JPH0159342B2 - - Google Patents
Info
- Publication number
- JPH0159342B2 JPH0159342B2 JP5230882A JP5230882A JPH0159342B2 JP H0159342 B2 JPH0159342 B2 JP H0159342B2 JP 5230882 A JP5230882 A JP 5230882A JP 5230882 A JP5230882 A JP 5230882A JP H0159342 B2 JPH0159342 B2 JP H0159342B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- lead
- coal
- ore
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 34
- 239000003245 coal Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 238000002309 gasification Methods 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 19
- 229910001887 tin oxide Inorganic materials 0.000 claims description 17
- 229910000464 lead oxide Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 description 29
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 5
- 239000002956 ash Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 229910052949 galena Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 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
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は改良されたスズおよび鉛の精錬方法に
関するものであり、さらに詳しくは、石炭類の接
触ガス化工程と組み合せたスズまたは鉛の精錬方
法に関するものである。
スズの精錬は酸化スズを含有する鉱石中の不純
物を機械的選鉱によつて除去したのち、石炭、コ
ークスなどと共に空気を断つて加熱する焙焼還元
法によつて行なわれている。
また、鉛の精錬は、古くから多くの方法が知ら
れているが、その一つとして、鉛鉱石の主成分で
ある方鉛鉱（PbS）を空気により酸化鉛とし、こ
の酸化鉛を石炭、重油などを用いて還元する方法
が知られている。
一方、石炭のガス化については、古くから多く
の方法が知られている。また、石油危機以後、多
くのガス化方法の研究開発が進められているが、
約1000℃、数十気圧の高温、高圧が必要なものが
多く、ガス化炉の炉材、石炭の供給機構など技術
的、経済的な点で、解決さるべき課題を多く残し
ているのが現状である。
本発明者らは、スズおよび鉛の精錬法と石炭の
ガス化とを組み合せて両者の特長を生かす方法を
検討した結果、スズおよび鉛が、800℃以上の温
度において石炭のガス化速度を増大せしめ、また
このようなガス化条件においてはスズおよび鉛が
金属状態にあることを見出して本発明を完成し
た。
本発明の石炭類の接触ガス化法と組み合せたス
ズおよび鉛精錬法は石炭または炭化物と酸化スズ
含有鉱石または酸化鉛含有鉱石とを混合し、得ら
れた混合物を800℃以上の温度において二酸化炭
素または／および水蒸気と接触させて該石炭また
は炭化物をガス化させるとともに該鉱石中の酸化
スズまたは酸化鉛を金属に還元し、得られた金属
スズまたは金属鉛をガス化残渣から分離すること
を特徴とするものである。
本発明において用いるスズ鉱石は主としてスズ
石であり、広い含有率を酸化スズを含有するもの
が用いられるが、特に50〜70重量％の酸化スズを
含有するものが好適に用いられる。本発明で用い
られる鉛鉱石は、好ましくは方鉛鉱を焙焼して得
られる酸化鉛含有鉱石が用いられる。この鉱石中
の酸化鉛含有率は70〜80重量％であることが好ま
しい。
本発明で用いられる石炭の種類は特に限定され
ず、褐炭などの低品位の石炭をも含めて広範囲の
石炭が使用可能である。石炭の灰分中のカルシウ
ム、ケイ素、鉄などの成分は方鉛鉱から酸化鉛、
金属鉛を生成する際の触媒や還元剤として作用す
るからである。また、石炭の炭化物も同様に使用
することができる。さらに、石炭以外の物質の炭
化物を使用可能である。用いられる石炭などの粒
度は採用される反応方式によつて広範囲に変り得
るが、好ましくは粒径0.1mm以下、特に好ましく
は0.01〜0.05mmである。
酸化スズ含有鉱石または酸化鉛含有鉱石と石炭
または炭化物との混合比率は石炭または炭化物中
の炭素100重量部に対してSnO2またはPbOとし
て、それぞれ５〜10重量部または10〜15重量部が
好ましい。
この混合比率の下限値以下ではガス化残渣から
金属スズまたは金属鉛を効率よく分離するのが困
難であり、また上限値以上では酸化スズまたは酸
化鉛の還元速度が充分に速くないからである。下
限値以下ではガス化速度が小さいこともその理由
である。
上記鉱石と石炭などを混合するには、鉱石を、
好ましくは粒径0.1mm以下として石炭などと機械
的に混合するなど適当な方法が用いられる。
石炭などのガス化剤である二酸化炭素および水
蒸気は単独で、または混合して添加される。混合
比率は生成ガスの組成に応じて決定されるが、例
えばCO2／H2Oモル比で0.1〜1.0の範囲が用いら
れる。これらのガス化剤は、さらに水素または酸
