JP2000017276A - Equipment and process for desulfurization and reforming of hydrocarbon feedstock - Google Patents
Equipment and process for desulfurization and reforming of hydrocarbon feedstockInfo
- Publication number
- JP2000017276A JP2000017276A JP10182267A JP18226798A JP2000017276A JP 2000017276 A JP2000017276 A JP 2000017276A JP 10182267 A JP10182267 A JP 10182267A JP 18226798 A JP18226798 A JP 18226798A JP 2000017276 A JP2000017276 A JP 2000017276A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- steam reforming
- desulfurization
- section
- unit
- 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.)
- Withdrawn
Links
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 101
- 230000023556 desulfurization Effects 0.000 title claims abstract description 101
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 100
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 100
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 79
- 238000002407 reforming Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 206
- 239000001257 hydrogen Substances 0.000 claims abstract description 206
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000000629 steam reforming Methods 0.000 claims abstract description 107
- 239000012528 membrane Substances 0.000 claims abstract description 72
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 39
- 238000005192 partition Methods 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- 239000012466 permeate Substances 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 71
- 238000000926 separation method Methods 0.000 claims description 68
- 239000007789 gas Substances 0.000 claims description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 40
- 238000011084 recovery Methods 0.000 claims description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000003915 liquefied petroleum gas Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002737 fuel gas Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- WZRJTRPJURQBRM-UHFFFAOYSA-N 4-amino-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide;5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidine-2,4-diamine Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1.COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 WZRJTRPJURQBRM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 naphtha Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、原料炭化水素の脱
硫改質装置およびその方法、詳しくはＬＰＧ，ナフサ，
天然ガスなどの原料炭化水素を脱硫改質して、都市ガス
や高純度水素などを製造するにあたって、装置のコンパ
クト化および熱エネルギーの効率利用化が図れる原料炭
化水素の脱硫改質装置およびその方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for desulfurizing and reforming a raw hydrocarbon, and more particularly, to an LPG, naphtha,
A desulfurization reforming apparatus and method for raw material hydrocarbons that can achieve compactness of equipment and efficient use of heat energy when desulfurizing and reforming raw material hydrocarbons such as natural gas to produce city gas, high-purity hydrogen, etc. About.
【０００２】[0002]
【従来の技術】従来、都市ガス，天然ガス，ナフサ，灯
油，ＬＰＧなどの炭化水素に水蒸気を添加して白金，ル
テニウムまたはニッケルなどの元素をアルミナなどの担
体に担持した改質触媒と高温下で接触させて水蒸気改質
し、水素含有ガスを得る技術が実施されている。2. Description of the Related Art Conventionally, a reforming catalyst in which water vapor is added to hydrocarbons such as city gas, natural gas, naphtha, kerosene, and LPG to carry an element such as platinum, ruthenium or nickel on a carrier such as alumina is used at a high temperature. A technique of obtaining a hydrogen-containing gas by performing steam reforming by contacting with a gas.
【０００３】なお、改質触媒は硫黄分によって極めて被
毒されやすく、ニッケル担持触媒にあっては、特に硫黄
分の影響を受けやすく、被毒されて活性を失う恐れがあ
るため、通常は原料炭化水素中の硫黄分を脱硫処理して
おり、その脱硫方法としては、炭化水素に純水素または
水素含有ガスを添加し、高温・高圧下でコバルト−モリ
ブデン、またはニッケル−モリブデンなどを担持した触
媒と接触させて水素化処理して硫黄分を硫化水素とした
のち、酸化亜鉛や酸化ニッケルなどの脱硫剤で脱硫する
水素化脱硫方法が一般的に用いられている。[0003] The reforming catalyst is extremely susceptible to poisoning by sulfur, and the nickel-carrying catalyst is particularly susceptible to the effect of sulfur and may lose its activity due to poisoning. The sulfur content in hydrocarbons is desulfurized, and as a desulfurization method, a catalyst in which pure hydrogen or a hydrogen-containing gas is added to hydrocarbons and cobalt-molybdenum or nickel-molybdenum is supported under high temperature and high pressure A hydrodesulfurization method is generally used in which a sulfur component is converted into hydrogen sulfide by contacting with hydrogen to form hydrogen sulfide, and then desulfurized with a desulfurizing agent such as zinc oxide or nickel oxide.
【０００４】また、炭化水素を水蒸気改質して得られた
水素含有ガスから水素を精製回収している。この回収さ
れた水素は、燃料電池用の水素源や半導体製造工業など
で使用されており、その精製回収方法としては、溶液吸
収法、吸着法または深冷分離法などで不純物を分離除去
する方法や、有機または無機の水素分離膜によって水素
を溶解拡散分離する膜分離方法などがある。その中で
も、膜分離方法は、省エネルギー、分離効率、装置の簡
易な構成および運転の容易性などの観点から注目されて
いる。[0004] Further, hydrogen is purified and recovered from a hydrogen-containing gas obtained by steam reforming a hydrocarbon. This recovered hydrogen is used in the hydrogen source for fuel cells and in the semiconductor manufacturing industry, etc. As a method for purifying and recovering it, a method of separating and removing impurities by a solution absorption method, an adsorption method, a cryogenic separation method, or the like. And a membrane separation method in which hydrogen is dissolved and separated by an organic or inorganic hydrogen separation membrane. Above all, the membrane separation method has attracted attention from the viewpoint of energy saving, separation efficiency, simple configuration of the apparatus and easiness of operation.
