JPH0249241B2 - - Google Patents
Info
- Publication number
- JPH0249241B2 JPH0249241B2 JP56069463A JP6946381A JPH0249241B2 JP H0249241 B2 JPH0249241 B2 JP H0249241B2 JP 56069463 A JP56069463 A JP 56069463A JP 6946381 A JP6946381 A JP 6946381A JP H0249241 B2 JPH0249241 B2 JP H0249241B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- gas
- iron
- crude gas
- temperature
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
- 239000007858 starting material Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000011651 chromium Substances 0.000 claims description 10
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003034 coal gas Substances 0.000 claims description 6
- 235000014413 iron hydroxide Nutrition 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 48
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- 229910005965 SO 2 Inorganic materials 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VZQAQPGIOPQBGU-UHFFFAOYSA-N oxidoiminoiron(1+) Chemical compound [Fe]N=O VZQAQPGIOPQBGU-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UBUHAZKODAUXCP-UHFFFAOYSA-N iron(2+);oxygen(2-);hydrate Chemical class O.[O-2].[Fe+2] UBUHAZKODAUXCP-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
Description
【発明の詳細な説明】
本発明は固体および（または）液体の炭素含有
材料を1000〜2000℃の温度で部分酸化（ガス化）
することによつて製造した粗ガスの触媒による処
理法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the partial oxidation (gasification) of solid and/or liquid carbon-containing materials at temperatures between 1000 and 2000°C.
This invention relates to a method for catalytically treating crude gas produced by.
炭素含有出発材料の部分酸化による粗ガスの製
造および引続くこの粗ガスの種々の目的たとえば
加熱ガス、合成ガスまたは還元ガスとして使用す
るための処理はすでに古くから公知であり、多数
の大工業的装置が好結果をもつて実現されてい
る。上記目的にしばしば使用される前記温度範囲
で作業する公知ガス化法の１つはたとえばガス化
する出発材料をいわゆる気流ガス化するコツパー
ス−トチエツク法である。この方法の本質的利点
はとくに炭素含有出発材料がきわめて融通性に富
むことである。すなわちこの方法によれば天然に
産出するすべての種類の石炭ならびに他の固体お
よび（または）液体燃料たとえば石油化学工業か
らのピツチ、タール、石油コークス、重い炭化水
素および蒸留または製造残渣もガス化することが
できる。得られた粗ガスの次の処理はもちろんそ
れぞれの使用目的によつて異なる。たとえば粗ガ
スはアンモニア製造のためには次の処理の途中で
多くの場合、種々の強さの圧縮および深冷温度で
の処理たとえばメタノール低温洗浄または液体チ
ツ素洗浄を行わなければならない。 The production of crude gas by partial oxidation of carbon-containing starting materials and the subsequent treatment of this crude gas for its use for various purposes, for example as heating gas, synthesis gas or reducing gas, has been known for a long time and is used in numerous large-scale industrial processes. The device has been implemented with good results. One of the known gasification processes operating in the temperature ranges mentioned which is often used for the above purpose is, for example, the so-called gas-stream gasification process of the starting material to be gasified. The essential advantage of this process is, inter alia, the great flexibility of the carbon-containing starting materials. This process therefore gasifies all types of naturally occurring coal as well as other solid and/or liquid fuels, such as pitch, tar, petroleum coke, heavy hydrocarbons and distillation or production residues from the petrochemical industry. be able to. The further processing of the crude gas obtained will of course depend on the respective intended use. For example, the crude gas for ammonia production often has to be subjected to various degrees of compression and treatment at cryogenic temperatures, such as methanol cold washing or liquid nitrogen washing, during further processing.
しかしこれら２つの処理工程を実施する際、場
合により作業装置に種々の問題および困難が生ず
ることが明らかになつた。たとえば粗ガスコンプ
レツサのインペラおよび付属の中間冷却器にイオ
ウ、硫化物およびニトロシル鉄錯塩（いわゆるル
ツサン塩）の沈積が確認された。メタノール低温
洗浄の場合、イオウおよびメタノールに可溶のイ
オウ−鉄化合物の形成により熱交換器内に不所望
の沈積が生ずる。液体チツ素洗浄の深冷温度部分
において同様不所望の沈積が熱交換器内に生じ、
これは凝固したNO字に起因するものであり、解
凍によつてしか除去することができなかつた。 However, it has become apparent that when carrying out these two process steps, various problems and difficulties may arise with the working equipment. For example, deposits of sulfur, sulfides and nitrosyl iron complex salts (so-called Lutusan salts) were found on the impeller of the crude gas compressor and attached intercooler. In the case of methanol cold cleaning, undesirable deposits occur in the heat exchanger due to the formation of sulfur and methanol-soluble sulfur-iron compounds. Similar undesirable deposits occur in the heat exchanger during the cryogenic temperature portion of the liquid nitrogen wash;
This was due to the solidified NO letters and could only be removed by thawing.
