CN102173438A - Method for producing gypsum as byproduct in preparation of lithium carbonate by using lepidolite from tantalum-niobium tailings - Google Patents
Method for producing gypsum as byproduct in preparation of lithium carbonate by using lepidolite from tantalum-niobium tailings Download PDFInfo
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- CN102173438A CN102173438A CN2011100264167A CN201110026416A CN102173438A CN 102173438 A CN102173438 A CN 102173438A CN 2011100264167 A CN2011100264167 A CN 2011100264167A CN 201110026416 A CN201110026416 A CN 201110026416A CN 102173438 A CN102173438 A CN 102173438A
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Abstract
The invention provides a method for producing gypsum which is a byproduct in preparation of lithium carbonate by using lepidolite from tantalum-niobium tailings. The method comprises an acid dipping step in which a dilute sulfuric acid solution is added to a lepidolite raw material and a neutralization fluoride removal step. The invention is characterized in that the method comprises the following steps: pulverizing lepidolite to form lepidolite powders with a particle size of about 200 meshes; feeding the lepidolite powders into a reactor together with a sulfuric acid solution with a concentration of 30% to 70%, with a solid-liquid mass ratio of 1:(2-8); allowing fluoride removal reactions to take place for 3 to 10 hours under such a condition that the reaction temperature ranges from 60 DEG C to 200 DEG C; separating the produced hydrofluoric acid under vacuum after the reactions are completed to form a solid-liquid mixture; filtering off residues to form a mother liquid; performing neutralization fluoride removal, which is implemented by adding equivalent amount of water to the hydrofluoric acid solution that is separated under vacuum into the solid-liquid mixture and then adding calcium hydroxide; adjusting the pH of the liquid within the range from 5 to 7; and filtering to obtain high-purity gypsum.
Description
Technical field
The invention belongs to chemical field, relate to a kind of tantalum niobium mine tailing lithionite that utilizes and prepare the method that Quilonum Retard obtains the by product gypsum.
Background technology
The tantalum niobium lithium ore deposit of Yichuan is the tantalum niobium lithium ore deposit of present Asia maximum, and it contains abundant Rare Metals Materials, as tantalum, niobium, lithium, potassium, sodium, rubidium, caesium etc.Lithionite is that tantalum niobium exploitation mine tailing is through flotation gained byproduct, prepare Quilonum Retard with lithionite and can control reaction conditions well and can obtain a large amount of high-quality by-produced gypsums, this tantalum niobium lithium ore deposit to the comprehensive development and utilization Yichuan has very important economy and strategic value.
Gypsum mainly is hydrous calcium sulfate (CaSO
42H
2O), often accompany organism, sulfide etc., and contain elements such as small amount of aluminum, silicon, magnesium, iron and micro strontium, barium, plaster of paris is anhydrous calciumsulphate (CaSO
4).Be generally white, colourless, colourless transparent crystal is called selenite, sometimes because of impure ash, pale yellow, the shallow brown isochrome of forming.The gypsum of compact mass is with its soft and non-foaming can the difference with carbonate of chance acid.
Maximum in the world gypsum producing country is the U.S..In the U.S., gypsum deposit is distributed in 22 states, has 69 mines, and the maximum place of production is at A Yihua state Fort Dodge.Next is a Canada.France occupies first place in European gypsum production.Be West Germany, Britain, Spain once more.China's Gypsum Mine aboundresources.There is the Gypsum Mine output in 23 provinces in the whole nation (district).There are 169 places in the mining area of proven reserve, 57,600,000,000 tons in total retained reserve ore.Distribute from the area, maximum with the Shandong Gypsum Mine, account for 65% of national reserves; Take second place in the Inner Mongol, Qinghai, Hunan.Main gypsum mining area has Di Ge town, Zaozhuang, Shandong, Etuoke Banner, the Inner Mongol, Yingcheng City, Hubei, Jilin Huijiang, Nanjing, Dawenkou, Shandong, Qiezhou, Guangxi, Taiyuan, Shanxi, Ningxia centre halfback's Gypsum Mine etc.Gypsum Mine is based on the appositional pattern mineral deposit, and reserves account for the whole nation more than 90%, and epigenotype and hydrothermal metasomatism type Gypsum Mine are not really important.Gypsum Mine all has output in each geologic time, with cretaceous period morning and the tertiary period appositional pattern Gypsum Mine be most important.
