JPS60238144A - Arsenic compound removing agent - Google Patents
Arsenic compound removing agentInfo
- Publication number
- JPS60238144A JPS60238144A JP59093032A JP9303284A JPS60238144A JP S60238144 A JPS60238144 A JP S60238144A JP 59093032 A JP59093032 A JP 59093032A JP 9303284 A JP9303284 A JP 9303284A JP S60238144 A JPS60238144 A JP S60238144A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- arsenic
- group compound
- compound
- chromium
- 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.)
- Granted
Links
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、活性炭に所定金属化合物を相持させて砒素化
合物の吸着除去率を高めた砒素化合物除去剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an arsenic compound remover in which a predetermined metal compound is supported on activated carbon to increase the rate of adsorption and removal of arsenic compounds.
〔発明の技術的背景とその問題点９
石油精製工業においては、各種の触媒を用いて流動接触
分解装置等で原油留出留分を分解し、高オクタン価ガソ
リンを製造することが行なわれている。仁のような接触
分解工程において副生ずるガスは石油化学原料として利
用されている。原油の種類によっては、副生ずる液化石
油ガス特にプロピレンを主成分とするガス中に多量の砒
素化合物が含まれてくることがある。このガス中に含ま
れている砒、素化合物例えばアルシンは、一般的に徒の
工程において触媒毒となる。また、砒素化合物は有毒で
あるため、最終生成物中にたとえ極微量であっても含ま
れていてはならない。[Technical background of the invention and its problems 9] In the petroleum refining industry, crude oil distillate fractions are cracked in fluid catalytic crackers using various catalysts to produce high-octane gasoline. . Gases produced by-product in the catalytic cracking process, such as kerosene, are used as petrochemical raw materials. Depending on the type of crude oil, a large amount of arsenic compounds may be contained in the by-produced liquefied petroleum gas, particularly gas mainly composed of propylene. Arsenic and elementary compounds such as arsine contained in this gas generally become catalyst poisons in unfavorable processes. Furthermore, since arsenic compounds are toxic, they must not be included in the final product, even in trace amounts.
このようなことから、ガス又は液体に存在する砒素化合
物を除去するために、これまでは、活性炭による吸着除
去法や酸化剤による酸化分離除失法が適用されているが
、これらの方法はいずれも砒素化合物の除去率が低く満
足すべきものではなかった。For this reason, in order to remove arsenic compounds present in gases or liquids, adsorption removal methods using activated carbon and oxidative separation removal methods using oxidizing agents have been applied, but these methods have However, the removal rate of arsenic compounds was low and unsatisfactory.
本発明は、上記問題点を解消し、気体・液体中に含まれ
ている砒素化合物を高い除去率で吸着除去できる砒素化
合物除去剤の提供を目的とする。An object of the present invention is to solve the above-mentioned problems and provide an arsenic compound removing agent capable of adsorbing and removing arsenic compounds contained in gases and liquids at a high removal rate.
本発明者らは、上記した目的を達成すべく、炭化水素ガ
ス中の砒素化合物特にアルシン類（アルシン、シアルシ
ン、アルキルアルシン等）の除去に有効な除去剤を種々
探索した結果、銅族化合物およびクロム族化合物を担持
した活性炭はアルシン類の吸着除去率が高く極めて有用
であることを見出し本発明の砒素化合物除去剤を開発す
るに到った。In order to achieve the above object, the present inventors have searched for various removal agents that are effective in removing arsenic compounds, particularly arsine compounds (arsine, siarsine, alkylarsine, etc.) from hydrocarbon gases, and have found that copper group compounds and The inventors discovered that activated carbon supporting a chromium group compound has a high rate of adsorption and removal of arsine compounds and is extremely useful, leading to the development of the arsenic compound remover of the present invention.
すなわち、本発明砒素化合物除去剤は、活性炭と、該活
性炭に担持された銅族化合物及びクロム族化合物とから
成ることを特徴とする。That is, the arsenic compound remover of the present invention is characterized by comprising activated carbon, and a copper group compound and a chromium group compound supported on the activated carbon.
まず、本発明砒素化合物除去剤の基材は活性炭であり、
後述の銅族化合物及びりｐム族化合物がこれに相持され
ている。活性炭としては、木材。First, the base material of the arsenic compound remover of the present invention is activated carbon,
Copper group compounds and PM group compounds, which will be described later, are supported therein. Wood is the activated carbon.