これら障害の原因としてまずもつぱらチツ素酸
化物NOxの存在が考えられ、これは粗ガス中に
痕跡成分として通常100ppm以下の程度で含まれ
る。それゆえ最近石炭ガス化によつて製造した合
成ガスからアンモニアを製造する場合、チツ素酸
化物をガスからモリブデン酸コバルト痕跡で処理
して除去することがすでに提案されている
（Chem.Eng.1980年２月、88〜90、94ページ参
照）。 The first possible cause of these disturbances is the presence of nitrogen oxide NO x , which is normally contained in crude gas as a trace component in amounts of 100 ppm or less. For the production of ammonia from synthesis gas produced by coal gasification, it has therefore recently been already proposed to remove the nitrogen oxides from the gas by treating it with traces of cobalt molybdate (Chem.Eng.1980 (February, pp. 88-90, 94).
しかし本出願人の研究により前記障害の１部に
対してチツ素酸化物のほかに同様粗ガス中に痕跡
成分として＜50ppmまたは＜150ppmの程度存在
するSO2および酸素も影響することが明らかにな
つた。さらに前記痕跡成分は一般に粗ガスの次の
処理の際導管、コンプレツサ、洗浄器、熱交換器
等の内部に障害（沈積）をひき起こすことを前提
としなければならない。 However, the applicant's research has revealed that, in addition to nitrogen oxides, SO 2 and oxygen, which are present as trace components in the crude gas at levels of <50 ppm or <150 ppm, are also responsible for some of the above-mentioned disturbances. Summer. Furthermore, it must be assumed that these trace components generally cause disturbances (deposits) inside lines, compressors, scrubbers, heat exchangers, etc. during the subsequent processing of the raw gas.
それゆえ本発明の目的は部分酸化によつて製造
した粗ガスの、チツ素酸化物のほかにSO2および
酸素も除去する触媒による処理法を得ることであ
る。同時にこの方法の経済性の点でできるだけと
くに安価な触媒で処理しなければならない。さら
にランニング作業費はもちろんできるだけ低く保
持しなければならない。それゆえ本発明の方法は
粗ガスの強力な加熱および再冷却を避けるように
できるだけ低い温度レベルで実施しうることを目
標としなければならない。さらに触媒による圧力
降下はできるだけ低く保たなければならない。 It is therefore an object of the present invention to provide a process for the catalytic treatment of crude gas produced by partial oxidation, which removes not only the nitrogen oxides but also SO 2 and oxygen. At the same time, in view of the economy of the process, it is necessary to work with particularly inexpensive catalysts as far as possible. Furthermore, running costs must of course be kept as low as possible. The process of the invention must therefore be aimed at being able to be carried out at as low a temperature level as possible, so as to avoid intensive heating and recooling of the crude gas. Furthermore, the pressure drop across the catalyst must be kept as low as possible.
この目的は本発明によりダスト状不純物を除去
した70〜250℃の温度に冷却した粗ガスを次のガ
ス処理の前に１〜100バールの圧力および3000〜
30000Nm3ガス／m3触媒・時間の空間速度で、活
性成分として硫化物の形で存在する鉄２〜65重量
％（触媒全重量に対し）を含む触媒を介して導く
ことを特徴とする首記の方法によつて解決され
る。 The purpose of this is to prepare the crude gas, which has been cooled to a temperature of 70-250°C from which dusty impurities have been removed according to the invention, at a pressure of 1-100 bar and at a temperature of 3000-3000 bar before further gas treatment.
The neck is characterized in that it is conducted through a catalyst containing 2 to 65% by weight (relative to the total weight of the catalyst) of iron present in the form of sulfides as an active component, at a space velocity of 30000 Nm 3 gas/m 3 catalyst/hour. The problem is solved by the method described below.
触媒による粗ガスの処理を90〜200℃の温度お
よび２〜60バールの圧力で実施するのがとくに有
利なことが明らかになつた。 It has proven particularly advantageous to carry out the treatment of the crude gas with the catalyst at temperatures of 90 DEG to 200 DEG C. and pressures of 2 to 60 bar.
