JPH0469083B2 - - Google Patents
Info
- Publication number
- JPH0469083B2 JPH0469083B2 JP2632785A JP2632785A JPH0469083B2 JP H0469083 B2 JPH0469083 B2 JP H0469083B2 JP 2632785 A JP2632785 A JP 2632785A JP 2632785 A JP2632785 A JP 2632785A JP H0469083 B2 JPH0469083 B2 JP H0469083B2
- Authority
- JP
- Japan
- Prior art keywords
- coke oven
- oven gas
- temperature
- hydrogenation step
- hydrogenation
- 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
- 239000007789 gas Substances 0.000 claims description 67
- 239000000571 coke Substances 0.000 claims description 50
- 238000005984 hydrogenation reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000002641 tar oil Substances 0.000 claims description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001993 dienes Chemical class 0.000 claims description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims 4
- 230000000694 effects Effects 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002754 natural gas substitute Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Industrial Gases (AREA)
Description
〔発明の利用分野〕
本発明はコークス炉ガスから不純物を除去する
方法に係り、特にコークス炉ガス中のタール油
分、ガム物質、ジエン類、酸素、オレフイン類及
び硫黄化合物を除去するのに好適なコークス炉ガ
スの精製法に関する。
〔発明の背景〕
従来のコークス炉ガスの精製方法としては、例
えばニツケル及び／又はコバルトとモリブデンと
を含有する触媒系を用いる水添脱硫工程によりジ
エン類、酸素、オレフイン類及び硫黄化合物を水
添する方法が知られている。例えば「プロセシズ
フオア ザ マニユフアクチユア オブ ナチ
ユラル−ガス サブステイチユーツ」
（PROCESSES FOR THE MANUFACTURE
OF NATURAL−GAS SUBSTITUTES）、ガ
ス カウンシル リサーチ コミユニケーシヨン
ジーシー155（Gas Council Reserch
Communication GC155）、1968年11月．第14〜
15頁参照。しかし乍ら、これらの従来方法ではコ
ークス炉ガス中に含有されているタール油分が触
媒活性点を覆つてしまうため、著しく触媒活性を
低下させるという問題がある。
さらにコークス炉ガス中のジエン類と酸素、一
酸化窒素が重合し、ガム状物質を生成して、触媒
層上流の機器類、配管等を閉塞させかつ触媒層の
閉塞等の問題点を生じる等の欠点があつた。
〔発明の目的〕
本発明の目的は、コークス炉ガス中に含有され
るタール油分、ガム物質、ジエン類、酸素、オレ
フイン類及び硫黄化合物を工程の組合せによつて
効率良く除去するコークス炉ガスの精製法を提供
することにある。
〔発明の概要〕
本発明を概説すれば、本発明は不純物として少
なくともタール油分及びガム物質を含有するコー
クス炉ガスを精製する方法において、該コークス
炉ガスを多孔質物質と接触させて該タール油分お
よびガム物質を吸着除去する吸着工程、ニツケル
とコバルトの少なくとも１つを担体に担持した触
媒の存在下で前記吸着工程よりのコークス炉ガス
中に残存するジエン類、酸素を主として水素化す
る第１水添工程、前記第１水添工程よりのコーク
ス炉ガス中に残存するオレフイン類、硫黄化合物
を主として水素化する第２水添工程及び前記第２
水添工程よりのコークス炉ガス中の硫化水素を吸
収除去する硫化水素除去工程の各工程を包含する
ことを特徴とする。
第１工程である吸着工程で使用する多孔質物質
（以下、吸着剤と略記する）の例には、アルミナ、
シリカ、ゼオライト、酸化鉄、チタニア、マグネ
シア、ケイ藻土、酸化カルシウム、ジルコニア、
活性炭及びそれらの混合物よりなる群から選択し
たものがある。特にアルミナ、シリカ、活性炭が
好ましい。
吸着剤は、BET表面積で10m2／ｇ以上を有す
ることが好ましく、特に好ましくは20m2〜1000
m2／ｇの範囲である。細孔容積は0.10ml／ｇ以上
を有することが好ましく、特に好ましくは0.15〜
0.60ml／ｇの範囲である。吸着剤は、吸湿性が高
く、空気中の水分を吸着して吸着性能が低下する
ので、使用前には適当な温度、好ましくは300〜
400℃の温度で乾燥するのが好ましい。吸着剤を