素含有ガスと共に用いることができる。これらの
ガスの量は、生成ガスの希望する組成および反応
温度を保持するに必要な量とされる。二酸化炭素
または水蒸気の量は石炭または炭化物中の炭素１
モル当り、CO21〜２モルまたはH2O1〜２モルが
好ましい。
反応圧力は特に制限はないが常圧〜10Kg／cm2Ｇ
であることが好ましい。
反応温度はスズまたは鉛が溶融金属状態を示す
800℃以上とされるが、特に850℃以上が好まし
い。800℃以上では石炭または炭化物のガス化に
対するスズまたは鉛の触媒活性が増大する。これ
は溶融スズまたは鉛の表面張力が小さいので反応
条件下で石炭類と触媒との接触が良いためと考え
られる。
反応方式は固定床、流動床、輸送床、溶融床な
どの各方式が用いられる。また連続式、非連続式
あるいは内熱式、外熱式のいずれの方式も用いら
れる。好ましいのは連続内熱式である。
石炭のガス化率はガス化残渣（石灰の灰分、未
ガス化炭素、スズまたは鉛あるいは鉱石中の不純
物からなる）中に炭素が５〜10％残留するような
範囲がよい。炭素の残留量を上記の範囲に保つこ
とによつてスズまたは鉛は金属状態に保たれる。
ガス化残渣からスズおよび鉛を金属として分離
するには次のような方法によるのが好ましい。
スズまたは鉛とも400℃程度の低温でも溶融し
ているので、この性質を利用して分離するのが好
ましい。すなわち、スズは、300〜400℃に保つた
ガス化残渣から上層の炭素質に富む部分と下部
Fe、Cuなど主要な成分の中間部を分別採取する。
一方、鉛もスズと同様に約400℃で比重選別によ
り下層部の鉛を分別した。
スズまたは鉛を分離したガス化残渣は、ガス化
炉に再循環されるか、その中に含まれる炭素を燃
焼させてプロセス用の熱として用いられる。生成
ガスの一部は反応炉中で酸化スズまたは酸化鉛の
還元に消費されるが大部分は燃料または化学合成
原料として用いられる。
第１図および第２図を参照して本発明方法を具
体的に説明する。第１図において酸化スズ含有鉱
石は酸化スズ含量50〜60重量％まで選鉱され、粒
径0.01〜0.1mmの石炭またはコークスと混合され
る。酸化スズ含有鉱石の粒径は0.01〜0.1mmとさ
れる。混合物は適当な方式のガス化炉に供給さ
れ、800℃以上の温度で二酸化炭素または／およ
び水蒸気と接触せしめられて、石炭またはコーク
スはガス化される。生成されたガスの一部は酸化
スズを金属スズに還元する。生成した金属スズは
溶融状態で未反応炭素、石炭の灰分および鉱石中
の不純物とともにガス化残渣としてガス化炉から
取り出され、前述したように未反応炭素、石炭の
灰分および鉱石中の不純物から分離される。分離
された粗スズは公知の乾式法または電解法により
精製され、ヒ素、銅、ビスマス、アンチモンなど
の不純物を除去されて製品とされる。一方、粗ス
ズから分離された残渣は空気を供給して未反応炭
素を燃焼させ、この際の熱はガス化工程に供給さ
れてもよい。
第２図は本発明方法において酸化鉛含有鉱石を
用いるプロセスであり、第１図のプロセスと同様
である。ただ、方鉛鉱を選鉱して空気酸化して硫
化鉛を酸化鉛に転化させてのちに石炭またはコー
クスと混合する点のみが異なる。得られた粗鉛は
金、銀、銅、ビスマス、ヒ素、アンチモン、スズ
などの不純物を含有するので、公知の乾式法また
は電解法でこれらの不純物を除去して製品とされ
る。
本発明によれば、石炭の接触ガス化とスズまた
は鉛の精錬とを組み合せることにより、石炭の接
触ガス化がスズまたは鉛の触媒作用によつて従来
のガス化温度よりも低温でかつ高効率で行なわ
れ、同時に接触ガス化工程に供給された酸化スズ
含有鉱石または酸化鉛含有鉱石を精錬することが
できる。
以下に実施例を示して本発明をさらに説明す
る。
実施例 １
内径５cm、高さ80cmの試験用ガス化炉に表−１
の組成を有する石炭0.1KgとSnO2を50重量％含有
する酸化スズ鉱石0.02Kgとの混合物を充填した。
The present invention relates to an improved method for refining tin and lead, and more particularly to a method for refining tin or lead in combination with a catalytic gasification process of coals. Tin smelting is carried out by mechanical beneficiation to remove impurities in ore containing tin oxide, and then by roasting and reduction, in which the mineral is heated together with coal, coke, etc., with no air allowed. In addition, many methods have been known for refining lead for a long time, one of which is to convert galena (PbS), the main component of lead ore, into lead oxide using air, and convert this lead oxide into coal, A method of reducing using heavy oil or the like is known. On the other hand, many methods for gasifying coal have been known for a long time. In addition, since the oil crisis, research and development of many gasification methods has been progressing.
