JP2012162618A - 炭化水素油の製造方法 - Google Patents
炭化水素油の製造方法 Download PDFInfo
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 45
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/36—Controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
【解決手段】被処理ワックスを下記式(1)で定義される分解率が下記式(2)を満たすX1(%)となる条件で水素化分解を行う期間と、前記分解率が下記式(3)を満たすX2(%)となる条件で水素化分解を行う期間と、を交互に設ける。分解率(%)=[(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量)−(水素化分解生成物1g中の沸点が360℃を超える炭化水素の含有量)]×100/(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量)…(1)30≦X1≦90…(2)0.1≦X2/X1≦0.9…(3)
【選択図】図2
Description
分解率(%)=[(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量)−(水素化分解生成物1g中の沸点が360℃を超える炭化水素の含有量)]×100/(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量) …(1)
30≦X1≦90 …(2)
0.1≦X2/X1≦0.9 …(3)
分解率(%)=[(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量)−(水素化分解生成物1g中の沸点が360℃を超える炭化水素の含有量)]×100/(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量) …(1)
30≦X1≦90 …(2)
0.1≦X2/X1≦0.9 …(3)
なお、ここで「LHSV(liquid hourly space velocity;液空間速度)」とは、固定床流通式反応器に充填された触媒からなる層(触媒層)の容量当たりの、標準状態(25℃、101325Pa)におけるワックス留分の体積流量のことであり、単位「h−1」は時間の逆数である。また、水素ガス/油比における水素容量の単位である「NL」は、標準状態(0℃、101325Pa)における水素容量(L)を示す。
<水素化分解触媒の調製>
粉末状の平均粒子径0.4μmのUSYゼオライト(シリカ/アルミナのモル比:37)を3.0質量%、粉末状のアルミナボリア(アルミナ/ボリアの質量比:5.6)を57.0質量%、および粉末状のアルミナを40.0質量%含有する組成物を、常法により直径約1.5mm、長さ約3mmの円柱状に押出成型し、得られた成型体を空気中500℃で1時間焼成して担体を得た。この担体に、白金原子として担体の質量を基準として0.8質量%となる量のジクロロテトラアンミン白金(II)の水溶液を含浸した後、これを120℃で3時間乾燥し、その後500℃にて1時間、空気中で焼成することにより、水素化分解触媒を得た。
FT合成反応により製造された合成油(FT合成油)を360℃をカット・ポイントとして精留塔において分留し、得られたボトム油をFTワックス留分として使用した。このFTワックス留分の組成を分析したところ、炭素数が20〜80である直鎖状炭化水素を主成分とし、沸点が360℃を超える直鎖状炭化水素の含有量が、FTワックス留分全体の質量を基準として95質量%であった。
先ず、上記水素化分解触媒を固定床流通式反応器に充填し、水素気流下、345℃で4時間の還元処理を行って触媒を活性化した。次に、上記FTワックス留分、水素ガスおよび後述する水素化分解生成物から分留により回収、リサイクルした未分解ワックスを連続的に前記反応器に供給し、高分解率での水素化分解の期間と、低分解率での水素化分解の期間とを交互に設けるブロック・オペレーションにより、水素化分解を行った。
実施例1と同一の反応器、水素化分解触媒およびFTワックス留分を用いて、全運転期間を通じて一定の分解率および一定のFTワックス留分供給量とする水素化分解を行った。運転条件を表1に示す。
実施例1と同一の反応器、水素化分解触媒およびFTワックス留分を用いて、実施例1と同様の手順、表2に記載の運転条件により、高分解率(78%)/低分解率(20%)のブロック・オペレーションによる水素化分解を行った。最初の高分解率での水素化分解の運転において、運転開始時に分解率を78%とするための補正反応温度は314℃であった。また、最初の低分解率での水素化分解の運転の運転開始時に分解率を20%とするための補正反応温度は309℃であった。中間留分の収率は全期間を通じて75%であった。
実施例2に対して、前述の実施例1と比較例1との関係と同様の関係、すなわち、FTワックス留分供給量を、実施例2におけるFTワックス留分の時間加重平均供給量と等しくなるように一定に設定し、また、表2に示す条件により、全運転期間を通じて、中間留分の収率が実施例2の中間留分収率(75%)と同一となるように調整することにより、一定の分解率(70%)とする水素化分解を行った。運転開始時に分解率を70%とするための補正反応温度は313℃であった。
Claims (2)
- 水素化分解触媒を収容する水素化分解反応器に、沸点が360℃を超える直鎖状炭化水素を70質量%以上含有する原料ワックスと、前記反応器から流出する水素化分解生成物から分離され、沸点が360℃を超える直鎖状炭化水素を70質量%以上含有する未分解ワックスと、を含む被処理ワックスを、連続的に供給して水素化分解することにより、沸点が360℃以下の炭化水素が含まれる炭化水素油を得る方法であって、
前記被処理ワックスを下記式(1)で定義される分解率が下記式(2)を満たすX1(%)となる条件で水素化分解を行う期間と、前記分解率が下記式(3)を満たすX2(%)となる条件で水素化分解を行う期間と、を交互に設けることを特徴とする炭化水素油の製造方法。
分解率(%)=[(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量)−(水素化分解生成物1g中の沸点が360℃を超える炭化水素の含有量)]×100/(被処理ワックス1g中の沸点が360℃を超える炭化水素の含有量) …(1)
30≦X1≦90 …(2)
0.1≦X2/X1≦0.9 …(3) - 前記原料ワックスがフィッシャー・トロプシュ合成反応により得られるワックスを含むことを特徴とする請求項1記載の炭化水素油の製造方法。
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CA2826363A CA2826363C (en) | 2011-02-04 | 2012-01-31 | Method for producing hydrocarbon oil |
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