Gypsum is a kind of broad-spectrum Industrial materials and material of construction.Can be used for cement setting retarder, gypsum building products, Modelling, medical foodstuff additive, gas washing in SA production, filler, paint filler etc.The microvoid structure of gypsum and goods thereof and thermal dehydration make it the good sound insulation of tool, heat insulation and fire resistance.
1. industrial application
Gypsum is heated to 100～200 ℃, loses partial crystallization water, can obtain semi-hydrated gypsum.It is a kind of air hardening cementitious materials, has two kinds of forms of α and β, the crystallization that all assumes diamond in shape, but physicals difference.Alpha semi-hydrated gypsum well-crystallized, solid; Beta-type semi-hydrated gypsum is sheet and the crystal that crackle is arranged, and crystallization is very thin, and specific surface area is more much bigger than alpha semi-hydrated gypsum.Alpha semi-hydrated gypsum lacks than β type water requirement, and goods have higher degree of compactness and intensity.Usually steam in the saturation steam medium with autoclave that to refine what form be alpha semi-hydrated gypsum, also claim high strength gypsum; What open wide that the device enure forms with frying pan or rotary kiln is beta-type semi-hydrated gypsum, that is plaster of Paris.The industry byproduct chemical gypsum has the same performance of the plaster of paris, does not need too much processing.
Gypsum is a main raw material of producing gypsum plaster and gypsum building products, also is the retardant of silicate cement.Gypsum is after 600～800 ℃ of calcinings, and it is levigate jointly to add catalyzer such as a small amount of lime, can obtain keene's cement (also claiming the Jin Shi agglutinate); Through 900～1000 ℃ of calcinings and levigate, can obtain high-temperature calcined gypsum.With these two kinds of goods that gypsum makes, intensity is higher than building gypsum products, and keene's cement has thermal insulation preferably, and high-temperature calcined gypsum has wear resistance and water resisting property preferably.
2. gypsum building products
(1) Thistle board
In plaster of Paris, add a small amount of tackiness agent, fiber, foaming agent etc. and water and mix and stir the back continuous pouring between two-layer mask paper, again through roll-in, solidify, cutting, drying form.9～25 millimeters of thicknesss of slab, 750～850 kilograms/meter 3 of unit dry weights, the sheet material good toughness does not fire, dimensional stabilizing, surfacing can sawing, is convenient to construction.Be mainly used in internal partition wall, interior wall veneer, top ceiling, acoustic board etc.
(2) fibrous plaster
Will be mixed with the plaster of Paris slip of fiber and other admixtures, after method moulding such as winding, press filtration or roll-in, through cut, solidify, drying forms.Thickness is generally 8～12 millimeters, and with the Thistle board ratio, its bending strength is higher, and without mask paper and tackiness agent, purposes is identical with Thistle board.
(3) decorated gypsum board
With the plaster of Paris slip of preparation, be cast in bed die and have in decorative pattern framed, through floating, solidify, the demoulding, drying form, thickness of slab is 10 millimeter.In order to improve its acoustically effective, also can be made into the sheet material of tape punching and blind hole, be commonly used for top ceiling and decorated wall surface.
(4) gypsum hollow lath and gypsum block
The plaster of Paris slip casting is gone into mould, through vibratory compaction and the demoulding after solidifying, drying form.The thickness of hollow lath is generally 60～100 millimeters, hole ratio 30～40%; The building block size is generally 600 * 600 millimeters, 60～100 millimeters of thickness, and periphery has tongue and groove, also can make the holllow building block of band circular hole sometimes.Hollow lath and building block are all built by laying bricks or stones with special-purpose gypsum, and easy construction is commonly used for the non-bearing internal partition wall.
(5) feature of plaster of Paris
The a fast solidifying.
Volume microdilatancy during the b sclerosis.Often produce contraction during the sclerosis of gelling material such as lime and cement, and plaster of Paris expands slightly (rate of expansion is 0.05%～0.15%), this can make the plastering smooth surface full, and corner angle are clear, do not ftracture when dry.
