention, recovery rate of fluorine is more than 80%, content of available calcium fluoride in the fluorine-containing sludge can be improved to more than or equal to 85%, content of silicon dioxide in the fluorine-containing sludge can be reduced to less than 1.5%, and a recycled product can be used as crude product calcium fluoride industrial raw material resource; besides, fluorine resource in the fluorine-containing sludge can be efficiently recycled, discharge amount of sludge is greatly reduced, environmental pollution is reduced, and sludge treatment cost is saved. The method does not use other chemical agent except water, waste acid discharged by an enterprise self is mainly used for reacting with the fluorine-containing sludge for purification, waste is treated by utilizing waste, and production cost is low.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to purification and the decrement treatment technology of crystal silicon solar energy battery and the discharged fluorine-containing sludge of glass thinning industry.
Technical background
Crystal silicon solar energy battery production is the important step of photovoltaic industry chain, and it all employs larger amount of Fluohydric acid. in the production processes such as making herbs into wool, pickling and etching.Glass thinning production is raw material manufacturing process important during liquid crystal panel produces, and chemical method glass thinning also using relatively large Fluohydric acid. in producing.Crystal silicon solar energy battery produces in producing with glass thinning the Fluohydric acid. used and all causes fluorinion concentration in its waste discharge high, research shows, fluorinion concentration on average about more than 1000mg/L in China's crystal silicon solar energy battery and chemical method the discharged fluoride waste of glass thinning industry (including fluorine-containing spent acid).At present, the fluoride waste that enterprise produces is generally adopted feeding lime, carbide slag or calcium salt reaction precipitation and processes fluorine removal, and by reaction precipitation, the fluorion in waste water is converted into calcium fluoride, forms mud, discharges with fluorine-containing sludge form.Generally, the fluorion in processed waste water needs to be reduced to below 10mg/L, is equivalent to the fluorion of more than 99% in waste water and transfers in fluorine-containing sludge.
Owing to wastewater treatment requires that fluorine removing rate is significantly high, so the calcium salt added in generally processing or amount of lime are much larger than its theoretical requirement, further need exist for adding coagulant and the flocculant such as relatively large aluminum sulfate, aluminium polychlorid, polyacrylamide, fluorinion concentration just can be reduced to below permission discharge standard, and a large amount of unemployed calcium can enter mud with coprecipitations such as the forms such as calcium hydroxide, calcium carbonate, calcium sulfate, calcium silicates and coagulant.It addition, manufacture of solar cells and glass thinning produce containing impurity such as relatively large silicic acid, hexafluosilicic acid in the waste water of discharge, mud can be entered by coprecipitation in the treatment of waste water.It is big that above reason all causes discharged fluorine-containing sludge amount in fluoride wastewater treatment, and wherein effectively calcium fluoride constituent content is relatively low, impurity content is high.
Research shows, in manufacture of solar cells wastewater treatment, about 6t/MW is measured in fluorine-containing sludge generation, for an enterprise producing 1GW solaode per year, its year discharge dehydration fluorine-containing sludge more than about 6000 tons.And this kind of moisture percentage in sewage sludge is higher, general moisture content more than 50%, the effective content of fluoride of butt is low, purity difference, wherein effectively Calcium Fluoride Content is generally no greater than 70%, impurity content is high, as wherein dioxide-containing silica, more than 5%, additionally contains the plurality of impurities such as sulfate, aluminium salt, hydrochlorate, it is substantially free of use value and approach, disposes only as sludge waste.The discharge of a large amount of fluorine-containing sludges causes problems with:
1) sludge treatment cost is high: the fluorine-containing sludge of a large amount of discharges causes enterprise rationally to dispose costly for mud, and this kind of fluorine-containing sludge is attributed to hazardous waste by China some areas, causes that business economic pressure is bigger.For a manufacturing enterprise producing 1GW/a polycrystal silicon cell per year, if the disposal costs such as Sludge landfill are with 500 yuan/ton of calculating, then the expense for fluorine-containing sludge disposal is often only just up to more than 3,000,000 yuan by enterprise；If pressing dangerous waste disposal, its disposal costs to be also multiplied.