用いて行われる吸着の好ましい温度は常温〜300
℃の範囲であり、特に好しくは常温〜200℃の範
囲である。300℃を超えると吸着性能が低下する。
この吸着剤に対するコークス炉ガスの供給速度
は、空間速度で100h-1〜10000h-1が好適である。
空間速度が100h-1未満では使用する吸着量が多く
なつて経済的でなく、10000h-1を超えると吸着能
が低下する。吸着を行う圧力は限定はされない
が、特に２〜100気圧が好ましい。
タール油分及びガム状物質を吸着後の第１水添
工程で使用する触媒は、ニツケルとコバルトの少
なくとも１つを担体に担持した触媒で担体として
は、アルミナ、チタニア又はマグネシアを用いる
ことが望ましい。触媒の組成はニツケルとコバル
トの少なくとも１つを１〜25重量％、担体を99〜
75重量％の割合で含有するものが特に好適であ
る。これらの触媒によりコークス炉ガス中の不純
物であるジエン類及び酸素がほぼ完全に水素化さ
れる。本発明者らは、コークス炉ガス中に含まれ
る酸素、一酸化窒素、ジエン類が重合してガム状
物質を生成し触媒層及び触媒層上流の機器類、配
管等を閉塞したり、触媒活性を低下させたりする
ことを実験により確認した。この重合物の生成を
防ぐために主にオレフイン類、硫黄化合物を水添
する工程の前に低温域で閉塞の原因となるジエン
類と酸素を水添処理する第１水添工程を設けたと
ころオレフイン類と硫黄化合物を水素化する第２
水添工程の触媒の活性低下も非常に小さくなるこ
とを確認した。
第１水添工程後の第２水添工程にはオレフイン
類と硫黄化合物を水素化する触媒として、ニツケ
ル及び／又はコバルトとモリブデンとを含む触媒
を用いるのが好適である。例をあげれば、NiO−
MoO3−Al2O3、CoO−MoO3−Al2O3などであ
り、通常使用に際しては還元される。また水添脱
硫活性を高めるために、そしてメタネーシヨン反
応の抑制のために硫化水素、二硫化炭素、チオフ
エン等で硫化してから使用することが好ましい。
第２水添用触媒の好適な組成はニツケルおよび／
又はコバルトが１〜15重量％、モリブデンが３〜
45重量％、残部アルミナである。
第１水添工程における水添反応の温度は入口温
度100〜230℃、好ましくは150〜200℃の範囲内の
温度にすべきであり、そして触媒層は100〜350
℃、好ましくは150〜300℃の範囲内の温度にすべ
きである。第１水添工程の入口温度が100℃未満
では水添活性が充分でなくジエン類、酸素が第１
水添工程から第２水添工程に流出する。
第２水添工程における水添反応の温度は450℃
を越えないようにすべきであり、好ましくは410
℃以下である。450℃を超えると一酸化炭素及び
炭酸ガスのメタネーシヨンの反応率の割合が大き
く触媒層の温度上昇が大となり触媒の半融現象を
引起す。500℃を超えると炭化水素の分解による
炭素析出のトラブルを招くことがある。一方250
℃未満では水添脱硫活性が充分でない。硫黄化合
物の中で特にチオフエンの水添活性を高めるため
には300℃以上、好ましくは、350℃以上に温度を
保持する。水添脱硫後の硫化水素の除去方法とし
ては公知の方法がいずれも使用されうる。例を挙
げればZnO、Fe2O3、CuO、活性炭などの固体吸
着剤を使用する方法である。
コークス炉ガス中には、酸素が0.1〜2.0容量％
含有されており、酸素が1.0容量％反応すると150
℃の温度上昇がある。また、コークス炉ガス中に
はオレフイン類が3.0〜5.0容量％含有するが、オ
レフインが1.0容量％反応すると30℃の温度上昇
がある。この反応熱を抑制するには触媒層の温度
上昇を監視して精製後のガスの一部を再循環して
入口の酸素、オレフイン濃度を希釈すればよい。
本発明においては、このようにして精製された
コークス炉ガスの一部を吸着工程の前段又は後段
に循環する工程を含んでもよい。精製ガスを循環
することにより第１水添工程の水添反応の温度制
御が容易に行えるという効果がある。この時のガ
スの循環量は、原料コークス炉ガスの供給量に対
し10〜1000％の割合の範囲にあることが好まし
い。循環するガス量としては第１水添工程の温度
を350℃以下、及び第２水添工程の温度を450℃以
下に抑えるような範囲が選ばれガス量が調節され
る。
第１水添工程及び第２水添工程のコークス炉ガ
スの供給速度は空間速度（Ｓ、Ｖ）で500h-1〜
50000h-1が好ましい。空間速度が500h-1未満では
使用する触媒量が多くなつて経済的でなくなり、
一方50000h-1を超えると水添活性が充分でなくな
る。圧力は２〜100気圧で良いが特に限定されな
い。高圧下になる程副反応としてコークス炉ガス
中の一酸化炭素、炭酸ガスのメタネーシヨン反応
の割合が大となる。
次に本発明を実施するためのプロセスを図面に
よつて具体的に説明する。すなわち第１図は、本
発明の一実施の態様を示す工程図であり、１はコ
ークス炉ガス、２は吸着塔、３は第１水添塔、４
は加熱炉、５は第２水添塔、６は硫化水素吸収
塔、８は精製ガスを意味する。また第２図は、本
発明において精製ガスの一部を吸着工程の入口又
は出口へ再循環させた場合の一実施の態様を示す
工程図であり、１〜６及び８は第１図と同義であ
り、７は循環ラインを意味する。図面は、本発明
を理解するために必要な主要部のみを含み、それ
以外の循環機、冷却器、測定器及び制御装置、そ
の他の装置は、省略されている。
〔発明の実施例〕
次に本発明を実施例により更に説明するが、本
発明はこれにより限定されない。
実施例 １
第１図においてコークス炉ガス１は、約150〜