C sclerosis back porosity is bigger, and apparent density and intensity are lower.
The d heat insulation and acoustic absorption is functional.
The e fire resistance is good.Meet flint, the crystal water evaporation in the main component dihydrate gypsum after the gypsum sclerosis also absorbs heat, and product surface forms steam curtain, can effectively stop spreading of fire.
F has certain conditioning
G water tolerance and frost resistance are poor.
The h good processability.Plastering can be sawed, and can dig, can follow closely, but perforating.
3. the traditional Chinese medical science is used
(1) the refrigeration function plaster stone does not have cooling effect to normal body temperature, and the artificial fever animal is had certain refrigeration function, the artificial fever rabbit is had tangible antipyretic effect, and its antipyretic effect may be irrelevant with the effect of its main component calcium. and plaster stone decoction 15g/kg irritates stomach does not have antipyretic effect to the heating rabbit due to the injection typhoid fever pentavaccine; If irritate stomach plaster stone decoction 15g/kg to rabbit earlier, to inject the typhoid fever pentavaccine again and can not cause that then body temperature raises significantly. gypsum has rapidly but the short refrigeration function of holding time, the heating rabbit that Typhoid Vaccine is caused, the cooling-down effect of 5g/kg plaster stone is similar to the 0.2g/kg quinizine, drop to significantly with back body temperature half an hour of taking medicine, the strongest effect in 1～1.5 hour.
Baihu Tang and single gypsum decoction all have certain antipyretic effect to experimental pyrogenicity rabbit; Not gypseous wind-weed licorice mixture and go calcium Baihu Tang etc. to there is no the effect of obviously bringing down a fever, can think that gypsum is the main medicine of Baihu Tang antipyretic effect, the gypsum effect can be strengthened by the other drug in the prescription, but the consumption with gypsum does not increase. calcium level before and after the laboratory animal administration is measured, show that blood calcium elevated levels and antipyretic effect are in close relations. there is report to point out, the effect of bringing down a fever that the gypsum and the wind-weed share is more singly used to strong, the analgesic composition of the wind-weed is a Mengiferin, pure calcium sulfate is invalid, and the refrigeration function of therefore inferring gypsum is for due to the composition beyond its contained calcium sulfate. and experiment shows: MAXINGSHIGAN TANG and gypsum use the antipyretic effect of (pulverize after the decoction and reuse) MAXINGSHIGAN TANG all to be better than gypsum and gypsum water decocting liquid more again.
Report is also arranged, add gypsum powder with the supernatant liquor part of 1: 1 decocting liquid of plaster stone and supernatant liquor and give the heating rabbit that Typhoid Vaccine causes, do not see obvious antipyretic effect. experimental results show that of external useful experimental heating rat: gypsum gavages, subcutaneous injection or intravenous injection there is no tangible refrigeration function, but when with forbid drinking-water, intracellular toxin cause heating, give diuretic(s), hello when raising salt and causing animal " thirsty " state with methods such as radiant heat, gypsum can reduce the amount of drinking water of rat, can alleviate its " thirsty " state.
(2) the effect gypsum immersion liquid of cardiovascular systems there is not influence to the heart on the throne of the frog, low dose of gypsum immersion liquid has excitation for the stripped toad heart and the rabbit heart, heavy dose then produces restraining effect, heart can recover normal after changing liquid. during intravenous injection 4% gypsum supernatant liquor 0.1ml/kg, to rabbit, the breathing of cat, blood pressure and volume of blood flow do not have influence, and injection 1ml/kg is when above, present respiration inhibition, blood pressure drops, volume of blood flow reduces, decreased heart rate. intravenous injection gypsum liquid 0.2ml/kg can make the volume of blood flow of the thigh artery of rabbit and cat be momentary minimizing, increase, and coronary artery blood flow is reduced thereafter.
(3) to the low dose of gypsum supernatant liquor of the effect of unstriated muscle rat small intestine in vitro of rabbit and uterus amplitude are increased, heavy dose then tonus reduces, amplitude reduces. and gypsum can also make the mouse retention output increase, and the small intestine propulsion functions slows down, and increases the bile excretion of rat and cat.