2) harm of environmental pollution and latency environment is serious: a large amount of fluorine-containing sludges are improper to be deposited, transport or disposal can cause environmental pollution or harm.Fluorine-containing sludge fills not only land occupation, and it would furthermore be possible to can due to contaminated soil, subsoil water or surface water such as mud leachings.Fluorine-containing sludge is adulterated brickmaking, it is possible to causing the pollutant severe overweights such as brickmaking Fluoride Factors in Tail Gas, and institute's brickmaking in use may produce new environmental problem owing to the pouring of fluorine goes out, potential hazard is more serious.Under the pressure of higher cost of disposal, Some Enterprises is reluctant to adopt or beyond one's means regular or reasonably deposit or Disposal Measures, arbitrarily stacks, illegal disposes, illegal inversion fluorine-containing sludge, causes serious harm.
3) serious waste of resources: a large amount of fluorions are with mud discharging, it does not have obtain resource reclaim recycling, cause the more serious fluorine wasting of resources.Fluorine is the main component of fluorite, belongs to non-renewable resources, it is accordingly required in particular to protection.From 1999, fluorite was protected by China as strategic resource.Carrying out the recycling of fluorine resource and opening up new fluorine resource is with the same problem demanding prompt solution of protection fluorine resource.In 2010 " General Office of the State Council is about the notice taking aggregate measures that exploitation and the production of fire clay fluorite are controlled " (Office of the State Council sends out [2010] No. 1), it was shown that the recycling of fluorine resource will be encouraged.
In sum, crystal silicon solar energy battery industry is with glass thinning industry, and a large amount of fluorine-containing sludges that wastewater treatment is discharged cause environmental pollution, fluorine serious waste of resources and bring heavy financial burden and environmental protection and social pressure for enterprise.
Therefore, such fluorine-containing sludge is purified process, improve the effective content of calcium fluoride component, mud is turned waste into wealth, both can realize resource reuse, fluorine-containing sludge outer discharge capacity can be greatly lowered again, reduce sludge treatment expense, meanwhile, reclaim product and can produce economic worth, reduce environmental protection of enterprise burden and economic pressures.Carry out fluorine-containing sludge purification resource reuse and there is important environment, economy and social meaning.At present, the correlation technique report of the sector fluorine-containing sludge purification also it is not related to both at home and abroad.
Summary of the invention
The present invention proposes a kind of solaode or glass thinning industry fluorine-containing sludge purification and decrement method, the method can fluorine resource in high efficiente callback fluorine-containing sludge, produce calcium fluoride, it is achieved resource recycling, produce economic benefit；Mud outer discharge capacity can also be greatly decreased, reduce environmental pollution and harm, and save environmental protection of enterprise cost.
A kind of solaode that the present invention proposes or glass thinning industry fluorine-containing sludge purification and decrement method, it is characterised in that the method comprises the steps:
1) first time washing: by the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge and water mix and blend, be then filtered or centrifuge dehydration, obtain solid filter cake and filtrate；
2) pickling: by step 1) the fluorine-containing spent acid mix and blend that discharges with enterprise of gained filter cake reacts, is then filtered or centrifuge dehydration, obtains solid filter cake and filtrate；
3) second time washing: by step 2) gained solid filter cake and water mix and blend, then it is filtered or centrifuge dehydration, is washed with water and washs, then dry, be recycled product；
4) wastewater treatment: by above step 1) 3) filtrate collection that discharges is waste water, enters scale wastewater treatment station and processes together or individual processing, or for reclaiming wherein fluorine resource further.
The feature of the present invention and having the beneficial effects that: adopt fluorine-containing sludge purification provided by the invention and decrement method, can fluorine resource in the fluorine-containing sludge that produces of high efficiente callback crystal silicon solar energy battery or glass thinning industry, produce the calcium fluoride product that purity is higher, realize resource recycling, produce economic benefit；Mud outer discharge capacity can also be greatly decreased, reduce environmental pollution and harm, and save environmental protection cost for enterprise.It addition, the inventive method is in fluorine-containing sludge process, except with not using other chemical agents except water, only using the spent acid of enterprise discharge itself, the treatment of wastes with processes of wastes against one another, production cost is low, also can suitably reduce fluorine-containing spent acid treating capacity and pollution level.
