JP6046136B2 - 溶存水素を含む原料の沸騰床プロセス - Google Patents
溶存水素を含む原料の沸騰床プロセス Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 108
- 239000001257 hydrogen Substances 0.000 title claims description 85
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 62
- 230000008569 process Effects 0.000 title claims description 61
- 238000009835 boiling Methods 0.000 title claims description 41
- 239000002994 raw material Substances 0.000 title claims description 14
- 239000007788 liquid Substances 0.000 claims description 64
- 150000002430 hydrocarbons Chemical class 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 48
- 229930195733 hydrocarbon Natural products 0.000 claims description 46
- 239000004215 Carbon black (E152) Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000012465 retentate Substances 0.000 claims 2
- 238000004064 recycling Methods 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 238000012958 reprocessing Methods 0.000 description 1
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- -1 stream combination Chemical compound 0.000 description 1
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Description
本願は、2011年7月29日に出願された米国仮特許出願第61/513,055号の利益を主張するものであり、その開示は参照により本明細書によって援用される。
水素化分解または水素化処理操作の共通の目的は、特に残油原料(residue feedstock)中における硫黄、窒素および/または金属などの不純物を除去し、また重質フィード(heavy feed)を低沸点の低分子量炭化水素類にクラッキングし、ガソリンおよびディーゼルなどの輸送燃料を得ることである。水素化分解/水素化処理操作で生じる反応には、水素化脱硫(HDS)、炭素残油還元(carbon residue reduction)(CRR)、窒素除去(HDN)、およびクラッキングが含まれる。
混合ゾーンにおいて新鮮かつリサイクルされた液体炭化水素原料および過剰な水素ガスを混合して、一部の水素ガスを液体炭化水素原料中に溶解させ、水素に富む液体炭化水素原料を生成し;
水素に富む液体炭化水素原料および過剰な水素をフラッシングゾーンへ運び、そこで少なくとも一部の非溶存水素ガスがフラッシュされ;
水素に富む液体炭化水素原料をフラッシングゾーンから沸騰床反応器のフィード注入口へ移動させ、原料から低分子量炭化水素類への変換を含む反応を行わせ;
変換された低重量の炭化水素生成物を、沸騰床反応器の実質的に触媒フリーのゾーンから回収し;並びに
再処理のために、新鮮な原料と混合するために、未変換フィードをリサイクリングする、
ことを含むプロセスに関する。
本発明のプロセスにおいて、水素化処理/水素化分解反応に要求される水素ガスのかなりの部分は、液体原料中に溶解している。水素分配装置(hydrogen distributor apparatus)を利用して、沸騰床反応器の上流にある原料を処理し、必要な反応水素ガスの少なくともかなりの部分を液体原料中に溶解させ、沸騰床反応器流入液として混合フィード/水素ストリーム(combined feed/hydrogen stream)を生成する。
アラビアン重質原油(Arabian heavy crude oil)から得た減圧残油(その特性は表1に示される)を、一段階(single-stage)沸騰床反応器中、440℃、150バールの水素分圧で、反応器容積1リットルに対して0.3リットルの油および減圧残油1トンに対して0.8kgの触媒で、水素化分解した。全水素ガス割合(rate)は、水素がプロセスで消費される割合の4倍に設定する。沸騰床反応器を、リサイクルと原料の比率10:1で運転した。