(4) other effect gypsum are for oral administration through the hydrochloric acid in gastric juice effect, a part becomes soluble calcium salt, go into blood to intestinal absorption and can increase calcium ion concn in the serum, can suppress neural stress ability (the thermoregulation function that comprises nervus centralis), lower the excitability of skeletal muscle, relieve muscle spasms can reduce vascular permeability again.In the vitro culture experiment, 1: 1 gypsum Hanks liquid can obviously strengthen the phagocytic activity of rabbit pulmonary alveolar macrophage to Staphylococcus albus and Radioactive colloidal gold, and can promote cytophagous ripe .Ca++ can improve the catch rate of pulmonary alveolar macrophage, strengthen its activate the phagocytic capacity and quicken its removing grit, keep on the scavenger cell physiological function significant. therefore can think that Ca++ plays an important role in the above-mentioned functions of gypsum.The long-term feed gypsum can make the calcium contents of rat pituitary, suprarenal gland, submaxilary, pancreas and thymus gland etc. increase. and, the thymus gland calcium contents is increased to extracing Tiroidina, parathyroid rat, and spleen content reduces.Gypsum ATP in vivo exists down, through the effect of enzyme and APG, produces the fractionation of sulfur isotope, the Plasma Concentration of 34S is increased, thereby play antivirus action.
4. traditional Chinese medical science utensil
(1) gypsum pillow: adopting the elaboration (striate gypsum) in the plaster of paris ore is raw material, and manual engraving meticulously grinds a kind of medicine-filled pillow with the analgesic effect of the pest of dispelling that forms.
Qing Dynasty last years of a dynasty or reign, the artisan among the people in area just outside a city gate, Yingcheng City just makes gypsum pillow or square cushion, can heat-clearing separate cold, goes the effect of " vexed, coma " in addition.
The gypsum pillow is more and more paid close attention to by people as local famous-brand and high-quality special product, carves already to promote the well-being of mankind for the cream of Yingcheng City and has made another contribution." the not false carving of surface transparent, cold as spring snow Bai Ruyao, towards sending on bamboo couch, be not afraid of scorching pin of wind day." when the poet Xue Shi Tang Dynasty chanted this head " chanting the cream pillow " poem, yingcheng gypsum did not see generation as yet.To modern age Yingcheng City can dab hand the arts ﹠ crafts products factory be devoted to the development of gypsum product, just successively develop the healthy pillow of " gypsum health blood pressure lowering pillow ", " Pu Yang Yuzhen " tens all series such as " new-type Pu Yang Yuzhen ", multinomial gain the national patent and National Gold Prize are arranged.
The yingcheng gypsum pillow is the several generations folk artisan of Yingcheng City crystallization of wisdom, is yingcheng gypsum pharmaceutical use and consummate artistic perfection bonded product.Moulding uniqueness, elegant style, existing characteristic among the people has the artistic style of jade carving again, can be rated as exquisite works of art, and sky above Hubei and Hunan one is exhausted.
(2) plaster stone: remove assorted only stone, clean earth, be broken into fritter.Plaster of paris: get clean plaster block, put in the crucible, in smokeless stove fire, forge, take out, cool, pulverize to loose shape.1. Lei Gong's Treatise on Preparation and Broiling of Materia Medica: " all gypsum that makes must be smash into powder in the stone mortar, the square-bottomed bamboo basket mistake, and Radix Glycyrrhizae water flies over, and is clear, shine, grind usefulness." 2. " detailed outline ": " and gypsum, ancient method is only smashed as beans big, and thin,tough silk wraps into soup and boils it, and the person of modern times is cold because of it, and fire was forged usefulness, or sugar stirred, and then there is no harm in taste." 3. " medicine justice ": " gypsum is slightly forged band and is given birth to usefulness, forges then the greasy property of body more and holds back.”
Summary of the invention
The tantalum niobium lithium ore deposit of Yichuan is the tantalum niobium lithium ore deposit of present Asia maximum, and it contains abundant Rare Metals Materials, and as tantalum, niobium, lithium, potassium, sodium, rubidium, caesium etc., lithionite is that tantalum niobium exploitation mine tailing is through flotation gained byproduct.Because meeting, the compound of the lithium in the different ores place of production and forming process difference thereof, ore thing produce very big difference, extraction process difference to lithium compound wherein is also very big, purpose of the present invention to provide exactly relate to a kind of suitable Asia lithium all Yichuan tantalum niobium lithium ore deposit lithionite prepare battery-level lithium carbonate and obtain the method for byproduct calcium sulfate (gypsum).
