CN108383089A - A method of restoring ardealite and titanium dioxide waste residue green vitriol Sulphuric acid simultaneously using pyrite - Google Patents

A method of restoring ardealite and titanium dioxide waste residue green vitriol Sulphuric acid simultaneously using pyrite Download PDF

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Publication number
CN108383089A
CN108383089A CN201810285442.3A CN201810285442A CN108383089A CN 108383089 A CN108383089 A CN 108383089A CN 201810285442 A CN201810285442 A CN 201810285442A CN 108383089 A CN108383089 A CN 108383089A
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ardealite
titanium dioxide
waste residue
pyrite
green vitriol
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吕莉
唐盛伟
郑东钥
陈彦逍
张涛
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/508—Preparation of sulfur dioxide by oxidation of sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/076—Use of slags or fluxes as treating agents
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of method preparing sulfuric acid and calcium ferrite simultaneously using pyrite titanium dioxide waste residue green vitriol ardealite, technical process includes：(1) pyrite for being finely ground to certain particle size, ardealite and titanium dioxide waste residue green vitriol are uniformly mixed by a certain percentage；(2) mixed material directly will be reacted into after mixture tabletting or at a certain temperature certain time, obtain solid reduction product and contains SO2Tail gas；Obtained solid reduzate can be used as pre-melted type steelmaking slag agent；(3) SO will be contained obtained by step (2)2Feeding sulfate system prepares sulfuric acid finished product after tail gas is dusted purification.This technology utilization pyrite restores ardealite and titanium dioxide waste residue green vitriol Sulphuric acid simultaneously, realizes ardealite, titanium dioxide waste residue green vitriol fixed-end forces and recycling, and obtain sulfuric acid and steelmaking slag agent ferrous acid calcium product.The resolution ratio of ardealite of the present invention is up to 98wt% or more, kiln gas SO2Concentration is relatively up to 15vol% or more, and solid product calcium ferrite purity is up to 90wt% or more.Present invention process is simple, no waste discharge, and environment and economic benefit advantage are notable.

