JP2019090416A - 閉鎖型サイクル急冷を伴う部分酸化反応 - Google Patents
閉鎖型サイクル急冷を伴う部分酸化反応 Download PDFInfo
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- JP2019090416A JP2019090416A JP2018245962A JP2018245962A JP2019090416A JP 2019090416 A JP2019090416 A JP 2019090416A JP 2018245962 A JP2018245962 A JP 2018245962A JP 2018245962 A JP2018245962 A JP 2018245962A JP 2019090416 A JP2019090416 A JP 2019090416A
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
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- C10J2300/00—Details of gasification processes
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Abstract
Description
CO+CO=C+CO2 (1)
当該管は、石炭および褐炭のような固体燃料中に存在する揮発性無機構成成分の凝縮に由来する固体析出物が、定期的水洗浄により除去されるよう設計されなければならない。
・ 急冷、固体灰分除去およびPPSからの再循環高圧CO2を伴う熱交換による冷却後のPOX系からのPOX燃料ガス中に存在する炭素系または炭化水素燃料、POX工程、および酸素プラント(例えば空気分離ユニット)から得られる酸素に由来するすべての不純物が、PPS中で燃焼される。例示的不純物は、過剰量のH2、CO、CH4、CO2、H2O、N2およびAr中に存在する不純物であり得る。
・ POX燃料ガス中に存在するすべての酸化可能不純物は、PPS燃焼により酸化され得る。
・ POX燃料ガス中に存在するイオウ化合物、例えばH2S、COSおよびCS2は、SO2、SO3、H2OおよびCO2に酸化され得る。POX燃料ガス中に存在する任意のNH3およびHCNは、NO、NO2、H2OおよびCO2に酸化され得る。
・ POX工程は、好ましくは、約2MPa以上の圧力で操作する。
・ PPSは、約10MPa以上の入口圧を有するタービンを利用する出力の発生により明示され得る。
・ PPSは、約12以下の圧力比(入口対出口)を有するタービンを利用する出力の発生により明示される。
・ POX反応は、約1300℃〜約1600℃の断熱火炎温度で実行され得る。
・ POX反応器への供給物は、水、CO2またはその組合せ中の粉末化固体燃料でスラリー化され得る。
・ POX反応器への供給物は、粉末化固体燃料の伴出流を含むと定義され得る。
・ POX反応器への供給物は、ビチューメンの加熱流のような液体を含むと定義され得る。
・ POX反応器は、約250℃以上の温度でPPSから獲得され、そしてPPSレキュペレータ熱交換器を出る高圧再循環流の出口温度より低い温度でPPSに戻される高圧再循環流の一部分に輻射熱を伝達する内部伝熱セクションを包含するよう適応され得る。
・ POX反応の直接生成物は、急冷POX燃料ガスの再循環部分と、急冷POX燃料ガスから凝縮される液体水の一部分と、PPSから再循環されるCO2と、あるいはこれら3つの組合せと直接混合することにより急冷され得る。
・ POX工程に用いられる燃料から生じる灰分は、POX生成物の急冷後、そしてPOX燃料ガスのさらなる冷却前に、除去され得る。
・ POX流の急冷において達成される温度は、炭素沈着またはメタルダスティング腐食がPOX系またはPPSにおける任意の下流設備で起きないよう、約400℃またはそれより低い温度、あるいはブードワ反応の速度が十分に低い温度であり得る。
・ 急冷および灰分除去後のPOX生成物は、PPSから獲得され、そして戻される高圧再循環流体流を加熱することを用いることにより、約100℃以下の温度に冷却され得る。
・ PPSは、PPS燃焼器中の燃焼生成物を加圧再循環流と混合し、そして全体流を出力発生のために適応される少なくとも1つのPPSタービンに通すことにより、明確にされ得る。
・ PPSは、約0.1MPa以上、他の実施形態では、約1MPa以上の最終放出圧での単数または複数のタービンの操作により明確にされ得る。
・ PPSは、少なくとも全タービン排気流(単数または複数)に対して予め圧縮された高圧再循環流を加熱する1つ以上のレキュペレータ熱交換器の使用により明確にされ得る。
・ PPSは、O2、液体H2O、NO2およびNOとの反応により、SO2およびSO3をH2SO4に変換することにより明確にされ得る。
・ PPSは、NO、NO2および液体H2OをHNO3に変換することにより明確にされ得る。