It is characterized in that the lithionite powder is crushed to about 200 orders, to be 30%～70% sulphuric acid soln drop into reaction unit in solid-liquid mass ratio 1: 2～8 ratios carries out acidleach defluorination reaction 3～10 hours, 60～200 ℃ of temperature of reaction with concentration; Reaction finishes, and the hydrofluoric acid of generation vacuumizes separation, gets the solid, liquid mixing solutions, and filter cleaner gets mother liquor 1.
In the method for the present invention and defluorination be in the solid, liquid mixed solution, add vacuumize the suitable water of isolated hydrofluoric acid solution after, add alkaline earth metal oxide (or oxyhydroxide) neutralization again and remove sulfate radical, it is characterized in that it is that PH is 5～7 in adding calcium oxide (or calcium hydroxide) the control solution that sulfate radical is removed in neutralization, filters the gypsum that obtains higher degree.
Preparing Quilonum Retard with lithionite can control reaction conditions well and can obtain a large amount of high-quality by-produced gypsums, this tantalum niobium lithium ore deposit to the comprehensive development and utilization Yichuan has very important economy and strategic value, thereby can significantly reduce its production cost, improve comprehensive benefit.
In the production process of the present invention, the equation of the main chemical reactions that relates to is as follows:
Li
2O
2+H
2SO
4＝＝Li
2SO
4+2H
2O
K
2O+H
2SO
4＝＝K
2SO
4+H
2O
Na
2O+H
2SO
4＝＝Na
2SO
4+H
2O
2Al
2O
3+3H
2SO
4＝＝2Al
2(SO
4)
3+3H
2O
Rb
2O
3+3H
2SO
4＝＝Rb
2(SO
4)
3+3H
2O
Cs
2O+H
2SO
4＝＝Cs
2SO
4+H
2O
Rb
2(SO
4)
3+Al
2(SO
4)
3＝＝2Rb?Al(SO
4)
3
Cs
2(SO
4)
3+Al
2(SO
4)
3＝＝2Cs?Al(SO
4)
3
K
2SO
4+Al
2(SO
4)
3＝＝2K?Al(SO
4)
3
Li
2SO
4+Ca(OH)
2＝＝2LiOH+CaSO
4
Embodiment
Embodiment 1
. relating to concentration among the embodiment and be mass concentration, now is that the technological process of raw material extraction lithium or salt of wormwood illustrates the method for preparing the gypsum of preparation higher degree the Quilonum Retard from lithionite with the lithionite.
The lithionite ore deposit that present embodiment is selected for use is adopted and is originated from tantalum niobium lithium ore deposit, Yichuan, its each main chemical such as following table:
| Li 2O | K 2O+Na 2O | Al 2O 3 | SiO 2 | Fe 2O 3 | Rb 2O | Cs 2O | F |
| 4.4％ | 9.1％ | 23.2％ | 53.7％ | 0.2％ | 1.3％ | 0.2％ | 4.1％ |
Be crushed to above-mentioned lithionite powder about 200 orders and concentration to be the 30%-70% sulphuric acid soln drop into reaction unit in solid-liquid mass ratio 1: 2～8 ratios carries out acidleach defluorination reaction 3～10 hours, 60～200 ℃ of temperature of reaction; Reaction finishes, drive material after, feed liquid removes the gred through centrifugation, feed liquid is a mother liquor, mother liquor is removed potassium handle, and adopts pressurization, alternating temperature to analyse potassium earlier, be with mother liquor pressurize, alternating temperature handles, in determining solution, form potassium aluminium sulfate after, K in the detection solution
+, Al
3+The change in concentration situation, K in detecting solution
+The potassium that sinks during concentration excess is handled, can obtain the compound alum of potassium, sedimentation and filtration, add alkaline earth metal oxide (or oxyhydroxide) neutralization afterwards in the solution and remove sulfate radical, it is characterized in that it is that PH is 5～7 in adding calcium oxide (or calcium hydroxide) the control solution that sulfate radical is removed in neutralization, filter to obtain gypsum 209.6 grams that purity is 85%-95%.When from the lithionite raw material, carrying lithium or salt of wormwood like this, significantly improved its percentage composition; Improve the quality product of lithium, Quilonum Retard, also improved the product production of gypsum, thereby improved the comprehensive utilization ratio of lithionite, reduced production cost.