Many require high temperatures and pressures of approximately 1000℃ and tens of atmospheres, and many technical and economic issues remain to be resolved, such as gasifier materials and coal supply mechanisms. This is the current situation. The present inventors investigated a method of combining tin and lead refining methods and coal gasification to take advantage of the advantages of both, and found that tin and lead increase the gasification rate of coal at temperatures of 800°C or higher. Furthermore, the present invention was completed by discovering that tin and lead are in a metallic state under such gasification conditions. The tin and lead refining method combined with the coal catalytic gasification method of the present invention involves mixing coal or carbide with tin oxide-containing ore or lead oxide-containing ore, and heating the resulting mixture with carbon dioxide at a temperature of 800°C or higher. or/and gasifying the coal or carbide by contacting with water vapor and reducing the tin oxide or lead oxide in the ore to metal, and separating the obtained metallic tin or metallic lead from the gasification residue. That is. The tin ore used in the present invention is mainly cassiterite, and those containing tin oxide in a wide range of contents are used, but those containing 50 to 70% by weight of tin oxide are particularly preferably used. The lead ore used in the present invention is preferably a lead oxide-containing ore obtained by roasting galena. The lead oxide content in this ore is preferably 70 to 80% by weight. The type of coal used in the present invention is not particularly limited, and a wide range of coals can be used, including low-grade coal such as lignite. Components such as calcium, silicon, and iron in coal ash are derived from galena, lead oxide,
This is because it acts as a catalyst and reducing agent when producing metallic lead. Moreover, carbide of coal can be used similarly. Additionally, carbides of materials other than coal can be used. The particle size of the coal used can vary widely depending on the reaction method employed, but is preferably 0.1 mm or less, particularly preferably 0.01 to 0.05 mm. The mixing ratio of tin oxide-containing ore or lead oxide-containing ore and coal or carbide is preferably 5 to 10 parts by weight or 10 to 15 parts by weight as SnO 2 or PbO, respectively, based on 100 parts by weight of carbon in the coal or carbide. . This is because if the mixing ratio is below the lower limit value, it is difficult to efficiently separate metallic tin or metallic lead from the gasification residue, and if it is above the upper limit value, the reduction rate of tin oxide or lead oxide is not fast enough. Another reason for this is that the gasification rate is low below the lower limit. To mix the above ore with coal, etc., add ore,
Preferably, the particle size is 0.1 mm or less, and an appropriate method such as mechanical mixing with coal or the like is used. Carbon dioxide, which is a gasifying agent such as coal, and steam are added alone or in a mixture. The mixing ratio is determined depending on the composition of the generated gas, and for example, a CO 2 /H 2 O molar ratio in the range of 0.1 to 1.0 is used. These gasifying agents can further be used with hydrogen or oxygen-containing gases. The amounts of these gases are those necessary to maintain the desired composition of the product gas and reaction temperature. The amount of carbon dioxide or water vapor is 1 carbon in coal or carbide
1 to 2 moles of CO2 or 1 to 2 moles of H2O per mole are preferred. There is no particular restriction on the reaction pressure, but normal pressure to 10Kg/cm 2 G
It is preferable that The reaction temperature indicates that tin or lead is in a molten metal state.