・ PPS酸変換は、レキュペレータ熱交換器の冷却終了時に水および酸が冷却タービン排気ガスから分離される温度より低い、水が凝縮する点に対応する操作温度で実行され得る。
・ 酸+酸との反応により生成され、任意にPPS燃焼器からの凝縮水で希釈される可溶性無機構成成分は、さらなる処理のために除去され得る。
・ 高圧CO2再循環流体流(単数または複数)は、灰分除去後に急冷POX生成物ガスを冷却するために用いられ得る。
・ 高圧CO2再循環流体流は、任意に、1つより多い温度レベルで、PPSから獲得される1つより多い流体流を含み得る。
・ 1つより多い高圧CO2再循環流体流は、1つより多い温度レベルでPPSに戻され得る。
・ 一流体流は、PPSから獲得され、1つより多い温度レベルで、1つより多い流れとしてPPSに戻され得る。
・ 1つより多い流体流は、PPSから獲得され、単一加熱流としてPPSに戻され得る。
・ 冷却正味POX燃料ガス生成物は、POX急冷再循環流体の冷却および分離後、それがPOX系を出る圧力からPPS燃焼器の入口圧と実質的に同一の圧力に圧縮され得る。
・ 急冷POX生成物ガスを冷却するのに用いるためのPPSから獲得される流体流は、PPSからの加圧再循環流の一部であり得る。
・ POX系に用いられる酸素は、90モル%より高い、好ましくは95モル%より高い純度を有し得る。
・ 部分酸化ガスは水で急冷されて、少なくともH2、CO、CO2、1つ以上のイオウ化合物(例えばH2S)およびH2Oを含有するガス混合物を生じる。
・ 急冷POX燃料ガスの冷却は、PPSからの加圧再循環ガスの2つの流れを伴って実行され得る;POX熱変換器に進入する第一再循環流の入口温度は、PPS再循環CO2圧縮器の放出温度であり得る;そしてPOX熱交換器に進入する第二再循環CO2流の入口温度は、PPSタービン排出流における水露点の20℃以内であり得る。
・ 燃料ガスを含むPOX流は、水で急冷されて、存在する過剰な液体水を有する水蒸気で飽和されたPOXガスを生成し;そしてPPSからの加圧再循環ガス2つの入口流は、POXガス露点温度の20℃以内の温度で単一流としてPOX熱変換器を退出し得る。
・ POX流は、水で急冷されて、その露点温度を上回り、そして400℃より低い急冷POX流を生じ得る;POX熱交換器に進入する2つの入口流は、加熱され、第二入口流温度に対応する温度点で併合され得る;第一出口加熱流体流は、POX流露点温度の20℃以内の温度で除去され、そして残りの流れはさらに加熱され、約380℃〜399℃の温度でPOX熱交換器を出る。
・ 急冷後のPOX燃料ガスの一部分は、除去され、触媒シフト反応器に通されて、COおよびH2OをH2およびCO2に変換し得る。
・ シフト反応器からの出口ガスは、PPSから獲得され、そしてPPSに戻される再循環ガスに対して急冷POX熱交換器中で冷却され得る。
・ シフト化ガスは、非シフト化ガスの一部分と混合され、さらに加工処理されて、水、CO2、イオウ化合物、水銀およびその他の揮発性無機構成成分を分離して、H2およびCOを0.8:1〜2.5:1の割合であとに残す。
・ シフト化ガス単独は、さらに加工処理されて、99モル%より高い純度のH2流を生じ得る。
・ H2またはH2およびCO流中のイオウ化合物、NH3、HCNおよび水の含量は、各々、1ppmモル未満であり得る。
・ 分離装置は、多床型圧力変動吸着(PSA)系として明示され得る。
・ PSA系からの吸着生成物を含む前記PSAからの低圧廃棄ガスは、PPS燃焼器により必要とされる圧力に圧縮され、PPS燃焼器への総POX燃料ガス流中に混合され得る。
・ 第一燃料のPOXのために用いられる酸素は、POX熱変換器中で350℃までの温度に加熱され得る。
・ PPS燃焼器中で用いられる酸素は、POX熱変換器中で350℃までの温度に加熱され得る。
燃料を部分的に酸化して、燃料ガスを含むPOX流を生成するのに十分な条件下で、POX反応器中で固体または液体燃料および酸素を併合すること;
約400℃以下の温度で急冷POX流を生成し、POX流中に存在する任意の溶融固体の少なくとも一部分を固化するのに十分な条件下で、急冷流体との組合せによりPOX流を急冷すること;
そこに存在する任意の固体の少なくとも一部分を除去するために、急冷POX流を処理すること;
急冷POX流をPOX熱交換器に送り、冷却流に対して急冷POX流を約100℃以下の温度に冷却することにより急冷POX流からある量の熱を引き出して、POX燃料ガス流を生成すること;
POX燃料ガスを分離容器に通して、POX燃料ガス流中に存在する任意の水の少なくとも一部分を分離すること;
POX燃料ガス流を約12MPa以上の圧力に圧縮すること;
少なくとも約10MPaの圧力で、少なくとも約800℃の温度で、PPS燃焼器中で(任意に過剰量酸素の一部分を伴って)POX燃料ガスを燃焼して、燃焼生成物流を形成すること;
PPSタービンを横断して燃焼生成物流を拡張して、出力を生成し、拡張PPS燃焼生成物流を形成すること
を包含する方法に関する。
拡張PPS燃焼生成物流をPPSレキュペレータ熱交換器に通して、それによりPPS燃焼生成物流から熱を引き出して、冷却PPS燃焼生成物流を形成すること;