Claims (5)
1. one kind is utilized tantalum niobium mine tailing lithionite to prepare the method that Quilonum Retard obtains the by product gypsum, it is characterized in that the lithionite powder is crushed to about 100～200 orders, being 30%～70% sulphuric acid soln with concentration drops into reaction unit in solid-liquid mass ratio 1: 2～8 ratios, react 3～10 hours defluorinations in 60～200 ℃, must contain Li
+Sulphuric acid soln, separate and to remove fluorine-containing solution.
2. separating according to claim 1 is to contain Li
+Sulphuric acid soln carry out filtering separation, filter residue water thorough washing is removed filter residue and is got filtrate, is mother liquor 1.
3. separating according to the alternating temperature of claim 2 is with mother liquor 1 under agitation, alternating temperature to 10～100 ℃, isolate solid rubidium, caesium, alum after, filtering separation, the washing filter residue, filtrate is recovered as mother liquor 2.
4. the neutralization according to claim 3 is to add calcium oxide (or calcium hydroxide) in mother liquor 2, and the solid that gets neutralization reaction is the gypsum of higher degree.
5. prepare the method that Quilonum Retard obtains the by product gypsum according to the described a kind of tantalum niobium mine tailing lithionite that utilizes of claim 1～4, it is characterized in that it is that PH is 5～7 in adding calcium oxide (or calcium hydroxide) the control solution that sulfate radical is removed in neutralization, filters the gypsum that obtains higher degree.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430260A (en) * | 2016-12-13 | 2017-02-22 | 宜春银锂新能源有限责任公司 | Method for preparing high-purity lithium carbonate from Lizhimu |
| US10450630B2 (en) * | 2014-10-10 | 2019-10-22 | Li-Technology Pty Ltd. | Recovery process |
| CN111646767A (en) * | 2020-05-21 | 2020-09-11 | 贵州开磷磷石膏综合利用有限公司 | Application of heat-preservation refractory gypsum powder |
| CN114634246A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Method for deep denitrification by utilizing sulfur paste autotrophic nitrogen |
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|---|---|---|---|---|
| CN85101989A (en) * | 1985-04-01 | 1986-09-17 | 广州有色金属研究院 | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 |
| CN1067028A (en) * | 1992-06-23 | 1992-12-16 | 中南工业大学 | Pressurized boiling process for preparing lithium carbonate with lithium mica ore and mixed base |
| CN101186968A (en) * | 2006-11-24 | 2008-05-28 | 江西赣锋锂业有限公司 | Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process |
-
2011
- 2011-01-25 CN CN2011100264167A patent/CN102173438A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101989A (en) * | 1985-04-01 | 1986-09-17 | 广州有色金属研究院 | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 |
| CN1067028A (en) * | 1992-06-23 | 1992-12-16 | 中南工业大学 | Pressurized boiling process for preparing lithium carbonate with lithium mica ore and mixed base |
| CN101186968A (en) * | 2006-11-24 | 2008-05-28 | 江西赣锋锂业有限公司 | Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10450630B2 (en) * | 2014-10-10 | 2019-10-22 | Li-Technology Pty Ltd. | Recovery process |
| CN106430260A (en) * | 2016-12-13 | 2017-02-22 | 宜春银锂新能源有限责任公司 | Method for preparing high-purity lithium carbonate from Lizhimu |
| CN111646767A (en) * | 2020-05-21 | 2020-09-11 | 贵州开磷磷石膏综合利用有限公司 | Application of heat-preservation refractory gypsum powder |
| CN114634246A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Method for deep denitrification by utilizing sulfur paste autotrophic nitrogen |
| CN114634246B (en) * | 2022-04-15 | 2024-02-02 | 合肥工业大学 | Autotrophic deep denitrification method utilizing sulfur paste |
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Application publication date: 20110907 |