The temperature is said to be 800°C or higher, and particularly preferably 850°C or higher. Above 800°C, the catalytic activity of tin or lead for coal or carbide gasification increases. This is thought to be because the surface tension of molten tin or lead is small, so that the coals and catalyst can come into good contact under the reaction conditions. As the reaction method, various methods such as fixed bed, fluidized bed, transport bed, and molten bed are used. Further, any of a continuous type, a discontinuous type, an internal heating type, and an external heating type can be used. Continuous internal heating is preferred. The gasification rate of coal is preferably in a range such that 5 to 10% of carbon remains in the gasification residue (consisting of lime ash, ungasified carbon, tin or lead, or impurities in ore). By maintaining the residual amount of carbon within the above range, tin or lead is maintained in a metallic state. The following method is preferably used to separate tin and lead as metals from the gasification residue. Since both tin and lead melt even at low temperatures of around 400°C, it is preferable to separate them by taking advantage of this property. In other words, tin is extracted from the upper carbon-rich part and the lower part of the gasification residue kept at 300 to 400°C.
Separately collect the intermediate parts of major components such as Fe and Cu.
On the other hand, as with tin, the lower layer of lead was separated by specific gravity sorting at approximately 400℃. The gasification residue from which the tin or lead has been separated is recycled to the gasifier or the carbon contained therein is combusted and used as heat for the process. A part of the produced gas is consumed in the reaction furnace to reduce tin oxide or lead oxide, but the majority is used as fuel or a raw material for chemical synthesis. The method of the present invention will be specifically explained with reference to FIGS. 1 and 2. In FIG. 1, tin oxide-containing ore is beneficent to a tin oxide content of 50-60% by weight and mixed with coal or coke having a particle size of 0.01-0.1 mm. The particle size of the tin oxide-containing ore is 0.01 to 0.1 mm. The mixture is fed to a suitable type of gasifier and brought into contact with carbon dioxide and/or steam at temperatures above 800°C to gasify the coal or coke. A portion of the gas produced reduces the tin oxide to metallic tin. The produced metal tin is taken out of the gasifier in a molten state as a gasification residue along with unreacted carbon, coal ash, and impurities in the ore, and is separated from the unreacted carbon, coal ash, and impurities in the ore as described above. be done. The separated crude tin is purified by a known dry method or electrolytic method to remove impurities such as arsenic, copper, bismuth, and antimony, and is made into a product. On the other hand, the residue separated from the crude tin may be supplied with air to burn unreacted carbon, and the heat at this time may be supplied to the gasification step. FIG. 2 shows a process using a lead oxide-containing ore in the method of the present invention, which is similar to the process shown in FIG. The only difference is that galena is beneficent and air oxidized to convert lead sulfide to lead oxide, which is then mixed with coal or coke. Since the obtained crude lead contains impurities such as gold, silver, copper, bismuth, arsenic, antimony, and tin, these impurities are removed by a known dry method or electrolytic method to obtain a product. According to the present invention, by combining the catalytic gasification of coal and the refining of tin or lead, the catalytic gasification of coal can be performed at a lower temperature and higher temperature than the conventional gasification temperature by the catalytic action of tin or lead. It is possible to refine the tin oxide-containing or lead oxide-containing ore fed to the catalytic gasification process at the same time. The present invention will be further explained by showing examples below. Example 1 Table 1 was installed in a test gasifier with an inner diameter of 5 cm and a height of 80 cm.
A mixture of 0.1 Kg of coal with a composition of 0.02 Kg of tin oxide ore containing 50% by weight of SnO 2 was filled.
【表】
このガス化炉に炉底部から空気を供給し、石炭
の燃焼熱で炉内温度を850℃に上昇させた。つい
で、空気の代わりに炉底部からCO20.1m3／hrス
チーム0.1m3／hrおよびO20.1m3／hrを供給するこ
とによつて炉内温度を850℃に保つてガス化およ
び酸化スズの還元を行つた。なお、ガス化剤の供
給量は時間の経過とともに減少する石炭の量に応
じて減少させた。反応開始から１時間後にガス化
剤の供給を止め、金属スズ60重量％灰分10重量％
および未反応炭素30重量％を含むガス化残渣をガ
ス化炉から抜き出して温度を約300℃程度に保ち、
溶融している金属スズを灰分、未反応炭素から分
別採取する。得られた粗スズの量は0.01Kgであつ
た。
一方、生成ガスの、ガス化剤供給開始10分後の
乾ガス組成はH218％、CO57％、CO225％および
CH40.1％であつた。
実施例 ２
酸化スズ含有鉱石の代わりに、方鉛鉱を焙焼し
て得られたPbO80重量％を含有する酸化鉛含有鉱
石0.02Kgを用いた他は実施例１と同様に操作を実
施した。
得られたガス化残渣から金属鉛を約350℃の温
度で下層の溶融物として取り出し、灰分、鉱滓な
どから分別した。分離された粗鉛は0.015Kgであ
つた。
なお、ガス化開始10分後の生成乾ガス組成は次
のとおりであつた。
H215％、CO55％、CO230％およびCH40.1％。[Table] Air was supplied to this gasifier from the bottom of the furnace, and the temperature inside the furnace was raised to 850℃ using the heat of coal combustion. Next, gasification and oxidation were carried out by keeping the temperature inside the furnace at 850°C by supplying CO 2 0.1m 3 / hr steam and O 2 0.1m 3 /hr from the bottom of the furnace instead of air. We carried out tin reduction. Note that the amount of gasifier supplied was decreased in accordance with the amount of coal that decreased over time. One hour after the start of the reaction, the supply of the gasifying agent was stopped, and the metal tin content was 60% by weight and the ash content was 10% by weight.