Adopting the inventive method, the fluorine response rate, more than 80%, obtains in product that butt Calcium Fluoride Content is more than 85%, and butt dioxide-containing silica is lower than 1.5%.Product can use as the calcium fluoride raw material of industry.
Detailed description of the invention
Solaode or glass thinning industry fluorine-containing sludge purification that the present invention proposes describe in detail as follows with decrement method:
This method comprises the steps:
1) first time washing: by the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge and water mix and blend, be then filtered or centrifuge dehydration, obtain solid filter cake and filtrate；Implement and include:
1 1) adding water in the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge, water used is tap water or deionized water, and the fluorine-containing sludge absolute dry mass that water used adds in unit volume is 125 250kg/m3；
1 2) with the speed of agitator of 80 120rpm, stir 60 120min, make solid disperse and make solid-liquid be sufficiently mixed；
1 3) by 1 2) gained solidliquid mixture adopts centrifuge or filter dehydration, obtains solid filter cake and liquid filtrate.
2) pickling: to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's discharge, mix and blend reacts, and is then filtered or centrifuge dehydration, obtains solid filter cake and filtrate；Implement and include:
2 1) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's production line discharge.Fluorine-containing spent acid used refers to the acid pickle that the making herbs into wool, etching or the acid pickling groove liquid that are raw material with Fluohydric acid., hydrochloric acid or nitric acid in enterprise's production line discharge, and its pH is less than 1.5, and fluorinion concentration is more than 50g/L；The consumption of described fluorine-containing spent acid is: the fluorine-containing sludge absolute dry mass that spent acid used adds in unit volume is 125 250kg/m3；
2 2) by 2 1) gained mixed liquor at 20 60 DEG C of speeds of agitator with 80 120rpm, stir 120 240min, make solid filter cake disperse and make solid-liquid be sufficiently mixed reaction, obtaining solidliquid mixture；
2 3) by 2 2) gained solidliquid mixture adopts centrifuge or filter dehydration, respectively obtains solid filter cake and filtrate；
3) second time washing: by step 2) gained solid filter cake and water mix and blend, then it is filtered or centrifuge dehydration, is washed with water and washs, then dry, be recycled product；Wherein, Cake Wash to the pH value discharging filtrate reaches more than 6.0；Water used is tap water or deionized water；In recovery product, calcium fluoride purity is more than 85%, and dioxide-containing silica, less than 1.5%, has recycle value.
4) wastewater treatment: by step 1) 3) produced by filtrate collection be waste water, scale wastewater treatment station can be entered and process together or individual processing, its defluorination method is referred to patented technology " ZL201010286071.4 ".Can also be used for reclaiming wherein fluorine resource further, method is referred to Patents technology.
Embodiment one
A polysilicon solar battery slice manufacturing enterprise, its cell piece production capacity 900MW/a.Enterprise's day waste discharge is about 1500m3/ d, fluorinion concentration is about about 300mg/L, additionally discharges fluorine-containing spent acid day and is about 40m3/ d, wherein fluorinion concentration 60 120g/L.Scale wastewater treatment station adopts two-stage reaction precipitation fluorine removal, and pharmacy response used includes Calx, calcium chloride, sodium hydroxide etc., and coagulant used is aluminium polychlorid and polyacrylamide.Scale wastewater treatment station fluorine removal facility discharges fluorine-containing sludge and be about 15t/d every day, and detection shows, moisture content about 55% in this fluorine-containing sludge, butt Calcium Fluoride Content about 67%, butt dioxide-containing silica about 5.6%.
Adopt the present invention to provide method to be purified and decrement this enterprise's fluorine-containing sludge, comprise the following steps that
1) by the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge and water mix and blend, then it is filtered dehydration, obtains solid filter cake and filter liquor；Implement and include:
1 1) water used by is tap water, and the fluorine-containing sludge absolute dry mass that water used adds in unit volume is 250kg/m3；
1 2) with the speed of agitator of 120rpm, stir 60min, make solid dispersion solid-liquid be sufficiently mixed；
1 3) by 1 2) the employing filter dehydration of gained solidliquid mixture, respectively obtain solid filter cake and liquid filtrate.
2) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's discharge, mix and blend reacts, and is then filtered dehydration, obtains solid filter cake and filtrate；Implement and include:
2 1) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's production line discharge.Spent acid pH used less than 1.5, fluorinion concentration 60 120g/L；
2 2) consumption of described fluorine-containing spent acid is: the fluorine-containing sludge absolute dry mass that spent acid used adds in unit volume is 125kg/m3；
2 3) by 2 2) gained mixed liquor at 20 30 DEG C of speeds of agitator with 80rpm, stir 240min, make solid dispersion solid-liquid be sufficiently mixed reaction；
2 4) by 2 3) the employing filter dehydration of gained solidliquid mixture, respectively obtain solid filter cake and liquid filtrate.
3) by step 2) gained solid filter cake and water mix and blend, and carry out filtering means dehydration, then filter cake is washed.It is washed to discharge filtrate pH and reaches more than 6.0；Water used is tap water.Then gained filter cake is dried and is recycled product.
4) by step 1) 3) produced by filtrate collection be waste water, include scale wastewater treatment station in and carry out fluorine removal and denitrogenation processing together.
Obtaining product by above method, detect its butt Calcium Fluoride Content 88%, dioxide-containing silica 1.2%, after processing above, per kilogram butt fluorine-containing sludge obtains product 0.86 kilogram, and the fluorine response rate is high, and mud decrement rate is more than 70%.
Embodiment two
Domestic certain medium-scale glass thinning manufacturing enterprise, day discharge fluoride waste is about 1000m3/ d, fluorinion concentration is about about 250mg/L, it addition, collect discharge fluorine-containing spent acid enterprise's day to be about 15m3/ d, wherein fluorinion concentration is about 85g/L.Scale wastewater treatment station adopts two-stage reaction precipitation fluorine removal, and pharmacy response used includes carbide slag, Calx, calcium chloride etc., and coagulant used is aluminium polychlorid and polyacrylamide.Scale wastewater treatment station fluorine removal facility day discharge fluorine-containing sludge is about 10t/d, and detection shows, moisture content about 57% in this fluorine-containing sludge, butt Calcium Fluoride Content about 72%, butt dioxide-containing silica about 6.3%.
Apply the inventive method to this enterprise's mud purification and decrement, comprise the steps:
1) by the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge and water mix and blend, dehydration, gained solid filter cake and centrifugal filtrate then it are centrifuged；Implement and include:
1 1) water used by is deionized water, and consumption is: the fluorine-containing sludge absolute dry mass that water used adds in unit volume is 125kg/m3；
1 2) with the speed of agitator of 80rpm, stir 120min, make solid dispersion solid-liquid be sufficiently mixed；
1 3) by 1 2) gained solidliquid mixture employing centrifuge dewatering, respectively obtain solid filter cake and liquid filtrate.
2) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's discharge, mix and blend reacts, and is then centrifuged dehydration, obtains solid filter cake and filtrate；Implement and include:
2 1) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's production line discharge.Spent acid pH used is less than 1.5, and fluorion mean concentration is about 85g/L；
2 2) consumption of described fluorine-containing spent acid is: the fluorine-containing sludge absolute dry mass that spent acid used adds in unit volume is 250kg/m3；
2 3) by 2 2) gained mixed liquor at 50 60 DEG C of speeds of agitator with 120rpm, stir 120min, make solid dispersion solid-liquid be sufficiently mixed reaction；
2 4) by 2 3) gained solidliquid mixture employing centrifuge dewatering, respectively obtain solid filter cake and liquid filtrate.
3) by step 2) gained solid filter cake and water mix and blend, and centrifuge dehydration, then filter cake is washed, it is washed to discharge filtrate pH and reaches more than 6.0；Water used is deionized water.Then gained filter cake is dried, is recycled product.
4) by step 1) 3) produced by filtrate collection be waste water, include scale wastewater treatment station in and process together.