ノコギリクズ、ヤシガラ、コークス、石炭、各種の合成
樹脂などを常法により炭化したのち賦活して精製したも
のを使用することができる。活性炭の形状は、吸着させ
るガス・液体の処理方法に応じて適宜選定されるが、具
体的には、球状２円柱状、破砕状、ａｌｌ状状どである
。また、使用される好適な活性炭としては、ＢＥＴ表面
表面積１御０〜３０００
；平均細孔径５〜３０Ａ，特に好ましくは１０〜２５Ａ
；平均粒径ｏ．ｉ〜５ｍ，特に好ましくは０、３〜３１
ＩＬ；のものがよい。Sawdust, coconut shell, coke, coal, various synthetic resins, etc. can be carbonized by a conventional method and then activated and refined. The shape of the activated carbon is appropriately selected depending on the method of processing the gas/liquid to be adsorbed, and specifically, it is spherical, bicylindrical, crushed, all-shaped, etc. In addition, suitable activated carbon to be used has a BET surface area of 1 to 0 to 3000; an average pore diameter of 5 to 30A, particularly preferably 10 to 25A.
; Average particle size o. i~5m, particularly preferably 0,3~31
IL; is better.
本発明において、銅族化合物とは、銅，鎧．金の無機化
合物，無機酸塩，有機酸塩などである。In the present invention, copper group compounds include copper, armor, etc. These include inorganic compounds, inorganic acid salts, and organic acid salts of gold.
無機化合物としては、醸化物，ハロゲン化物，水酸化物
などがあげられる。無機酸塩としては、硝酸塩，硫酸塩
，リン酸塩，軟醗塩，塩基性炭酸塩。Examples of inorganic compounds include compounds, halides, and hydroxides. Inorganic acid salts include nitrates, sulfates, phosphates, soft salts, and basic carbonates.
アンモニウム塩などがあげられる。有機酸塩としては、
ギ酸塩，酢酸塩，シュウ酸塩などがあげられる。Examples include ammonium salts. As an organic acid salt,
Examples include formate, acetate, and oxalate.
りυム族化合物とは、クロム、モリブデン、タングステ
ンの無機化合物，無機酸塩，有機酸塩などである。無機
化合物としては、酸化物，へ四グン化物，水酸化物など
があげられる。無機酸塩としては、硝酸塩，硫酸塩，リ
ン酸塩，炭醗塩，塩基性炭酸塩，アンモニウム塩などが
あげられる。Rim group compounds include inorganic compounds, inorganic acid salts, and organic acid salts of chromium, molybdenum, and tungsten. Examples of inorganic compounds include oxides, hetetragides, hydroxides, and the like. Examples of inorganic acid salts include nitrates, sulfates, phosphates, carbonates, basic carbonates, and ammonium salts.
有機酸塩としては、ギ酸塩，酢酸塩，シュウ酸塩などが
あけられる。以上の銅族化合物，クロム族化合物のいず
れにあっても、それぞれは単独で活性炭に担持されても
よいし、又は２種以上の銅族化合物，クロム族化合物を
適宜に組合せて相持させてもよい。Examples of organic acid salts include formates, acetates, and oxalates. Any of the above copper group compounds and chromium group compounds may be supported on activated carbon alone, or two or more copper group compounds and chromium group compounds may be supported in an appropriate combination. good.
上述の如き活性炭に担持させる銅族化合物の担持量は銅
族金属に換算して０．５〜３０重量％，好ましくは３〜
９重量％であり、クロム族化合物の担持量は０．５〜２
０重量％，好ましくは１〜８重量％である。夫々の相持
量が、上記した値未満の場合には砒素化合物の吸着除去
率向上に資することがなく、逆にこれらの値を超えて担
持させたとしても格別吸着除去の効果があがるというこ
とはない。The amount of the copper group compound supported on the activated carbon as described above is 0.5 to 30% by weight, preferably 3 to 30% by weight in terms of copper group metal.
9% by weight, and the supported amount of chromium group compound is 0.5-2
0% by weight, preferably 1-8% by weight. If the amount of each supported is less than the above-mentioned values, it will not contribute to improving the adsorption removal rate of arsenic compounds, and conversely, even if supported in amounts exceeding these values, the effect of adsorption and removal will be particularly improved. do not have.