200℃の温度に加熱されて吸着塔２に導入される。
この吸着塔２には、BET表面積320m2／ｇ、平均
細孔容積0.18m2／ｇのアルミナが充填されてい
る。コークス炉ガスの主な成分の組成は、H2が
53.25％、COが5.89％、CO2が2.20％、CH4が
30.67％、C2H4が1.60％、C3H6が1.60％、O2が0.5
％、C4H6が0.10％、硫黄化合物が0.01％、N2が
4.18％であり、その中のタール油分及びガム物質
は10mg／Ｎm3であつた。吸着塔２のアルミナは、
コークス炉ガス中のタール油分及びガム物質を吸
着除去する。吸着塔出口のガス中のタール油分及
びガム物質は0.1mg／Ｎm3以下であり、99.0％以
上のタール油分及びガム物質が吸着除去されてい
た。
実施例 ２
本実施例ではアルミナ以外の吸着剤を用いたと
きのタール油分及びガム物質の吸着除去性能を調
べた結果を示す。吸着温度180℃、空間速度
（SV）2000h-1で行つた。得られた結果を第１表
に示す。
[Field of Application of the Invention] The present invention relates to a method for removing impurities from coke oven gas, and in particular, a method suitable for removing tar oil, gum substances, dienes, oxygen, olefins, and sulfur compounds from coke oven gas. Relating to a method for purifying coke oven gas. [Background of the Invention] Conventional coke oven gas purification methods include hydrogenation of dienes, oxygen, olefins, and sulfur compounds through a hydrodesulfurization process using a catalyst system containing nickel and/or cobalt and molybdenum. There are known ways to do this. For example, "Processes due to the Manufacture of Natural Gas Substituents"
(PROCESSES FOR THE MANUFACTURE
OF NATURAL-GAS SUBSTITUTES), Gas Council Research Community GC 155 (Gas Council Research
Communication GC155), November 1968. 14th~
See page 15. However, these conventional methods have the problem that the tar oil contained in the coke oven gas covers the catalytic active sites, significantly reducing the catalytic activity. Furthermore, the dienes, oxygen, and nitrogen monoxide in the coke oven gas polymerize, producing a gummy substance that clogs equipment, piping, etc. upstream of the catalyst layer, and causes problems such as blockage of the catalyst layer. There were some shortcomings. [Object of the Invention] The object of the present invention is to provide a coke oven gas that efficiently removes tar oil, gum substances, dienes, oxygen, olefins, and sulfur compounds contained in coke oven gas by a combination of steps. The objective is to provide a purification method. [Summary of the Invention] To summarize the invention, the present invention provides a method for purifying coke oven gas containing at least tar oil and gum material as impurities, wherein the coke oven gas is contacted with a porous material to purify the tar oil. and an adsorption step in which gum substances are adsorbed and removed; a first step in which dienes and oxygen remaining in the coke oven gas from the adsorption step are mainly hydrogenated in the presence of a catalyst having at least one of nickel and cobalt supported on a carrier; a hydrogenation step, a second hydrogenation step for mainly hydrogenating olefins and sulfur compounds remaining in the coke oven gas from the first hydrogenation step;