Description

It is a kind of to restore ardealite and titanium dioxide waste residue green vitriol Sulphuric acid simultaneously using pyrite Method
Technical field
The invention belongs to field of chemical metallurgical technology, relate generally to a kind of utilizing pyrite, titanium dioxide waste residue green vitriol, ardealite The method for preparing sulfuric acid and calcium ferrite simultaneously.
Background technology
Ardealite is the industrial residue of phosphorus ore and sulfuric acid reaction generation during Wet-process Phosphoric Acid Production, and main component is sulfuric acid Calcium, while also containing the impurity such as iron, aluminium, phosphorus, silicon.Ardealite mainly takes outdoor heap in addition to part is for production of construction materials at present The mode deposited is handled.The effective way that increasing exploitation ardealite utilizes on a large scale is to realizing sustainable development of phosphate fertilizer industry and avoiding Excessive land occupation resource and environmental protection are all of great significance.
Ardealite reduction Sulphuric acid can be coupled with wet method phosphoric acid manufacture process, and Sulphur ressource recycles, and be to have well The comprehensive Utilization Ways of the achievable extensive consumption ardealite of application prospect.The China of 101041439 A of Publication No. CN is specially Profit proposes a kind of method preparing wollastonite and sulfuric acid using residue phosphogypsum, by ardealite, powdered carbon, silica flour by chemistry Metering is cooled to room temperature to obtain wollastonite, in calcination than putting into reactor after mixing, being warming up to 1200 DEG C and keeping the temperature 2. 5h The SO of generation2Into for follow-up Sulphuric acid workshop section.The decomposable process of ardealite is reductive coke rate-determining steps in the invention, is existed Energy consumption is higher, SO in kiln gas2Concentration is low, the CO of generation2The problems such as unfriendly to environment.In 1884048 A of Publication No. CN State's patent proposes a kind of method with sulphur coal reducing and decomposing phosphogypsum, by the ardealite dried and sulphur coal（Sulphur contains Amount >=3%）It is sent into reduction decomposition stove after mixing, control furnace temperature is 800 ~ 1350 DEG C, carries out reduction decomposition reaction, output SO2As the unstripped gas of process for preparing sulfuric acid, CaO is used as the dispensing of production cement in solid product.The invention is substantially still Belong to reductive coke decomposing phosphogypsum, energy consumption is still higher.The Chinese patent of 101708826 A of Publication No. CN proposes one The method of kind sulphur reducing and decomposing phosphogypsum, first by the ardealite after preheating, the low temperature under inert atmosphere is anti-with gaseous state sulphur Answer 1 ~ 2h；It is uniformly mixed with ardealite after gained calcium sulfide material block is ground again, in non-oxidizing atmosphere, 1000 ~ 1400 DEG C 0.5 ~ 3h of lower roasting, CaO is used for manufacture of cement, the SO of generation as clinker in obtained solid slag charge2It is produced with the first workshop section Raw tail gas, which merges, is used for gas washing in SA production.The technique uses two sections of processes, and flow is not simple enough, and has centainly to equipment corrosion It is required that.
Pyrite（FeS2）It is the main Sulphur ressource source in China, rich reserves, before explored resource reserve occupies the world Row, the gas washing in SA production in China 40~50% is using troilite as raw material at present.The Chinese patent of 102530889 A of Publication No. CN carries A kind of method of pyrite reduction decomposition gypsum Sulphuric acid is gone out, has mixed after gypsum is ground with troilite and in proportion It is even, then the mixed material is added in the reactor of 800~1300 DEG C of temperature, it is roasted under inertia, weak oxide or reducing atmosphere 0.1 ~ 4h, the SO of generation2Tail gas is used for Sulphuric acid.The invention is not used to the solid residue that it is generated, main former Cause is the mixture that solid slag is calcium oxide and calcium ferrite, is isolated larger using difficulty；If stacking is handled, inevitable wave Take land resource, increases maintenance cost, thereby increases and it is possible to cause secondary pollution.