本発明の方法を実施するため担持材料を有する
または有しない酸化物と酸化クロムの混合物を含
む触媒出発材料から出発することができる。さら
にとくに水酸化鉄（）、酸化鉄水和物、ボーキ
サイト製造からの赤泥および酸化鉄または水酸化
鉄含有石炭ガス精製塊（いわゆる沼鉄鉱）を触媒
出発材料として使用することができる。 To carry out the process of the invention it is possible to start from a catalyst starting material comprising a mixture of oxides and chromium oxide with or without support materials. Furthermore, in particular iron hydroxide (), iron oxide hydrates, red mud from bauxite production and iron oxide- or iron hydroxide-containing coal-gas refined lumps (so-called swampite) can be used as catalyst starting materials.
触媒出発材料の鉄成分の所要の硫化は通常粗ガ
ス中に含まれるH2Sとの反応によつて行われる。
それゆえ本発明の方法を実施する際、粗ガス1N
m3当り７mgの最低イオウ量を下回らないのが有利
である。前記硫化の際、場合により存在するクロ
ム成分はまつたくまたはきわめて僅かな程度しか
反応しない。それゆえクロムは触媒中で酸化物の
形を維持し、とくに触媒の構造的補強材として機
能する。酸化鉄および酸化クロムの混合物を触媒
出発材料として使用する限り、この混合物中の
Fe：Crの重量比は５：１〜15：１が適当である。 The necessary sulfidation of the iron component of the catalyst starting material is usually carried out by reaction with H 2 S contained in the crude gas.
Therefore, when carrying out the method of the invention, the crude gas 1N
It is advantageous not to fall below a minimum sulfur content of 7 mg/m 3 . During the sulfurization, any chromium components present react only to a very small extent. Chromium therefore remains in the oxide form in the catalyst and acts, inter alia, as a structural reinforcement of the catalyst. As long as a mixture of iron oxide and chromium oxide is used as catalyst starting material, the
The weight ratio of Fe:Cr is suitably 5:1 to 15:1.
前述のように触媒の活性成分は担持材料ととも
にまたはなしで使用することができる。触媒が担
体材料を含む場合、とくにAl2O3またはSiO2が担
持材料として使用される。しかし他の公知担持材
料たとえばMgO、ZrO2およびTiO2ならびにその
混合物および化合物（スピネル）および粘土また
はバン土をこの目的に使用することもできる。 As mentioned above, the active components of the catalyst can be used with or without a support material. If the catalyst comprises a support material, in particular Al 2 O 3 or SiO 2 are used as support material. However, other known support materials such as MgO, ZrO 2 and TiO 2 and mixtures and compounds thereof (spinel) and clays or clays can also be used for this purpose.
本発明の方法を実施する空間速度が高いため、
場合により触媒の活性成分を担体に支持し、その
形状によつて触媒床を介する圧力降下を避けるの
が有利である。これはたとえば担体のハネカム構
造によつて達成される。 Due to the high space velocity of carrying out the method of the invention,
It is advantageous if the active components of the catalyst are optionally supported on a support, the shape of which avoids a pressure drop across the catalyst bed. This is achieved, for example, by a honeycomb structure of the carrier.
