RU2562180C1 - Method of recycling pyrite cinders - Google Patents
Method of recycling pyrite cinders Download PDFInfo
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- RU2562180C1 RU2562180C1 RU2014119076/02A RU2014119076A RU2562180C1 RU 2562180 C1 RU2562180 C1 RU 2562180C1 RU 2014119076/02 A RU2014119076/02 A RU 2014119076/02A RU 2014119076 A RU2014119076 A RU 2014119076A RU 2562180 C1 RU2562180 C1 RU 2562180C1
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- Prior art keywords
- iron
- chloride
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- pyrite cinders
- chlorination
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- 239000003818 cinder Substances 0.000 title claims abstract description 20
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 19
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000011028 pyrite Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004064 recycling Methods 0.000 title abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 18
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000859 sublimation Methods 0.000 claims abstract description 3
- 230000008022 sublimation Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000000762 glandular Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Изобретение относится к области химической технологии неорганических веществ и может быть использовано в случаях, когда необходимо получить металлическое железо.The invention relates to the field of chemical technology of inorganic substances and can be used in cases where it is necessary to obtain metallic iron.
Известен способ переработки пиритного огарка, патент US 4259106, опубл. 31.03.1981, взаимодействием огарка с хлоридом кальция при температуре выше 1200°C с выделением в газовую фазу хлоридов цветных и благородных металлов. Недостатком способа являются высокие энергозатраты.A known method of processing pyrite cinder, patent US 4259106, publ. 03/31/1981, by the interaction of cinder with calcium chloride at temperatures above 1200 ° C with the release of non-ferrous and noble metal chlorides into the gas phase. The disadvantage of this method is the high energy consumption.
Известен способ удаления примесей из пиритного огарка, патент GB 1236345, опубл. 23.06.1971, переводом оксидов железа до магнетита с последующим хлорированием хлором (хлороводородом, соляной кислотой) при температуре выше 650°C и сублимационным удалением цветных металлов и мышьяка. Недостатком способа является высокая коррозионная активность используемых хлорирующих реагентов.A known method of removing impurities from a pyrite cinder, patent GB 1236345, publ. 06/23/1971, transferring iron oxides to magnetite, followed by chlorination with chlorine (hydrogen chloride, hydrochloric acid) at temperatures above 650 ° C and sublimation removal of non-ferrous metals and arsenic. The disadvantage of this method is the high corrosivity of the used chlorinating reagents.
Известен способ выделения цветных металлов из пиритного огарка, патент EP 0538168, опубл. 21.04.1993, включающий обжиг пиритного огарка с последующим выщелачиванием сульфатов цветных металлов и цианидным извлечением золота и серебра. Недостатком способа является низкая рентабельность способа из-за малого содержания извлекаемых компонентов в сырье.A known method for the separation of non-ferrous metals from a pyrite cinder, patent EP 0538168, publ. 04/21/1993, including firing a pyrite cinder, followed by leaching of non-ferrous sulfates and cyanide extraction of gold and silver. The disadvantage of this method is the low profitability of the method due to the low content of recoverable components in the feed.
Известен способ (прототип) хлороаммонийного обезжелезивания минерального сырья, патент RU 2314354, опубл. 10.01.2008, включающий смешение сырья с хлоридом аммония, нагрев до температуры 320-350°C с выделением трихлорида железа. Недостатком способа является возможность получения одного железистого продукта - трихлорида железа.A known method (prototype) of chloroammonium deferrization of mineral raw materials, patent RU 2314354, publ. 01/10/2008, including the mixing of raw materials with ammonium chloride, heating to a temperature of 320-350 ° C with the release of iron trichloride. The disadvantage of this method is the possibility of obtaining one glandular product - iron trichloride.
Задачей настоящего изобретения является разработка промышленного способа выделения железа из пиритного огарка.An object of the present invention is to provide an industrial method for separating iron from a pyrite cinder.