The gasification residue containing 30% by weight of unreacted carbon is extracted from the gasification furnace, and the temperature is maintained at approximately 300℃.
The molten metal tin is collected separately from the ash and unreacted carbon. The amount of crude tin obtained was 0.01Kg. On the other hand, the dry gas composition of the produced gas 10 minutes after the start of gasifying agent supply is 18% H2 , 57% CO2, 25% CO2 , and
CH 4 was 0.1%. Example 2 The same procedure as in Example 1 was carried out except that 0.02 kg of lead oxide-containing ore containing 80% by weight of PbO obtained by roasting galena was used instead of the tin oxide-containing ore. Metallic lead was extracted from the resulting gasification residue as a melt in the lower layer at a temperature of approximately 350°C, and was separated from ash, slag, etc. The amount of crude lead separated was 0.015Kg. The composition of the dry gas produced 10 minutes after the start of gasification was as follows. H2 15%, CO2 55%, CO2 30% and CH4 0.1%.
第１図は本発明によるスズの精錬プロセスのフ
ローシート、第２図は本発明による鉛の精錬プロ
セスのフローシートである。
FIG. 1 is a flow sheet of a tin refining process according to the present invention, and FIG. 2 is a flow sheet of a lead refining process according to the present invention.
Claims (1)
酸化鉛含有鉱石とを混合し、得られた混合物を
800℃以上の温度において二酸化炭素または／お
よび水蒸気と接触させて該石炭または炭化物をガ
ス化させるとともに該鉱石中の酸化スズまたは酸
化鉛を金属に還元し、得られた金属スズまたは金
属鉛をガス化残渣から分離することを特徴とする
石炭類の接触ガス化法と組み合せたスズおよび鉛
精錬法。1. Mix coal or carbide with tin oxide-containing ore or lead oxide-containing ore, and mix the resulting mixture.
The coal or carbide is gasified by contacting with carbon dioxide or/and water vapor at a temperature of 800°C or higher, and the tin oxide or lead oxide in the ore is reduced to metal, and the obtained metal tin or lead is gasified. A tin and lead refining method combined with a catalytic gasification method for coal, which is characterized by separation from chemical residues.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57052308A JPS58171537A (en) | 1982-04-01 | 1982-04-01 | Method for refining tin and lead in combination with catalytic gasifying method for coal or the like |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57052308A JPS58171537A (en) | 1982-04-01 | 1982-04-01 | Method for refining tin and lead in combination with catalytic gasifying method for coal or the like |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58171537A JPS58171537A (en) | 1983-10-08 |
| JPH0159342B2 true JPH0159342B2 (en) | 1989-12-15 |
Family
ID=12911153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57052308A Granted JPS58171537A (en) | 1982-04-01 | 1982-04-01 | Method for refining tin and lead in combination with catalytic gasifying method for coal or the like |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58171537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236280U (en) * | 1988-08-31 | 1990-03-08 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4621914A (en) * | 1983-07-27 | 1986-11-11 | Minolta Camera Kk | Camera system |
| JP5918024B2 (en) * | 2012-05-22 | 2016-05-18 | Ｄｏｗａエコシステム株式会社 | Method for reducing tin oxide |
-
1982
- 1982-04-01 JP JP57052308A patent/JPS58171537A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236280U (en) * | 1988-08-31 | 1990-03-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58171537A (en) | 1983-10-08 |
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