粗ガスの本発明による処理はガス化装置から出
るガスを適当な手段たとえばサイクロン分離器お
よび（または）いわゆる湿式洗浄器内の処理によ
つてそのダスト状不純物を除去した後、次のガス
処理の前すなわち酸性ガス洗浄および場合により
変換の前に行われる。粗ガスの次の処理の途中で
圧縮が行われる場合、本発明によるガス処理は有
利に粗ガスの第１圧縮工程の前または間に実施さ
れる。この場合ガス中に存在する水素との反応に
よりSO2はH2Sに、チツ素酸化物はN2および（ま
たは）NH3になる。元素イオウ、ニトロシル鉄
錯塩（いわゆるルツサン塩）またはブードアール
平衡による炭素の形成はこの場合認められなかつ
た。これに反し粗ガス中に含まれる酸素は完全に
反応して水になる。これが本発明の方法を実施す
る比較的低温で可能なことは常用のガス精製の際
の関係を考慮すれば意外であり、予期されなかつ
た。常用のガス精製では本発明の温度レベルより
ごく僅か低い温度でチツ素酸化物は水酸化鉄
（）を含む石炭ガス精製塊によつて錯塩に結合
され、酸素はこの場合H2Sと反応して元素イオウ
を形成する。しかし本発明の方法の経済性にとつ
て、使用する比較的低い温度レベルはそれによつ
て粗ガス流れの特殊な加熱を必要としないのでと
くに重要である。 The inventive treatment of the crude gas involves removing the dusty impurities from the gas leaving the gasifier by suitable means, such as treatment in a cyclone separator and/or a so-called wet scrubber, before the subsequent gas treatment. before the acid gas scrubbing and optionally the conversion. If compression is carried out during the subsequent processing of the crude gas, the gas treatment according to the invention is preferably carried out before or during the first compression step of the crude gas. In this case, SO 2 becomes H 2 S and nitrogen oxide becomes N 2 and/or NH 3 by reaction with the hydrogen present in the gas. No formation of carbon by elemental sulfur, nitrosyl iron complexes (so-called lutusan salts) or Boudouard equilibrium was observed in this case. On the other hand, the oxygen contained in the crude gas completely reacts to water. That this is possible at the relatively low temperatures at which the process of the invention is carried out is surprising and unexpected in view of the context in conventional gas purification. In conventional gas refining, at temperatures only slightly lower than the temperature levels of the present invention, the nitrogen oxides are combined into complex salts by the coal gas refining mass containing iron hydroxide (), and the oxygen reacts with H 2 S in this case. to form elemental sulfur. However, the relatively low temperature levels used are particularly important for the economics of the process of the invention, since no special heating of the crude gas stream is thereby required.
本発明により使用する触媒は要求された反応条
件下には水性ガス平衡によるCOの変換もCOのメ
タン化も促進しない。硫化した触媒の水蒸気によ
る損傷は生じない。COSは初期濃度に応じて
COS−水素添加
COS＋H2CO＋H2S
とCOS−加水分解
COS＋H2SCO2＋H2O
の同時平衡に従つて形成または除去される。 The catalyst used according to the invention neither promotes the conversion of CO by water-gas equilibrium nor the methanation of CO under the required reaction conditions. No water vapor damage to the sulfided catalyst occurs. COS depends on the initial concentration
It is formed or removed according to the simultaneous equilibrium of COS - hydrogenated COS + H 2 CO + H 2 S and COS - hydrolyzed COS + H 2 SCO 2 + H 2 O.
次に本発明の方法の効果を４つの例により説明
する。例１、２および４で使用した装入ガス（粗
ガス）は石炭の部分酸化により、例３では重い炭
化水素の部分酸化によつて製造した。例１〜３の
場合触媒出発材料として酸化鉄と酸化クロムの混
合物、例４では触媒出発材料として水酸化鉄
（）を含む石炭ガス精製塊を使用した。触媒出
発材料の硫化は４つの場合すべて装入ガスの含有
H2Sにより行われた。次に例の詳細を示す：
例
(1) 触媒出発材料 Fe／Cr酸化物（Fe：Cr＝
９：１）
温 度 150℃
圧 力 2.5バール
空間速度 13000h-1
装入ガスH2 21.4容量％
CO 51.4 〃
CO2 8.0 〃
N2 12.1 〃
H2O 6.2 〃
H2S 0.9 〃
NO 100容量ppm
SO2 50 〃
O2 50 〃
生成ガス中 NO 0.5容量ppm
SO2 ＜２ 〃
NH3 70 〃
他の成分はほぼ変化なし。 Next, the effects of the method of the present invention will be explained using four examples. The feed gas (crude gas) used in Examples 1, 2 and 4 was produced by partial oxidation of coal and in Example 3 by partial oxidation of heavy hydrocarbons. In Examples 1 to 3, a mixture of iron oxide and chromium oxide was used as the catalyst starting material, and in Example 4, a coal gas purified lump containing iron hydroxide (2) was used as the catalyst starting material. The sulfidation of the catalyst starting material is carried out in all four cases by the inclusion of the charge gas.
Performed with H2S . The details of the example are as follows: Example (1) Catalyst starting material Fe/Cr oxide (Fe:Cr=
9:1) Temperature 150℃ Pressure 2.5 bar Space velocity 13000h -1 Charge gas H 2 21.4% by volume CO 51.4 〃 CO 2 8.0 〃 N 2 12.1 〃 H 2 O 6.2 〃 H 2 S 0.9 〃 NO 100 vol ppm SO 2 50 〃 O 2 50 〃 NO in generated gas 0.5 volume ppm SO 2 <2 〃 NH 3 70 〃 Other components remain almost unchanged.