Поставленная задача решается тем, что пиритный огарок подвергают окислительному обжигу для перевода железа в трехвалентную форму:The problem is solved in that the pyrite cinder is subjected to oxidative firing to convert iron to the trivalent form:
4Fe3O4+O2→6Fe2O3.4Fe 3 O 4 + O 2 → 6Fe 2 O 3 .
Окисленный пиритный огарок смешивают с хлоридом аммония, хлорид аммония берут в избытке до 30% от стехиометрического количества, необходимого для образования пентахлороферрата аммония:The oxidized pyrite cinder is mixed with ammonium chloride, ammonium chloride is taken in excess of up to 30% of the stoichiometric amount required for the formation of ammonium pentachloroferrate:
Fe2O3+10NH4Cl→2(NH4)2FeCl5+6NH3+3H2O.Fe 2 O 3 + 10NH 4 Cl → 2 (NH 4 ) 2 FeCl 5 + 6NH 3 + 3H 2 O.
Процесс ведут в интервале температур 200-310°C, происходит образование пентахлороферрата аммония с последующим его разложением до хлорида железа(III):The process is conducted in the temperature range 200-310 ° C, the formation of ammonium pentachloroferrate occurs, followed by its decomposition to iron (III) chloride:
(NH4)2FeCl5→FeCl3+2NH3+2HCl.(NH 4 ) 2 FeCl 5 → FeCl 3 + 2NH 3 + 2HCl.
Хлорированный продукт нагревают выше 320°C для сублимации хлорида железа(III).The chlorinated product is heated above 320 ° C to sublimate iron (III) chloride.
Газообразный хлорид железа(III) улавливают и обрабатывают водородом, получая металлическое железо:Gaseous iron (III) chloride is captured and treated with hydrogen to obtain metallic iron:
2FeCl3+3Н2→2Fe+6HCl.2FeCl 3 + 3H 2 → 2Fe + 6HCl.
Либо обрабатывают парами воды с целью получения оксида железа(III), который восстанавливают углем:Or they are treated with water vapor in order to obtain iron (III) oxide, which is reduced with coal:
2FeCl3+3H2O→Fe2O3+6HCl;2FeCl 3 + 3H 2 O → Fe 2 O 3 + 6HCl;
2Fe2O3+6С+3O2→4Fe+6CO2.2Fe 2 O 3 + 6C + 3O 2 → 4Fe + 6CO 2 .
Хлороводород и аммиак, выделившийся в результате хлорирования окисленного пиритного огарка, взаимодействуют с образованием хлорида аммония, таким образом, происходит регенерация хлорирующего реагента:Hydrogen chloride and ammonia released as a result of chlorination of the oxidized pyrite cinder interact with the formation of ammonium chloride, thus, the chlorination reagent is regenerated:
NH3+HCl→NH4Cl.NH 3 + HCl → NH 4 Cl.
ПРИМЕРЫEXAMPLES
Пример 1. Пиритный огарок, содержащий 46% Fe3O4 и 24% Fe2O3, массой 50 г подвергли обжигу в атмосфере воздуха при 700°C в течение 2 часов, масса окисленного пиритного огарка 50,79 г, степень перевода железа в трехвалентную форму 99%. Окисленный пиритный огарок смешали с 140 г хлорида аммония и выдержали при 300°C до прекращения выделения газообразных продуктов реакции. Полученный продукт нагревали до 350°C и выдерживали при этой температуре до полного удаления хлорида железа(III) в виде газа. Газообразный хлорид железа десублимировали и обрабатывали водородом при 600°C до прекращения выделения газообразных продуктов реакции. Масса полученного железа составила 24,55 г, выход продукта составил 98% от теоретически возможного.Example 1. Pyrite cinder containing 46% Fe 3 O 4 and 24% Fe 2 O 3 , weighing 50 g, was calcined in air at 700 ° C for 2 hours, the mass of oxidized pyrite cinder is 50.79 g, the degree of iron transfer in the trivalent form of 99%. The oxidized pyrite cinder was mixed with 140 g of ammonium chloride and kept at 300 ° C until the evolution of gaseous reaction products ceased. The resulting product was heated to 350 ° C and kept at this temperature until the iron (III) chloride was completely removed as a gas. Iron chloride gas was desublimated and treated with hydrogen at 600 ° C until the evolution of gaseous reaction products ceased. The mass of iron obtained was 24.55 g, the product yield was 98% of theoretically possible.