Titanium dioxide waste residue green vitriol is the waste residue of sulfate process titanium dioxide production by-product, often produces 1 t titanium dioxides output, 3~4 t sulfuric acid It is ferrous.Titanium dioxide waste residue green vitriol Processes For Effective Conversion is few at present, still based on stacking, cause sulphur, iron resource huge waste and Environmental pollution.The Chinese patent of 103539207 A of Publication No. CN proposes ferrous disulfide reduction decomposition ferric sulfate and prepares oxygen Change the method for iron oxide red, the sulfate of iron is mixed with ferrous disulfide by certain mol proportion, roasted at 550~800 DEG C by this method 0.5~3h is burnt, sulfur dioxide and iron oxide red are obtained.Iron oxide red product purity obtained by the inventive method reach 80wt% with On, it is suitble to utilize titanium dioxide waste residue green vitriol on a large scale.
The present invention restores ardealite and titanium dioxide waste residue green vitriol prepares sulfuric acid and calcium ferrite simultaneously using pyrite, 800~ At a temperature of 1150 DEG C, the S in pyrite-ardealite-titanium dioxide waste residue green vitriol is fully converted into SO2, kiln gas SO2Concentration is high；It is logical It crosses the CaO that rational proportion makes ardealite reaction generate and reacts the Fe generated with titanium dioxide waste residue green vitriol2O3In conjunction with the purer ferrous acid of generation Calcium, calcium ferrite can be directly used as pre-melted type steelmaking slag agent.This technique has coupled pyrite reducing and decomposing phosphogypsum and pyrite Two techniques of reduction decomposition green vitriol, can high efficiente callback utilize ardealite and the sulphur in titanium dioxide waste residue green vitriol, iron, calcium resource, without three Useless discharge, be a kind of ardealite, the comprehensive utilization of titanium dioxide waste residue green vitriol solid waste new method, environment and remarkable in economical benefits.
Invention content
The present invention restores ardealite and titanium dioxide waste residue green vitriol Sulphuric acid and calcium ferrite, technical process simultaneously using pyrite Include the following steps：(1) pyrite for being finely ground to certain particle size, titanium dioxide waste residue green vitriol, ardealite are uniformly mixed by a certain percentage With；(2) mixture input tablet press machine carries out tabletting；(3) sheet of mixed material is roasted into certain time at a certain temperature, Obtain solid reduction product and tail gas containing SO2；(4) fritting will be can be used as after the solid reduction product cooling obtained by step (3) Type steelmaking slag agent；(5) by the tail gas containing SO2 obtained by step (3) be dusted purification after be sent into sulfate system prepare sulfuric acid at Product.In the above method, the reaction that roasting process mainly occurs is as follows：
2 FeS2 + 11CaSO4 = Ca2Fe2O5 + 9CaO + 15SO2；
FeS2 + 11FeSO4 = 6Fe2O3 + 13SO2；
2CaO + Fe2O3 = Ca2Fe2O5；
Overall reaction is：
FeS2 + 3FeSO4+ 4CaSO4 = 2Ca2Fe2O5 + 9SO2。
Compared with the prior art, the present invention has the following advantages：（1）Compared to traditional reductive coke ardealite, this technique Reduction temperature reduces about 200 ~ 300 DEG C, and low energy consumption；（2）This technology utilization pyrite restores ardealite and green vitriol, the recycling of sulphur Rate is high, SO2Tail gas concentration is stable and high（More than 15vol%）, it is used directly for sulfur process unstripped gas；（3）It is useless using titanium white Slag green vitriol converts the CaO that decomposing ardealite generates to calcium ferrite, and solid product ingredient is simple, can be directly used as pre-melted type steel-making Slag former.（4）Present invention process it is simple, it can be achieved that in solid waste the high efficiente callback of sulphur, iron, calcium resource utilize, three wastes row Go out, environment and remarkable in economical benefits.
Specific implementation mode
It elaborates to the present invention with reference to embodiment, but protection scope of the present invention is not limited only to following reality Apply example.Titanium dioxide waste residue green vitriol, pyrite and the ardealite composition used in following instance see the table below：
1. titanium dioxide waste residue of table forms
Ingredient Fe S Mg Mn Ti V Cr Al Si
Content wt. % 35.61 17.63 0.76 0.24 0.95 <0.1 <0.1 <0.1 <0.1
2. pyrite of table forms
Ingredient Fe S Mg Ca Ti Al Si
Content wt. % 39.54 32.15 1.62 2.21 0.35 0.65 3.29
3. ardealite chemical composition of table
Chemical composition CaO SO3 P2O5 SiO2 MgO Al2O3 Fe2O3 F
Content wt. % 31.17 41.12 1.62 4.11 0.67 0.94 0.72 0.21
It is as follows that case is embodied.
Embodiment one