上記のような割合で銅族化合物とクロム族化合物が担持
された活性炭は、アルシン等砒素の水素化物の除去率が
高く、また、砒素の硫化物，酸化物，ハ四グン化物など
に対しても高い吸着除去率を示す。尚、必要に応じて、
マンガン族化合物、鉄，コバルト、ニッケル等の周期律
表■族金属の化合物及びマグネシウム、バリウム等のア
ルカリ土類金属の化合物を活性炭に更に担持させること
ができる。Activated carbon that supports copper group compounds and chromium group compounds in the above ratio has a high removal rate of arsenic hydrides such as arsine, and is also effective against arsenic sulfides, oxides, tetragonides, etc. also shows a high adsorption removal rate. In addition, if necessary,
Activated carbon can further support a manganese group compound, a compound of group I metals of the periodic table such as iron, cobalt, and nickel, and a compound of alkaline earth metals such as magnesium and barium.
本発明の砒素化合物除去剤の調製方法としては、沈浚法
，浸漬法，イオン交換法，熱分解法，融解法などが適用
可能であり、具体的には、上記したような銅族化合物と
り四ム族化合物とを水等の溶媒に所定量溶解又は懸濁さ
せたのち、得られた液を活性炭に含浸又は散布し、必要
に応じて乾燥。As a method for preparing the arsenic compound removing agent of the present invention, a dredging method, a dipping method, an ion exchange method, a thermal decomposition method, a melting method, etc. can be applied. After dissolving or suspending a predetermined amount of a group compound in a solvent such as water, the resulting liquid is impregnated or sprinkled on activated carbon and dried if necessary.
焼成する方法、又は活性炭原料に銅族化合物とクロム族
化合物を所定量添加したのち、常法により炭化，賦活す
る方法がある。There is a method of firing, or a method of adding a predetermined amount of a copper group compound and a chromium group compound to an activated carbon raw material, and then carbonizing and activating it by a conventional method.
以上のようにして製造される本発明の砒素化合物除去剤
に砒素化合物を含むガス又は液体を種々の方法により接
触させると、砒素化合物が本発明除去剤に吸着しガス・
液体中から除去される。本発明除去剤は、石油精製・石
油化学工業・電気化学工業・信金工業等使用される分野
において種々の使用態様をきり、砒素化合物除去剤に接
触させるガス・液体の処理条件もその分骨において異な
るＯ
例えば、石油精製において発生する炭化水素ガスに含有
されている砒素化合物を除去する場合に使用する際の好
適なガス処理条件に関していえば、分解装置は固定床、
移動床、流動床のいずれのタイプでもよく、砒素化合物
を含む炭化水素ガスの温度は２００℃以下好ましくは０
〜１００℃に設定し、ガスの圧力は５０ｋｇ／ｍ以下、
好ましくは１〜３０ｋｌｉ’／ｉに設定し、ガス空間時
間（ＧＨ８Ｖ）は１００００ Ｈｒ＝以下、好ましくは
２００〜２０００Ｈｒ”Ｋ設定すると、本発明除去剤が
効果的に作用する。When the arsenic compound remover of the present invention produced as described above is brought into contact with a gas or liquid containing an arsenic compound by various methods, the arsenic compound is adsorbed to the arsenic compound remover of the present invention and the gas and
removed from the liquid. The remover of the present invention can be used in various fields such as petroleum refining, petrochemical industry, electrochemical industry, and Shinkin industry, and the treatment conditions for gases and liquids that come into contact with the arsenic compound remover also vary accordingly. For example, in terms of suitable gas treatment conditions for use in removing arsenic compounds contained in hydrocarbon gases generated in petroleum refining, crackers are fixed bed,
Either type of moving bed or fluidized bed may be used, and the temperature of the hydrocarbon gas containing the arsenic compound is 200°C or less, preferably 0.
The temperature is set to ~100℃, the gas pressure is 50kg/m or less,
The removing agent of the present invention works effectively when the gas space time (GH8V) is preferably set to 1 to 30 kli'/i, and the gas space time (GH8V) is set to 10,000 Hr or less, preferably 200 to 2,000 Hr''K.
実施例１〜７
大慶油田から採掘された原油留分からガソリンを製造す
る際に副生ずるグロビレンを主成分とする原料ガスを使
用した。この原料ガスの組成は次のようになっている。Examples 1 to 7 A raw material gas containing globylene as a by-product when producing gasoline from a crude oil fraction extracted from the Daqing oil field was used. The composition of this raw material gas is as follows.