It is characterized in that it includes each step of the hydrogen sulfide removal step of absorbing and removing hydrogen sulfide in the coke oven gas from the hydrogenation step. Examples of porous materials (hereinafter abbreviated as adsorbents) used in the adsorption step, which is the first step, include alumina,
Silica, zeolite, iron oxide, titania, magnesia, diatomaceous earth, calcium oxide, zirconia,
selected from the group consisting of activated carbon and mixtures thereof; Particularly preferred are alumina, silica, and activated carbon. The adsorbent preferably has a BET surface area of 10 m 2 /g or more, particularly preferably 20 m 2 to 1000 m 2 /g.
It is in the range of m 2 /g. The pore volume is preferably 0.10ml/g or more, particularly preferably 0.15~
It is in the range of 0.60ml/g. The adsorbent has high hygroscopicity and adsorbs moisture in the air, reducing its adsorption performance. Therefore, before use, keep it at an appropriate temperature, preferably 300~300°C.
Drying at a temperature of 400°C is preferred. The preferred temperature for adsorption using an adsorbent is room temperature to 300°C.
℃ range, particularly preferably from room temperature to 200℃. Adsorption performance decreases when the temperature exceeds 300℃.
The feed rate of coke oven gas to this adsorbent is preferably 100 h -1 to 10000 h -1 in terms of space velocity.
When the space velocity is less than 100 h -1 , the amount of adsorption used becomes large, making it uneconomical, and when it exceeds 10,000 h -1 , the adsorption capacity decreases. The pressure at which adsorption is carried out is not limited, but 2 to 100 atmospheres is particularly preferred. The catalyst used in the first hydrogenation step after adsorbing tar oil and gummy substances is a catalyst in which at least one of nickel and cobalt is supported on a carrier, and it is preferable to use alumina, titania or magnesia as the carrier. The composition of the catalyst is 1 to 25% by weight of at least one of nickel and cobalt, and 99 to 99% by weight of the carrier.