(2) 触媒出発材料 Fe／Cr酸化物（Fe：Cr＝
９：１）
温 度 150℃
圧 力 2.5バール
空間速度 26000h-1
装入ガス 例１と同じ
生成ガス中 NO ３容量ppm
SO2 ＜２ 〃
NH3 50 〃
他の成分はほとんど変化なし。(2) Catalyst starting material Fe/Cr oxide (Fe:Cr=
9:1) Temperature: 150°C Pressure: 2.5 bar Space velocity: 26000h -1 Charge gas Same as Example 1 in the produced gas NO 3 volume ppm SO 2 <2 〃 NH 3 50 〃 Other components almost unchanged.
(3) 触媒出発材料 Fe／Cr酸化物（Fe：Cr＝
９：１）
温 度 150℃
圧 力 2.5バール
空間速度 26000h-1
装入ガスH2 34.8容量％
CO 42.0 〃
CO2 7.5 〃
N2 9.2 〃
H2O 6.2 〃
H2S 0.3 〃
NO 100容量ppm
SO2 50 〃
生成ガス中 NO 2.5容量ppm
SO2 ２ 〃
NH3 55 〃
他の成分はほとんど変化なし。(3) Catalyst starting material Fe/Cr oxide (Fe:Cr=
9:1) Temperature 150℃ Pressure 2.5 bar Space velocity 26000h -1 Charge gas H 2 34.8% by volume CO 42.0 〃 CO 2 7.5 〃 N 2 9.2 〃 H 2 O 6.2 〃 H 2 S 0.3 〃 NO 100 vol ppm SO 2 50 〃 NO 2.5 ppm by volume in the produced gas SO 2 2 〃 NH 3 55 〃 Almost no change in other components.
(4) 触媒出発材料 水酸化鉄（）（ガス洗浄材
料）
温 度 150℃
圧 力 2.5バール
空間速度 26000h-1
装入ガス 例１と同じ
生成ガス中 NO ２容量ppm
SO2 ２ 〃
NH3 60 〃
他の成分はほぼ変化なし。(4) Catalyst starting material Iron hydroxide (gas cleaning material) Temperature 150°C Pressure 2.5 bar Space velocity 26000h -1 Charge gas Same product gas as in Example 1 NO 2 volume ppm SO 2 2 〃 NH 3 60 〃 Other components remain almost unchanged.
これらの結果は４つのすべての例で装入ガス中
のSO2およびチツ素酸化物含量の有効な低下を達
成し得たことを示す。チツ素酸化物はこの場合主
としてNH3に還元される。例４はいわゆる石炭
ガス精製塊を触媒出発材料として使用したのでと
くに注目に値する。石炭ガス精製塊はもちろん例
１〜３に使用した酸化鉄と酸化クロムの混合物よ
り安価であり、きわめて経済的な方法である。 These results show that in all four cases an effective reduction in SO 2 and nitrogen oxide content in the charge gas could be achieved. Ni oxide is reduced in this case primarily to NH 3 . Example 4 is particularly noteworthy because it used so-called coal-gas refined lumps as catalyst starting material. The coal gas purified ingot is of course cheaper than the mixture of iron oxide and chromium oxide used in Examples 1 to 3, making it an extremely economical process.
Claims (1)
1000〜2000℃の温度で部分酸化（ガス化）するこ
とによつて製造した粗ガスを触媒により処理する
方法において、ダスト状不純物を除去した、70〜
250℃の温度に冷却した粗ガスを次のガス処理の
前に１〜100バールの圧力ならびに触媒１m3およ
び１時間当りガス3000〜30000Nm3の空間速度で、
活性成分として硫化物の形で存在する鉄２〜65重
量％（全触媒重量に対し）を含む触媒を介して導
くことを特徴とする部分酸化粗ガスを触媒により
処理する方法。 ２ 粗ガスの触媒による処理をとくに90〜200℃
の温度および２〜60バールの圧力で行う特許請求
の範囲第１項記載の方法。 ３ 鉄が触媒出発材料中でまず酸化物または水酸
化物として存在し、この鉄を粗ガス中に含まれる
H2Sとの反応によつて硫化物の形に変えた触媒を
使用する特許請求の範囲第１項または第２項記載
の方法。 ４ 触媒出発材料としてFe：Crの重量比がとく
に５：１〜15：１の鉄−クロム酸化物を使用する
特許請求の範囲第１項から第３項までのいずれか
１項記載の方法。 ５ 触媒出発材料として水酸化鉄（）を含む石
炭ガス精製塊を使用する特許請求の範囲第１項か
ら第３項までのいずれか１項記載の方法。 ６ 活性成分が担体の表面に担持された触媒を使
用し、この担体がその形状によつて触媒床を介す
る圧力降下を減少する特許請求の範囲第１項から
第５項までのいずれか１項記載の方法。[Claims] 1. Solid and/or liquid carbon-containing materials
A method in which crude gas produced by partial oxidation (gasification) at a temperature of 1000 to 2000°C is treated with a catalyst, from which dust-like impurities have been removed.