また、除去剤として表１の如きＢＥＴ表面積及び平均細
孔径を有する活性炭に酸化銅及び酸化クロムを表１の如
き担持量で担持させたものを使用した。このような除去
剤１ｇを直径１５１１ 高さ１０ｓｎｔの固定床反応器
へ充填した。上記の原料ガスを温度４０℃、圧力１０
ｋｌｌｃｒｌＧ、ＧＨ８Ｖ６００Ｈｒ−’に設定し上記
の固定床反応器へ供給した。In addition, activated carbon having a BET surface area and average pore diameter as shown in Table 1 and carrying copper oxide and chromium oxide in the amounts shown in Table 1 was used as a removing agent. 1 g of such removal agent was charged into a fixed bed reactor with a diameter of 1511 mm and a height of 10 snts. The above raw material gas was heated at a temperature of 40°C and a pressure of 10°C.
kllcrlG, GH8V600Hr-' and supplied to the above fixed bed reactor.
１ｋｇ、３ｋｌｉｌ、６に９の原料ガスを固定床反応器
へ供給したときの夫々の場合におけるアルシンの破過率
を測定し、その結果を表１に示した。硫化カルボニルの
破過率は原料ガス１ｋｌｉｌを処理した場合のみを表１
に示した。ここで、アルシン及び硫化カルビニルの破過
率は次式によりめた。When 1 kg, 3 kli, and 6 to 9 raw material gases were supplied to the fixed bed reactor, the breakthrough rate of arsine was measured in each case, and the results are shown in Table 1. Table 1 shows the breakthrough rate of carbonyl sulfide only when 1 kli of raw material gas is processed.
It was shown to. Here, the breakthrough rate of arsine and carbinyl sulfide was determined by the following formula.
比較例１〜２
銅族化合物又はクロム族化合物のどちらか一方のみを活
性炭に担持させた以外は、実施例と同様の条件で原料ガ
スを吸着させ、その結果を表１に示した。Comparative Examples 1 and 2 The raw material gas was adsorbed under the same conditions as in the example except that activated carbon supported only either the copper group compound or the chromium group compound, and the results are shown in Table 1.
以上、発明の実施例からも明らかなように、本発明除去
剤は、銅族化合物とクロム族化合物とを同時に活性炭に
相持委せていない除去剤と比較して、砒素化合物の吸着
除去率が高い。As mentioned above, as is clear from the examples of the invention, the removal agent of the present invention has a higher adsorption removal rate of arsenic compounds than a removal agent that does not simultaneously support copper group compounds and chromium group compounds with activated carbon. expensive.
本発明除去剤は、砒素化合物の除去率が極めて高いので
、石油精製業をはじめとして石油化学工業・電気化学工
業・冶金工業等種々の産業分野に適用できる。Since the removal agent of the present invention has an extremely high removal rate of arsenic compounds, it can be applied to various industrial fields such as the oil refining industry, the petrochemical industry, the electrochemical industry, and the metallurgical industry.
特に、石油精製２石油化学工業に本発明除去剤を適用し
た場合、本発明触媒はアルシン類の除去に有効であるの
みならず、硫化水素、硫化カルブニル等の硫化物の吸着
除去率も高いので、有用である。In particular, when the removing agent of the present invention is applied to the petroleum refining and petrochemical industries, the catalyst of the present invention is not only effective in removing arsine, but also has a high adsorption removal rate of sulfides such as hydrogen sulfide and carbunyl sulfide. , useful.
Claims (1)
ロム族化合物とから成ることを特徴とする砒素化合物除
去剤。 ２、該銅族化合物の相持量が銅族金属に換算して０．５
〜３０重量％、該クロム族化合物の担持量がクロム族金
属に換算して０．５〜２０重量％である特許請求の範囲
第１項記載の砒素化合物除去剤。[Scope of Claims] 1. An arsenic compound removing agent comprising activated carbon, and a copper group compound and a chromium group compound supported on the activated carbon. 2. The amount of the copper group compound supported is 0.5 in terms of copper group metal.