Пример 2. Отличается от примера 1 тем, что десублимированный хлорид железа(III) обрабатывали парами воды при 400°C до прекращения выделения газообразных продуктов реакции. Образовавшийся оксид железа(III) смешивали с угольной пылью и выдерживали при температуре выше 1100°C до прекращения выделения газообразных продуктов реакции. Масса полученного железа составила 24,15 г, выход продукта составил 96,4% от теоретически возможного.Example 2. It differs from example 1 in that the desublimated iron (III) chloride was treated with water vapor at 400 ° C until the evolution of gaseous reaction products ceased. The resulting iron (III) oxide was mixed with coal dust and kept at a temperature above 1100 ° C until the evolution of gaseous reaction products ceased. The mass of iron obtained was 24.15 g, the product yield was 96.4% of theoretically possible.
Техническим результатом изобретения является технология получения металлического железа из пиритных огарков.The technical result of the invention is a technology for producing metallic iron from pyrite cinder.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2014119076/02A RU2562180C1 (en) | 2014-05-12 | 2014-05-12 | Method of recycling pyrite cinders |
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| Application Number | Priority Date | Filing Date | Title |
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| RU2014119076/02A RU2562180C1 (en) | 2014-05-12 | 2014-05-12 | Method of recycling pyrite cinders |
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| RU2562180C1 true RU2562180C1 (en) | 2015-09-10 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1439227A (en) * | 1972-08-10 | 1976-06-16 | Swarsab Mining Exploration | Separation and purification of iridium |
| US5304359A (en) * | 1992-03-03 | 1994-04-19 | Bhp Minerals International Inc. | Dissolution of platinum group metals from materials containing said metals |
| RU2023031C1 (en) * | 1991-05-14 | 1994-11-15 | Казахский политехнический институт им.В.И.Ленина | Method of processing pyrite concentrate containing non-ferrous metals |
| US6455018B1 (en) * | 1993-05-12 | 2002-09-24 | Rhone-Poulenc Chimie | Recovery of precious metal and other values from spent compositions/materials |
| RU2305711C1 (en) * | 2005-12-07 | 2007-09-10 | Валерий Иванович Чернышев | Method of extraction of the noble metals from the ash-waste of the sulfuric acid production |
| RU2314354C2 (en) * | 2006-02-20 | 2008-01-10 | Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет | Method of chloro-ammonium deferrization of mineral raw materials |
-
2014
- 2014-05-12 RU RU2014119076/02A patent/RU2562180C1/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1439227A (en) * | 1972-08-10 | 1976-06-16 | Swarsab Mining Exploration | Separation and purification of iridium |
| RU2023031C1 (en) * | 1991-05-14 | 1994-11-15 | Казахский политехнический институт им.В.И.Ленина | Method of processing pyrite concentrate containing non-ferrous metals |
| US5304359A (en) * | 1992-03-03 | 1994-04-19 | Bhp Minerals International Inc. | Dissolution of platinum group metals from materials containing said metals |
| US6455018B1 (en) * | 1993-05-12 | 2002-09-24 | Rhone-Poulenc Chimie | Recovery of precious metal and other values from spent compositions/materials |
| RU2305711C1 (en) * | 2005-12-07 | 2007-09-10 | Валерий Иванович Чернышев | Method of extraction of the noble metals from the ash-waste of the sulfuric acid production |
| RU2314354C2 (en) * | 2006-02-20 | 2008-01-10 | Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет | Method of chloro-ammonium deferrization of mineral raw materials |
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