任意に、冷却PPS燃焼生成物流を冷水器に通すこと;
PPS燃焼生成物流をPPS洗浄器中で処理して、H2SO4、HNO3または水溶解化Hg塩のうちの少なくとも1つを分離して、再循環CO2流を形成すること;そして
再循環CO流をPPS圧縮器中で加圧して、圧縮再循環CO2流を形成すること
を包含し得る。
酸素の存在下で液体または固体燃料を部分的に酸化して、燃料ガスを含むPOX流を形成するよう適応されるPOX反応器;
POX流を急冷流体と接触するよう適応される1つ以上の構成要素;
POX燃料ガスからの急冷POX流中に存在する任意の固体を分離するよう適応される任意のPOX洗浄器;
圧縮再循環CO2流の一部分に対してPOX燃料ガスから熱を引き出し、冷却POX燃料ガスを出すよう適応されるPOX熱交換器;
POX燃料ガスから任意の液体水を分離するよう適応される任意の分離器;
冷却POX燃料ガスを約12MPa以上の圧力に圧縮するよう適応される圧縮器;
酸素および圧縮再循環CO2流の一部分の存在下でPOX燃料ガスを燃焼して、約12MPa以上の圧力でPPS燃焼生成物流を形成するよう適応されるPPS燃焼器;
PPS燃焼生成物を拡張し、連結発生器中で出力を発生するよう適応されるタービン;
拡張PPS燃焼生成物流から熱を引き出し、圧縮再循環CO2流に熱を付加するよう適応されるレキュペレータ熱交換器;
拡張PPS燃焼生成物流からの任意の酸化不純物を分離し、再循環CO2流を出すよう適応されるPPS洗浄塔;
再循環CO2流を約12MPa以上の圧力に圧縮して、圧縮再循環CO2流を形成するよう適応されるPPS圧縮器;
圧縮再循環CO2流の一部分をPOX熱変換器に向けるよう適応される流動構成要素;
圧縮再循環CO2流の一部分をPPSレキュペレータ熱変換器に向けるよう適応される流動構成要素;ならびに
POX熱交換器からの圧縮再循環CO2流をPPSレキュペレータ熱変換器に向けるよう適応される流動構成要素
を含み得る。
CO+H2O=H2+CO2 (2)
灰分除去後に約250℃〜約400℃の温度で得られる燃料ガスの一部分を用いて、そしてイオウ耐容性COシフト触媒、例えばシフト反応器中のコバルトをベースにしたものを用いることにより、これは成し遂げられ得る。H2を濃化された燃料ガスの部分は、次に、POX熱交換器を別個に通過することにより冷却され得る。放熱シフト反応において放出される熱は、PPSに伝達され得る。次に、出口シフト化ガスが残りの冷却POX流の一部分と混合され、併合流は、単一非吸着構成成分として必要とされるH2対CO比でH2およびCOを分離するよう意図された多床型圧力変動吸着器に通され、一方、吸着構成成分は、イオウ化合物、HCN、NH3、Hg、CO2、H2Oおよび大半のCH4のすべてを含有し得る。この非吸着分画は、石炭(あるいは他の固体または液体燃料)に由来する多少のN2およびAr、ならびにPOX反応器中で用いられる酸素も含有し得る。これらの不活性構成成分は、好ましくは、総濃度の5%より低く、これは、フィッシャー・トロプシュおよびメタノール反応器の両方へのガス供給のために許容可能である。純H2生成が必要とされる場合、シフト化冷却ガスのみがPSAに供給される。還元形態での石炭およびPOX由来不純物のすべてを伴うPSAからのほぼ大気圧の廃棄ガスは、圧縮され、PPS燃焼のために残留POX燃料ガスに戻される。
NO+1/2O2=NO (3)
NO2+SO2=SO3+NO (4)
SO3+H2O=H2SO4 (5)
2NO2+H2O=HNO2+HNO3 (6)
3HNO2=HNO3+2NO+H2O (7)
NO+1/2O2=NO2 (8)
H2O+CO=CO2+H2 (9)
実験
Claims (1)
- 部分酸化(POX)系および出力発生系(PPS)を備えるシステムの組合せを用いる出力発生方法であって、以下の:
燃料を部分的に酸化して、燃料ガスを含むPOX流を生成するのに十分な条件下で、POX反応器中で固体または液体燃料および酸素を併合すること;
400℃以下の温度で急冷POX流を生成し、POX流中に存在する任意の溶融固体の少なくとも一部分を固化するのに十分な条件下で急冷流体との組合せによりPOX流を急冷すること;
そこに存在する任意の固体の少なくとも一部分を除去するために、急冷POX流を処理すること;
急冷POX流をPOX熱交換器に送り、冷却流に対して急冷POX流を100℃以下の温度に冷却することにより急冷POX流からある量の熱を引き出して、POX燃料ガス流を生成すること;
POX燃料ガスを分離容器に通して、POX燃料ガス流中に存在する任意の水の少なくとも一部分を分離すること;
POX燃料ガス流を12MPa以上の圧力に圧縮すること;
少なくとも10MPaの圧力で、少なくとも800℃の温度で、PPS燃焼器中でPOX燃料ガスを燃焼して、燃焼生成物流を形成すること;
PPSタービンを横断して燃焼生成物流を拡張して、出力を生成し、拡張PPS燃焼生成物流を形成すること
を包含する方法。
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