(1) 500 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, it is effective in pyrite The active ingredient calcium sulfate mole in active ingredient ferrous sulfate, ardealite in ingredient ferrous disulfide, titanium dioxide waste residue green vitriol Than being 1：3：4；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 120 min under nitrogen protection atmosphere, obtains SO at 1000 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is 74 wt%；
(5) SO of tail gas is monitored in embodiment one with flue gas analyzer2Concentration, volumn concentration >=15% are calculated The resolution ratio of ardealite is 93%, and the resolution ratio of troilite is 98%, and the resolution ratio of titanium dioxide waste residue green vitriol is 96%.
Embodiment two
(1) 250 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, it is effective in pyrite The active ingredient calcium sulfate mole in active ingredient ferrous sulfate, ardealite in ingredient ferrous disulfide, titanium dioxide waste residue green vitriol Than being 1：2：3；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 180 min under nitrogen protection atmosphere, obtains SO at 1150 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is 87 wt%；
(5) SO of tail gas is monitored in embodiment two with flue gas analyzer2Concentration, volumn concentration >=15% are calculated The resolution ratio of ardealite is 95%, and the resolution ratio of troilite is 99%, and the resolution ratio of titanium dioxide waste residue green vitriol is 98%.
Embodiment three
250 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, the active ingredient in pyrite The active ingredient calcium sulfate molar ratio in active ingredient ferrous sulfate, ardealite in ferrous disulfide, titanium dioxide waste residue green vitriol is 1：3：4；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 120 min under nitrogen protection atmosphere, obtains SO at 1200 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is 79 wt%；
(5) SO of tail gas is monitored in embodiment three with flue gas analyzer2Concentration, volumn concentration >=15% are calculated The resolution ratio of ardealite is 90%, and the resolution ratio of troilite is 98%, and the resolution ratio of titanium dioxide waste residue green vitriol is 98%.
Example IV
(1) 150 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, it is effective in pyrite The active ingredient calcium sulfate mole in active ingredient ferrous sulfate, ardealite in ingredient ferrous disulfide, titanium dioxide waste residue green vitriol Than being 1：2：3；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 120 min under nitrogen protection atmosphere, obtains SO at 800 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is 50 wt%；
(5) SO of tail gas is monitored in example IV with flue gas analyzer2Concentration, volumn concentration >=10% are calculated The resolution ratio of ardealite is 90%, and the resolution ratio of troilite is 98%, and the resolution ratio of titanium dioxide waste residue green vitriol is 90%.
Embodiment five
(1) 250 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, it is effective in pyrite The active ingredient calcium sulfate mole in active ingredient ferrous sulfate, ardealite in ingredient ferrous disulfide, titanium dioxide waste residue green vitriol Than being 1：2：3；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 90 min under nitrogen protection atmosphere, obtains SO at 1200 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is 81 wt%；
(5) SO of tail gas is monitored in embodiment five with flue gas analyzer2Concentration, volumn concentration >=15% are calculated The resolution ratio of ardealite is 95%, and the resolution ratio of troilite is 99%, and the resolution ratio of titanium dioxide waste residue green vitriol is 97%.
Embodiment six
(1) 500 μm of pyrite below, titanium dioxide waste residue green vitriol, ardealite will be finely ground to be mixed evenly, it is effective in pyrite The active ingredient calcium sulfate mole in active ingredient ferrous sulfate, ardealite in ingredient ferrous disulfide, titanium dioxide waste residue green vitriol Than being 1：2：3；
(2) mixture is tabletted and puts into rotary kiln；
(3) ball material is roasted 180 min under nitrogen protection atmosphere, obtains SO at 900 DEG C2Tail gas and solid reduction production Object；
(4) SO will be contained obtained by step (3)2Feeding sulfate system prepares sulfuric acid finished product, solid after tail gas is dusted purification Reduzate is calcium ferrite, and purity is that purity is 63 wt%；
(5) SO of tail gas is monitored in embodiment six with flue gas analyzer2Concentration, volumn concentration >=15% are calculated The resolution ratio of ardealite is 90%, and the resolution ratio of troilite is 98%, and the resolution ratio of titanium dioxide waste residue green vitriol is 96%.