Claims (14)
- 沸騰床触媒水素化処理反応器中で液体炭化水素原料を低分子量炭化水素化合物に変換するプロセスであって、
沸騰床反応器は、沸騰床から液体リサイクル流出物を移動させるために、触媒床上方の実質的に触媒フリーのゾーンと流体連結している内部的リサイクル下降流導管を含み、
プロセスは、
a.混合ゾーンにおいて液体炭化水素原料を過剰な水素ガスと混合して、一部の水素ガスを液体炭化水素原料中に溶解させ、水素に富む液体炭化水素原料を生成し;
b.水素に富む液体炭化水素原料および非溶存水素をフラッシングゾーンへ運び、そこで少なくとも一部の非溶存水素ガスがフラッシュされ;
c.水素に富む液体炭化水素原料をフラッシングゾーンから沸騰床ポンプ入口へ移動させ;
d.沸騰床ポンプからの水素に富む液体炭化水素原料を沸騰床反応器のフィード注入口へ移動させ、原料から低分子量炭化水素類への変換を含む反応を行わせ;
e.変換された低分子量の炭化水素生成物を、沸騰床反応器の実質的に触媒フリーのゾーンから回収し;
f.液体炭化水素原料と混合するために、沸騰床反応器の内部的リサイクル導管からの液体リサイクル流出物を工程(a)の水素ガス混合ゾーンへ移動させる;
ことを含む、プロセス。 - 沸騰床触媒水素化処理反応器中で液体炭化水素原料を低分子量炭化水素化合物に変換するプロセスであって、
沸騰床反応器は、回収生成物よりも重質の炭化水素類を受けるために、触媒床上方の実質的に触媒フリーのゾーンと流体連結している内部的リサイクル下降流導管を含み、
プロセスは、
a.混合ゾーンにおいて液体炭化水素原料を過剰な水素ガスと混合して、一部の水素ガスを液体炭化水素原料中に溶解させ、水素に富む液体炭化水素原料を生成し;
b.水素に富む液体炭化水素原料および非溶存水素をフラッシングゾーンへ運び、そこで少なくとも一部の非溶存水素ガスがフラッシュされ;
c.水素に富む液体炭化水素原料をフラッシングゾーンから沸騰床反応器のフィード注入口へ移動させ、原料から低分子量炭化水素類への変換を含む反応を行わせ;
d.変換された低分子量の炭化水素生成物を、沸騰床反応器の実質的に触媒フリーのゾーンから回収し;
e.沸騰床反応器底部の内部的リサイクル下降流導管からの炭化水素を、内部的リサイクル下降流導管と流体連結している外部分離またはフラッシュ容器と、分離またはフラッシュ容器残液を沸騰床反応器入口に運ぶためのリサイクル沸騰ポンプと流体連結している出口とを含む外部的リサイクル分離ゾーンへ運び、ここで、軽質ガスおよび水素を含むトップ流の一部は、外部的リサイクル分離ゾーンから回収され、外部分離またはフラッシュ容器にリサイクルされる;
f.水素および軽質ガスが取り出される外部分離またはフラッシュ容器残液を、リサイクル沸騰ポンプへ運び;
g.リサイクル沸騰ポンプからの分離またはフラッシュ容器残液を、沸騰床反応器入口に運ぶ;
ことを含む、プロセス。 - 沸騰床反応器のガスホールドアップは総液体量の40V%未満である、請求項1または2に記載のプロセス。
- 沸騰床反応器のガスホールドアップは総液体量の1V%未満である、請求項1または2に記載のプロセス。
- 沸騰床リサイクルストリームは総液体量の10V%未満の蒸気量を含む、請求項1または2に記載のプロセス。
- 沸騰床リサイクルストリームは総液体量の0.1V%未満の蒸気量を含む、請求項1または2に記載のプロセス。
- 沸騰床反応器を350℃から500℃の範囲における温度で運転する、請求項1または2に記載のプロセス。
- 沸騰床反応器を400℃から450℃の範囲における温度で運転する、請求項1または2に記載のプロセス。
- 沸騰床反応器を50から300Kg/cm2の範囲における圧力で運転する、請求項1または2に記載のプロセス。
- 沸騰床反応器を100から250Kg/cm2の範囲における圧力で運転する、請求項1または2に記載のプロセス。
- 沸騰床反応器を150から200Kg/cm2の範囲における圧力で運転する、請求項1または2に記載のプロセス。
- 水素および原料の混合並びに飽和ゾーンを、原料の500から10,000標準立方フィート/バレル(SCFB)(89から1780m3/m3)の範囲における水素供給量で運転する、請求項1または2に記載のプロセス。
- 水素および原料の混合並びに飽和ゾーンを、原料の1500から5,000SCFB(267から890m3/m3)の範囲における水素供給量で運転する、請求項1または2に記載のプロセス。
- 外部的リサイクル分離ゾーン上流の沸騰床反応器底部からの炭化水素に水素を混合する、請求項2に記載のプロセス。
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