The recovery product adopting this method to obtain, detects its butt Calcium Fluoride Content 87%, dioxide-containing silica 1.5%, and per kilogram butt fluorine-containing sludge obtains product 0.82 kilogram.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (4)
1. a solaode or glass thinning industry fluorine-containing sludge purification and decrement method, it is characterised in that the method comprises the steps:
1) first time washing: by the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge and water mix and blend, be then filtered or centrifuge dehydration, obtain solid filter cake and filtrate；
2) pickling: by step 1) the fluorine-containing spent acid mix and blend that discharges with enterprise of gained filter cake reacts, is then filtered or centrifuge dehydration, obtains solid filter cake and filtrate；
3) second time washing: by step 2) gained solid filter cake and water mix and blend, then it is filtered or centrifuge dehydration, is washed with water and washs, then dry, be recycled product；
4) wastewater treatment: by above step 1) 3) filtrate collection that discharges is waste water, enters scale wastewater treatment station and processes together or individual processing, or for reclaiming wherein fluorine resource further.
2. such as claim 1) as described in solaode or glass thinning industry fluorine-containing sludge purification and decrement method, it is characterised in that described step 1) once wash, specifically include:
1 1) adding water in the fluorine-containing sludge after the dehydration of scale wastewater treatment station discharge, water used is tap water or deionized water, and the fluorine-containing sludge absolute dry mass that water used adds in unit volume is 125 250kg/m3；
1 2) with the speed of agitator of 80 120rpm, stir 60 120min, make solid disperse and make solid-liquid be sufficiently mixed；
1 3) by 1 2) gained solidliquid mixture adopts centrifuge or filter dehydration, respectively obtains solid filter cake and filtrate.
3. as claimed in claim 1 solaode or glass thinning industry fluorine-containing sludge purification and decrement method, it is characterised in that described step 2) pickling, specifically include:
2 1) to step 1) gained solid filter cake adds the fluorine-containing spent acid of enterprise's production line discharge.Fluorine-containing spent acid used refers to the acid pickle that the making herbs into wool, etching or the acid pickling groove liquid that are raw material with Fluohydric acid., hydrochloric acid or nitric acid in enterprise's production line discharge, and its pH is less than 1.5, and fluorinion concentration is more than 50g/L；The consumption of described fluorine-containing spent acid is: the fluorine-containing sludge absolute dry mass that spent acid used adds in unit volume is 125 250kg/m3；
2 2) by 2 1) gained mixed liquor at 20 60 DEG C of speeds of agitator with 80 120rpm, stir 120 240min, make solid dispersion and solid-liquid be sufficiently mixed reaction；
2 3) by 2 2) gained solidliquid mixture adopts centrifuge or filter dehydration, respectively obtains solid filter cake and filtrate.
4. as claimed in claim 3 solaode or glass thinning industry fluorine-containing sludge purification and decrement method, it is characterized in that, described step 3) secondary washing, specifically include: by step 2) gained solid filter cake and water mix and blend, then it is filtered or centrifuge dehydration, it is washed with water and washs, then dry, be recycled product；Wherein, Cake Wash to the pH value discharging filtrate reaches more than 6.0；Water used is tap water or deionized water.
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| CN201610217738.2A CN105753278A (en) | 2016-04-08 | 2016-04-08 | Method for purification and reduction of fluorine-containing sludge in solar cell or glass reduction industry |
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| CN201610217738.2A CN105753278A (en) | 2016-04-08 | 2016-04-08 | Method for purification and reduction of fluorine-containing sludge in solar cell or glass reduction industry |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013040716A1 (en) * | 2011-09-21 | 2013-03-28 | Ostara Nutrient Recovery Technologies Inc. | Treatment of phosphate-containing wastewater with fluorosilicate and phosphate recovery |
| CN103241758A (en) * | 2013-05-17 | 2013-08-14 | 崔岷 | Method of producing calcium fluoride through bottom mud generated by fluoride waste |
-
2016
- 2016-04-08 CN CN201610217738.2A patent/CN105753278A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013040716A1 (en) * | 2011-09-21 | 2013-03-28 | Ostara Nutrient Recovery Technologies Inc. | Treatment of phosphate-containing wastewater with fluorosilicate and phosphate recovery |
| CN103241758A (en) * | 2013-05-17 | 2013-08-14 | 崔岷 | Method of producing calcium fluoride through bottom mud generated by fluoride waste |
Non-Patent Citations (2)
| Title |
|---|
| 瞿露等: "钙盐法处理太阳能电池生产含氟废水的污泥产量及成分研究", 《环境工程》 * |
| 谢明: "用含氟污泥和含氟硫酸生产氟化钙的工艺研究", 《广州化工》 * |
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