Particularly preferred is one containing 75% by weight. These catalysts almost completely hydrogenate impurities such as dienes and oxygen in the coke oven gas. The present inventors have discovered that oxygen, nitrogen monoxide, and dienes contained in coke oven gas polymerize to form a gum-like substance that can block the catalyst layer and equipment and pipes upstream of the catalyst layer, and cause the catalyst to become inactive. It was confirmed through experiments that it lowers the In order to prevent the formation of this polymer, a first hydrogenation step was established to hydrogenate dienes and oxygen, which cause clogging at low temperatures, before the step of hydrogenating olefins and sulfur compounds. The second step is to hydrogenate sulfur compounds and sulfur compounds.
It was confirmed that the decrease in activity of the catalyst in the hydrogenation process was also very small. In the second hydrogenation step after the first hydrogenation step, it is preferable to use a catalyst containing nickel and/or cobalt and molybdenum as a catalyst for hydrogenating olefins and sulfur compounds. For example, NiO−
MoO3 - Al2O3 , CoO- MoO3 - Al2O3 , etc. , and are reduced during normal use . Further, in order to increase the hydrodesulfurization activity and to suppress the methanation reaction, it is preferable to sulfurize with hydrogen sulfide, carbon disulfide, thiophene, etc. before use.
The preferred composition of the second hydrogenation catalyst is nickel and/or
Or 1 to 15% by weight of cobalt and 3 to 15% of molybdenum
45% by weight, balance alumina. The temperature of the hydrogenation reaction in the first hydrogenation step should be within the inlet temperature range of 100-230℃, preferably 150-200℃, and the catalyst layer should be within the range of 100-350℃.
The temperature should preferably be in the range 150-300°C. If the inlet temperature of the first hydrogenation step is less than 100℃, the hydrogenation activity will not be sufficient and dienes and oxygen will enter the first hydrogenation step.
It flows out from the hydrogenation step to the second hydrogenation step. The temperature of the hydrogenation reaction in the second hydrogenation step is 450℃
should not exceed 410, preferably 410
below ℃. When the temperature exceeds 450°C, the reaction rate of carbon monoxide and carbon dioxide gas methanation increases, causing a large temperature rise in the catalyst layer and causing a half-melting phenomenon of the catalyst. If the temperature exceeds 500°C, troubles such as carbon precipitation due to decomposition of hydrocarbons may occur. while 250
Below ℃, the hydrodesulfurization activity is not sufficient. In order to particularly increase the hydrogenation activity of thiophene among sulfur compounds, the temperature is maintained at 300°C or higher, preferably 350°C or higher. Any known method can be used to remove hydrogen sulfide after hydrodesulfurization. Examples include methods using solid adsorbents such as ZnO, Fe 2 O 3 , CuO, and activated carbon. Oxygen in coke oven gas is 0.1 to 2.0% by volume.
Contains 150% when oxygen reacts with 1.0% by volume
There is a temperature rise of ℃. Further, coke oven gas contains 3.0 to 5.0% by volume of olefins, but when 1.0% by volume of olefins reacts, the temperature rises by 30°C. In order to suppress this reaction heat, the temperature rise in the catalyst layer may be monitored and a portion of the purified gas may be recirculated to dilute the oxygen and olefin concentrations at the inlet. The present invention may include a step of circulating a part of the coke oven gas purified in this manner to a stage before or after the adsorption step. By circulating the purified gas, it is possible to easily control the temperature of the hydrogenation reaction in the first hydrogenation step. The amount of gas circulated at this time is preferably in the range of 10 to 1000% of the amount of raw material coke oven gas supplied. The amount of gas to be circulated is selected and adjusted within a range such that the temperature in the first hydrogenation step is kept below 350°C and the temperature in the second hydrogenation step is kept below 450°C. The coke oven gas supply rate in the first hydrogenation step and the second hydrogenation step is space velocity (S, V) of 500h -1 ~
50000h -1 is preferred. When the space velocity is less than 500 h -1 , the amount of catalyst used becomes large and becomes uneconomical.