The crude gas cooled to a temperature of 250 ° C is subjected to a pressure of 1 to 100 bar and a space velocity of 1 m 3 of catalyst and 3000 to 30 000 Nm 3 of gas per hour before further gas treatment.
A process for the catalytic treatment of partially oxidized crude gas, characterized in that it is conducted through a catalyst containing 2 to 65% by weight (relative to the total catalyst weight) of iron present in the form of sulfides as an active component. 2 Treating crude gas with a catalyst at a temperature of 90 to 200℃
2. A process according to claim 1, which is carried out at a temperature of from 2 to 60 bar. 3 Iron is initially present as an oxide or hydroxide in the catalyst starting material, and this iron is present in the crude gas.
3. A process as claimed in claim 1, in which the catalyst is converted into the sulfide form by reaction with H2S . 4. Process according to one of the claims 1 to 3, characterized in that iron-chromium oxide is used as the catalyst starting material, with an Fe:Cr weight ratio of preferably 5:1 to 15:1. 5. The method according to any one of claims 1 to 3, wherein a coal gas refined lump containing iron hydroxide (2) is used as a catalyst starting material. 6. Use of a catalyst in which the active component is supported on the surface of a carrier, the shape of which reduces the pressure drop across the catalyst bed. Method described.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3017998A DE3017998C2 (en) | 1980-05-10 | 1980-05-10 | Process for the catalytic treatment of partial oxidation raw gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56169104A JPS56169104A (en) | 1981-12-25 |
| JPH0249241B2 true JPH0249241B2 (en) | 1990-10-29 |
Family
ID=6102108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6946381A Granted JPS56169104A (en) | 1980-05-10 | 1981-05-11 | Method of treating partial oxidizing coarse gas by catalyst |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS56169104A (en) |
| AU (1) | AU537231B2 (en) |
| DD (1) | DD158039A5 (en) |
| DE (1) | DE3017998C2 (en) |
| IN (1) | IN155094B (en) |
| ZA (1) | ZA812495B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62256708A (en) * | 1986-04-28 | 1987-11-09 | Kobe Steel Ltd | Method for purifying co |
| SE459584B (en) * | 1987-10-02 | 1989-07-17 | Studsvik Ab | PROCEDURES FOR PROCESSING OF RAAGAS MANUFACTURED FROM COAL CONTENTS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE958496C (en) * | 1954-11-10 | 1957-02-21 | Metallgesellschaft Ag | Process for the catalytic hydrogenating refining of hydrocarbons which are liquid or solid at room temperature, at elevated temperature and pressure in the gas phase and / or liquid phase in the presence of luminous gas, coke oven gas, carbonization gas or similar gases containing hydrogen |
| GB942029A (en) * | 1961-03-23 | 1963-11-20 | Metallgesellschaft Ag | A method of detoxifying town and trunk gases |
-
1980
- 1980-05-10 DE DE3017998A patent/DE3017998C2/en not_active Expired - Fee Related
-
1981
- 1981-04-15 ZA ZA00812495A patent/ZA812495B/en unknown
- 1981-05-05 DD DD81229742A patent/DD158039A5/en not_active IP Right Cessation
- 1981-05-08 AU AU70278/81A patent/AU537231B2/en not_active Ceased
- 1981-05-11 JP JP6946381A patent/JPS56169104A/en active Granted
- 1981-09-03 IN IN989/CAL/81A patent/IN155094B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DD158039A5 (en) | 1982-12-22 |
| ZA812495B (en) | 1982-04-28 |
| DE3017998C2 (en) | 1994-05-26 |
| AU7027881A (en) | 1981-11-19 |
| IN155094B (en) | 1984-12-29 |
| JPS56169104A (en) | 1981-12-25 |
| AU537231B2 (en) | 1984-06-14 |
| DE3017998A1 (en) | 1981-11-19 |
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