30% by weight, and the amount of the chromium group compound supported is 0.5 to 20% by weight in terms of chromium group metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093032A JPS60238144A (en) | 1984-05-11 | 1984-05-11 | Arsenic compound removing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093032A JPS60238144A (en) | 1984-05-11 | 1984-05-11 | Arsenic compound removing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60238144A true JPS60238144A (en) | 1985-11-27 |
| JPS6322183B2 JPS6322183B2 (en) | 1988-05-11 |
Family
ID=14071153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59093032A Granted JPS60238144A (en) | 1984-05-11 | 1984-05-11 | Arsenic compound removing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60238144A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63251496A (en) * | 1987-04-08 | 1988-10-18 | Kawasaki Steel Corp | Method of purifying gas mainly composed of carbon monoxide |
| JPS63270541A (en) * | 1987-04-30 | 1988-11-08 | Mitsubishi Heavy Ind Ltd | Adsorbent for arsenic compound and removing method for arsenic compound from combustion gas |
| JPH02139033A (en) * | 1988-11-18 | 1990-05-29 | Chiyoda Corp | Poisonous gas adsorbent, its manufacture and purification of exhaust gas using it |
| JP2005238184A (en) * | 2004-02-27 | 2005-09-08 | Japan Organo Co Ltd | Method for treating organoarsenic compound |
| JP2018069242A (en) * | 2012-05-07 | 2018-05-10 | カーボン テクノロジー ホールディングス， エルエルシー | Organism-originated active carbon, and method for creating and using the same |
| US10611977B2 (en) | 2011-04-15 | 2020-04-07 | Carbon Technology Holdings, LLC | Methods and apparatus for enhancing the energy content of carbonaceous materials from pyrolysis |
| US11213801B2 (en) | 2013-10-24 | 2022-01-04 | Carbon Technology Holdings, LLC | Methods and apparatus for producing activated carbon from biomass through carbonized ash intermediates |
| US11358119B2 (en) | 2014-01-16 | 2022-06-14 | Carbon Technology Holdings, LLC | Carbon micro-plant |
| US11413601B2 (en) | 2014-10-24 | 2022-08-16 | Carbon Technology Holdings, LLC | Halogenated activated carbon compositions and methods of making and using same |
| US11458452B2 (en) | 2014-02-24 | 2022-10-04 | Carbon Technology Holdings, LLC | Highly mesoporous activated carbon |
| US11753698B2 (en) | 2020-09-25 | 2023-09-12 | Carbon Technology Holdings, LLC | Bio-reduction of metal ores integrated with biomass pyrolysis |
| US11851723B2 (en) | 2021-02-18 | 2023-12-26 | Carbon Technology Holdings, LLC | Carbon-negative metallurgical products |
| US11932814B2 (en) | 2021-04-27 | 2024-03-19 | Carbon Technology Holdings, LLC | Biocarbon blends with optimized fixed carbon content, and methods for making and using the same |
| US11987763B2 (en) | 2021-07-09 | 2024-05-21 | Carbon Technology Holdings, LLC | Processes for producing biocarbon pellets with high fixed-carbon content and optimized reactivity, and biocarbon pellets obtained therefrom |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124856A (en) * | 1990-08-03 | 1992-06-23 | International Business Machines Corporation | Magnetic recording device with unitary filter medium to trap organic and inorganic chemical pollutants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5120769A (en) * | 1974-08-01 | 1976-02-19 | Dainippon Toryo Kk | HAIENDATSURYUSHORIHOHO |
| JPS59160535A (en) * | 1983-03-03 | 1984-09-11 | Takeda Chem Ind Ltd | Adsorbent for arsine and treatment of fluid containing arsine |
-
1984
- 1984-05-11 JP JP59093032A patent/JPS60238144A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5120769A (en) * | 1974-08-01 | 1976-02-19 | Dainippon Toryo Kk | HAIENDATSURYUSHORIHOHO |
| JPS59160535A (en) * | 1983-03-03 | 1984-09-11 | Takeda Chem Ind Ltd | Adsorbent for arsine and treatment of fluid containing arsine |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63251496A (en) * | 1987-04-08 | 1988-10-18 | Kawasaki Steel Corp | Method of purifying gas mainly composed of carbon monoxide |
| JPS63270541A (en) * | 1987-04-30 | 1988-11-08 | Mitsubishi Heavy Ind Ltd | Adsorbent for arsenic compound and removing method for arsenic compound from combustion gas |
| JPH0729049B2 (en) * | 1987-04-30 | 1995-04-05 | 三菱重工業株式会社 | Method for removing arsenic compounds in combustion exhaust gas |
| JPH02139033A (en) * | 1988-11-18 | 1990-05-29 | Chiyoda Corp | Poisonous gas adsorbent, its manufacture and purification of exhaust gas using it |
| JP2005238184A (en) * | 2004-02-27 | 2005-09-08 | Japan Organo Co Ltd | Method for treating organoarsenic compound |
| JP4598415B2 (en) * | 2004-02-27 | 2010-12-15 | オルガノ株式会社 | Organic arsenic compound processing method |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPS6322183B2 (en) | 1988-05-11 |
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