On the other hand, if it exceeds 50000 h -1 , hydrogenation activity will not be sufficient. The pressure may be 2 to 100 atmospheres, but is not particularly limited. The higher the pressure is, the higher the proportion of side reactions such as methanation reactions of carbon monoxide and carbon dioxide gas in the coke oven gas. Next, a process for carrying out the present invention will be specifically explained with reference to the drawings. That is, FIG. 1 is a process diagram showing an embodiment of the present invention, in which 1 is a coke oven gas, 2 is an adsorption tower, 3 is a first hydrogenation tower, and 4 is a process diagram showing an embodiment of the present invention.
5 means a heating furnace, 5 means a second hydrogenation tower, 6 means a hydrogen sulfide absorption tower, and 8 means purified gas. Further, FIG. 2 is a process diagram showing an embodiment in which a part of the purified gas is recirculated to the inlet or outlet of the adsorption step in the present invention, and 1 to 6 and 8 have the same meanings as in FIG. 1. and 7 means a circulation line. The drawings include only the main parts necessary for understanding the present invention, and other devices such as a circulator, a cooler, a measuring device, a control device, and other devices are omitted. [Examples of the Invention] Next, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto. Example 1 In FIG. 1, the coke oven gas 1 is about 150~
It is heated to a temperature of 200°C and introduced into the adsorption tower 2.
This adsorption tower 2 is filled with alumina having a BET surface area of 320 m 2 /g and an average pore volume of 0.18 m 2 /g. The composition of the main components of coke oven gas is that H2 is
53.25%, CO 5.89%, CO2 2.20%, CH4
30.67%, C2H4 1.60%, C3H6 1.60 %, O2 0.5
%, C4H6 0.10%, sulfur compounds 0.01% , N2
4.18%, and the tar oil and gum substances therein were 10 mg/Nm 3 . The alumina in adsorption tower 2 is
Adsorbs and removes tar oil and gum substances from coke oven gas. The tar oil content and gum substances in the gas at the outlet of the adsorption tower were less than 0.1 mg/Nm 3 , and more than 99.0% of the tar oil content and gum substances had been adsorbed and removed. Example 2 This example shows the results of investigating the adsorption and removal performance of tar oil and gum substances when using adsorbents other than alumina. The adsorption temperature was 180°C and the space velocity (SV) was 2000 h -1 . The results obtained are shown in Table 1.
【表】
実施例 ３
本実施例ではBET表面積320m2／ｇのアルミナ
を用いて空間速度（SV）5000h-1で吸着温度とタ
ール油分及びガム物質の吸着除去性能の関係を調
べた。結果を第２表に示す。[Table] Example 3 In this example, using alumina with a BET surface area of 320 m 2 /g, the relationship between adsorption temperature and adsorption removal performance of tar oil and gum substances was investigated at a space velocity (SV) of 5000 h -1 . The results are shown in Table 2.
以上、詳細な説明から明らかなように、本発明
によればコークス炉ガス中のタール油分、ガム物
質が効率良く除去され、かつコークス炉ガスに含
まれるジエン類、酸素、オレフイン類、硫黄化合
物のうち、先ず第１水添触媒により低温で主にジ
エン類、酸素を水添し、第２水添触媒で第１水添
触媒より残存したオレフイン類と硫黄化合物を水
添できるので、ジエン類重合によるガム状物質の
生成を抑制し、効率良くコークス炉ガスの精製が
できるという顕著な効果を持つている。
As is clear from the above detailed description, according to the present invention, tar oil and gum substances in coke oven gas can be efficiently removed, and dienes, oxygen, olefins, and sulfur compounds contained in coke oven gas can be efficiently removed. First, dienes and oxygen can be mainly hydrogenated at low temperature using the first hydrogenation catalyst, and olefins and sulfur compounds remaining from the first hydrogenation catalyst can be hydrogenated using the second hydrogenation catalyst. It has the remarkable effect of suppressing the formation of gummy substances caused by gas and making it possible to purify coke oven gas efficiently.