Claims (6)

1. a kind of method preparing sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, feature exist In including the following steps：(1) pyrite, titanium dioxide waste residue green vitriol, ardealite of being finely ground to certain particle size is equal by a certain percentage Even mixing；(2) mixed material directly will be reacted into after mixture tabletting or at a certain temperature certain time, obtains solid also It originates in object and contains SO2Tail gas；Obtained solid reduzate can be used as pre-melted type steelmaking slag agent；It (3) will be obtained by step (2) Contain SO2Feeding sulfate system prepares sulfuric acid finished product after tail gas is dusted purification.
2. according to the method that claim 1 prepares sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, It is characterized in that the certain particle size described in step 1 is 1 ~ 500 μm.
3. according to the method that claim 1 prepares sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, It is characterized in that ferrous disulfide in troilite described in step 1：Ferrous sulfate in green vitriol：Calcium sulfate molar ratio is in ardealite 1：1~4：1~5.
4. according to the method that claim 1 prepares sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, It is characterized in that the consersion unit described in step 2 is a kind of in fluid bed, fixed bed, rotary kiln or shaft furnace.
5. according to the method that claim 1 prepares sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, It is characterized in that the non-oxidizing atmosphere described in step 3 is at least one of nitrogen, carbon monoxide, sulfur dioxide, carbon dioxide.
6. according to the method that claim 1 prepares sulfuric acid and calcium ferrite simultaneously using pyrite, titanium dioxide waste residue green vitriol, ardealite, It is characterized in that calcination temperature described in step 3 is 800~1150 DEG C, heating rate is 3~10 DEG C, roasting time is 30~ 240 min。
CN201810285442.3A 2018-04-03 2018-04-03 A method of restoring ardealite and titanium dioxide waste residue green vitriol Sulphuric acid simultaneously using pyrite Pending CN108383089A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593953A (en) * 2018-12-20 2019-04-09 张家港宏昌钢板有限公司 The method that semi-dry desulphurization ash cooperates with resource utilization with titanium white by product green vitriol
CN109626339A (en) * 2018-12-18 2019-04-16 广州华润热电有限公司 A kind of method that gypsum prepares sulfuric acid
CN110372041A (en) * 2019-06-27 2019-10-25 西南科技大学 A kind of method that titanium gypsum tailing prepares calcium ferrite
CN110562933A (en) * 2019-09-18 2019-12-13 西南科技大学 Method for quickly separating calcium and sulfur of industrial byproduct gypsum
CN111118280A (en) * 2020-02-27 2020-05-08 北京矿冶科技集团有限公司 Method for producing sulfur-containing gas, calcium carbonate and iron ore concentrate by using phosphogypsum and pyrite
CN111454007A (en) * 2020-03-04 2020-07-28 西南科技大学 Method for preparing hydraulic cementing material from industrial byproduct calcium sulfide slag
CN115340074A (en) * 2022-08-16 2022-11-15 四川大学 Method and system for preparing phosphoric acid by using titanium white waste acid

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SU569532A1 (en) * 1975-04-11 1977-08-25 Предприятие П/Я В-8830 Method of preparing sulphurous anhydride
CN102556981A (en) * 2010-12-24 2012-07-11 漯河市兴茂钛业有限公司 Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide
CN103864150A (en) * 2014-04-04 2014-06-18 四川大学 Preparation method of calcium ferrite

Patent Citations (3)

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SU569532A1 (en) * 1975-04-11 1977-08-25 Предприятие П/Я В-8830 Method of preparing sulphurous anhydride
CN102556981A (en) * 2010-12-24 2012-07-11 漯河市兴茂钛业有限公司 Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide
CN103864150A (en) * 2014-04-04 2014-06-18 四川大学 Preparation method of calcium ferrite

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626339A (en) * 2018-12-18 2019-04-16 广州华润热电有限公司 A kind of method that gypsum prepares sulfuric acid
CN109593953A (en) * 2018-12-20 2019-04-09 张家港宏昌钢板有限公司 The method that semi-dry desulphurization ash cooperates with resource utilization with titanium white by product green vitriol
CN109593953B (en) * 2018-12-20 2021-02-12 张家港宏昌钢板有限公司 Method for synergistic resource utilization of semidry desulfurization ash and titanium dioxide byproduct copperas
CN110372041A (en) * 2019-06-27 2019-10-25 西南科技大学 A kind of method that titanium gypsum tailing prepares calcium ferrite
CN110372041B (en) * 2019-06-27 2021-11-05 西南科技大学 Method for preparing calcium ferrite from titanium gypsum tailings
CN110562933A (en) * 2019-09-18 2019-12-13 西南科技大学 Method for quickly separating calcium and sulfur of industrial byproduct gypsum
CN110562933B (en) * 2019-09-18 2022-01-28 西南科技大学 Method for quickly separating calcium and sulfur of industrial byproduct gypsum
CN111118280A (en) * 2020-02-27 2020-05-08 北京矿冶科技集团有限公司 Method for producing sulfur-containing gas, calcium carbonate and iron ore concentrate by using phosphogypsum and pyrite
CN111454007A (en) * 2020-03-04 2020-07-28 西南科技大学 Method for preparing hydraulic cementing material from industrial byproduct calcium sulfide slag
CN115340074A (en) * 2022-08-16 2022-11-15 四川大学 Method and system for preparing phosphoric acid by using titanium white waste acid

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Application publication date: 20180810