第１図は本発明の一実施の態様を示す工程図、
第２図は本発明において精製ガスの一部を吸着工
程の入口又は出口へ再循環させた場合の一実施の
態様を示す工程図である。
１……コークス炉ガス、２……吸着塔、３……
第１水添塔、４……加熱炉、５……第２水添塔、
６……硫化水素吸収塔、７……循環ライン、８…
…精製ガス。
FIG. 1 is a process diagram showing an embodiment of the present invention;
FIG. 2 is a process diagram showing an embodiment of the present invention in which a part of the purified gas is recycled to the inlet or outlet of the adsorption step. 1...Coke oven gas, 2...Adsorption tower, 3...
First hydrogenation tower, 4...Heating furnace, 5...Second hydrogenation tower,
6...Hydrogen sulfide absorption tower, 7...Circulation line, 8...
…Refined gas.
Claims (1)
ン類、酸素、オレフイン類及び硫黄化合物を含有
するコークス炉ガスを精製する方法において、該
コークス炉ガスを多孔質物質と接触させてタール
油分およびガム物質を吸着除去する吸着工程、前
記吸着工程よりのコークス炉ガス中に残存するジ
エン類及び酸素をニツケルとコバルトの少なくと
も１つを担体上に担持した触媒の存在下で水素化
する第１水添工程、前記第１水添工程よりのコー
クス炉ガス中に残存するオレフイン類及び硫黄化
合物を水素化する第２水添工程、及び前記第２水
添工程よりのコークス炉ガス中の硫化水素を吸収
除去する硫化水素除去工程の各工程を包含するこ
とを特徴とするコークス炉ガスの精製法。 ２ 該硫化水素除去工程からの精製ガスの一部を
該吸着工程の前段に再循環させ、該第１水添工程
の温度が350℃を越えず及び該第２水添工程の温
度が450℃を越えないように調節することを特徴
とする特許請求の範囲第１項記載のコークス炉ガ
スの精製法。 ３ 該硫化水素除去工程からの精製ガスの一部を
該吸着工程の後段に再循環させ、該第１水添工程
の温度が350℃を越えず及び該第２水添工程の温
度が450℃を越えないように調節することを特徴
とする特許請求の範囲第１項記載のコークス炉ガ
スの精製法。 ４ 該再循環ガスを原料コークス炉ガスの量に対
し10〜1000％の割合で供給することを特徴とする
特許請求の範囲第２項又は第３項記載のコークス
炉ガスの精製法。 ５ 該第１水添工程の入口温度を100〜230℃の範
囲内の温度に調節することを特徴とする特許請求
の範囲第１項記載のコークス炉ガスの精製法。 ６ 該吸着工程の温度を300℃以下に調節するこ
とを特徴とする特許請求の範囲第１項記載のコー
クス炉ガスの精製法。 ７ 該吸着工程で使用する多孔質物質のBET表
面積が10m2／ｇ以上であり、細孔容積が0.10ml／
ｇ以上であることを特徴とする特許請求の範囲第
１項記載のコークス炉ガスの精製法。 ８ 該多孔質物質がアルミナ、シリカ、活性炭の
少なくとも１つからなることを特徴とする特許請
求の範囲第１項記載のコークス炉ガスの精製法。 ９ 該第１水添工程に使用する触媒がニツケルと
コバルトの少なくとも１つ１〜25重量％、担体99
〜75重量％からなることを特徴とする特許請求の
範囲第１項記載のコークス炉ガスの精製法。 １０ 該第２水添工程に使用する触媒がニツケル
及び／又はコバルトを１〜15重量％、モリブデン
を３〜45重量％およびアルミナを96〜40重量％の
割合で含有するものであることを特徴とする特許
請求の範囲第１項記載のコークス炉ガスの精製
法。 １１ 該第１水添工程に使用する触媒の担体がア
ルミナ、チタニア、マグネシアの少なくとも１つ
よりなることを特徴とする特許請求の範囲第１項
記載のコークス炉ガスの精製法。[Claims] 1. A method for refining coke oven gas containing tar oil, gum substances, dienes, oxygen, olefins, and sulfur compounds as impurities, comprising: bringing the coke oven gas into contact with a porous substance; An adsorption step in which tar oil and gum substances are adsorbed and removed, and dienes and oxygen remaining in the coke oven gas from the adsorption step are hydrogenated in the presence of a catalyst having at least one of nickel and cobalt supported on a carrier. a first hydrogenation step; a second hydrogenation step for hydrogenating olefins and sulfur compounds remaining in the coke oven gas from the first hydrogenation step; A method for refining coke oven gas, characterized by including each step of a hydrogen sulfide removal step of absorbing and removing hydrogen sulfide. 2. Part of the purified gas from the hydrogen sulfide removal step is recycled to the previous stage of the adsorption step, and the temperature in the first hydrogenation step does not exceed 350°C and the temperature in the second hydrogenation step is 450°C. A coke oven gas refining method according to claim 1, wherein the coke oven gas purification method is adjusted so as not to exceed . 3. Part of the purified gas from the hydrogen sulfide removal step is recycled to the latter stage of the adsorption step, and the temperature in the first hydrogenation step does not exceed 350°C and the temperature in the second hydrogenation step is 450°C. A coke oven gas refining method according to claim 1, wherein the coke oven gas purification method is adjusted so as not to exceed . 4. The method for purifying coke oven gas according to claim 2 or 3, characterized in that the recirculated gas is supplied at a rate of 10 to 1000% of the amount of raw coke oven gas. 5. The coke oven gas purification method according to claim 1, characterized in that the inlet temperature of the first hydrogenation step is adjusted to a temperature within the range of 100 to 230°C. 6. The coke oven gas purification method according to claim 1, characterized in that the temperature of the adsorption step is adjusted to 300° C. or lower. 7 The BET surface area of the porous material used in the adsorption step is 10 m 2 /g or more, and the pore volume is 0.10 ml / g.
The method for purifying coke oven gas according to claim 1, characterized in that the coke oven gas purification method is at least 100 g. 8. The method for purifying coke oven gas according to claim 1, wherein the porous material is made of at least one of alumina, silica, and activated carbon. 9 The catalyst used in the first hydrogenation step is 1 to 25% by weight of at least one of nickel and cobalt, and a carrier 99
The method for purifying coke oven gas according to claim 1, characterized in that the coke oven gas contains 75% by weight. 10 The catalyst used in the second hydrogenation step contains 1 to 15% by weight of nickel and/or cobalt, 3 to 45% by weight of molybdenum, and 96 to 40% by weight of alumina. A method for purifying coke oven gas according to claim 1. 11. The coke oven gas purification method according to claim 1, wherein the catalyst carrier used in the first hydrogenation step is made of at least one of alumina, titania, and magnesia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2632785A JPS61186204A (en) | 1985-02-15 | 1985-02-15 | Purification of coke oven gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2632785A JPS61186204A (en) | 1985-02-15 | 1985-02-15 | Purification of coke oven gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61186204A JPS61186204A (en) | 1986-08-19 |
| JPH0469083B2 true JPH0469083B2 (en) | 1992-11-05 |
Family
ID=12190317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2632785A Granted JPS61186204A (en) | 1985-02-15 | 1985-02-15 | Purification of coke oven gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61186204A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0553838U (en) * | 1991-12-27 | 1993-07-20 | セイコー電子部品株式会社 | Ring parts continuous feeder |
| KR20000040628A (en) * | 1998-12-18 | 2000-07-05 | 신현준 | Adsorbent for high-boiling point hydrocarbons and method for continuous removal of hydrocarbons using the same adsorbent |
-
1985
- 1985-02-15 JP JP2632785A patent/JPS61186204A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61186204A (en) | 1986-08-19 |
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