【０００５】さらに、膜分離方法に用いられる水素分離
膜としては、ポリミイドやポリスルホンなどの有機高分
子膜および特開昭６２−１２１６１６号、特開昭６２−
２７３０３０号公報などに開示されている多孔質硝子、
多孔質セラミックスや多孔質酸化アルミニウムなどの無
機多孔質支持体の表面にパラジウムまたはパラジウム合
金膜を被着した無機膜などがある。Further, as the hydrogen separation membrane used in the membrane separation method, organic polymer membranes such as polyimide and polysulfone, and Japanese Patent Application Laid-Open Nos.
Porous glass disclosed in, for example, US Pat.
There is an inorganic film in which a palladium or palladium alloy film is applied to the surface of an inorganic porous support such as porous ceramics or porous aluminum oxide.
【０００６】また、本願出願人は、特開平９−２７８４
０３号で、炭化水素を水蒸気改質し、得られる水素含有
ガスから無機水素分離膜を用いて高純度水素を製造する
にあたり、水素含有ガスを前記ガス変成部を通すこと
で、一酸化炭素を二酸化炭素に転換して、パラジウム系
の無機水素分離膜の被毒化を防止したのち、硫黄分含有
の炭化水素の水素化脱硫用の水素として用いる高純度水
素の製造方法を提案した。[0006] The applicant of the present invention has disclosed in Japanese Patent Application Laid-Open No. 9-2784.
No. 03, steam reforming of hydrocarbons, to produce high-purity hydrogen from the resulting hydrogen-containing gas using an inorganic hydrogen separation membrane, by passing the hydrogen-containing gas through the gas shift section, carbon monoxide A method for producing high-purity hydrogen, which is used as hydrogen for hydrodesulfurization of hydrocarbons containing sulfur after conversion to carbon dioxide to prevent poisoning of the palladium-based inorganic hydrogen separation membrane, was proposed.
【０００７】[0007]
【発明が解決しようとする課題】上記従来の炭化水素を
水蒸気改質して得られた水素含有ガスから水素を精製し
高純度水素を製造する方法にあって、本願出願人が提案
した高純度水素の製造方で使用されている技術は、製造
された高純度水素の一部を水素化脱硫に用いることによ
り、炭化水素の水素化脱硫の効率化を図り、かつ廉価に
高純度水素を得る方法である。SUMMARY OF THE INVENTION The above-mentioned conventional method for producing high-purity hydrogen by purifying hydrogen from a hydrogen-containing gas obtained by steam reforming a hydrocarbon is disclosed. The technology used in the method of producing hydrogen uses a part of the produced high-purity hydrogen for hydrodesulfurization, thereby increasing the efficiency of hydrocarbon hydrodesulfurization and obtaining high-purity hydrogen at low cost. Is the way.
【０００８】しかしながら、この高純度水素の製造方法
においては、水素化脱硫部と、ガス変成部と、無機水素
分離膜を用いた高純度水素回収部とが、それぞれ離間し
た位置に独立して配備されているので、高純度水素の製
造設備が大型化し、かつ熱エネルギーの効率が悪いとい
う問題点があった。しかも、無機水素分離膜の非透過側
の水素含有ガスを、例えば濃縮水素回収部および濃縮水
素循環部などを通して、水素化脱硫部側へ循環させるよ
うに構成していたので、水添脱硫用の水素の使用が直接
的でなく、前述した高純度水素の製造設備が、さらに大
型化する恐れがある。However, in this method for producing high-purity hydrogen, the hydrodesulfurization section, the gas shift section, and the high-purity hydrogen recovery section using an inorganic hydrogen separation membrane are independently provided at separate positions. Therefore, there has been a problem that a high-purity hydrogen production facility becomes large and thermal energy efficiency is low. In addition, since the hydrogen-containing gas on the non-permeate side of the inorganic hydrogen separation membrane is circulated to the hydrodesulfurization section through, for example, a concentrated hydrogen recovery section and a concentrated hydrogen circulation section, the hydrogen desulfurization section is used. The use of hydrogen is not straightforward, and the above-described high-purity hydrogen production equipment may be further enlarged.
【０００９】本発明は、このような従来技術を背景にな
されたもので、装置のコンパクト化および熱エネルギー
の効率利用化が図れる原料炭化水素の脱硫改質装置およ
びその方法を提供するものである。The present invention has been made on the background of the prior art, and has as its object to provide a desulfurization reforming apparatus for raw material hydrocarbons and a method therefor, which can make the apparatus compact and efficiently use heat energy. .
【００１０】[0010]
【課題を解決するための手段】請求項１に記載の発明
は、原料炭化水素中の硫黄分を脱硫して除去する脱硫部
と、脱硫された炭化水素を水蒸気改質する水蒸気改質
部、とを備え、前記脱硫部と前記水蒸気改質部とは隔壁
を介して一体化され、かつ該隔壁の少なくとも一部を、
水素を透過する無機水素分離膜により構成することで、
前記水蒸気改質部で発生した水素を無機水素分離膜に透
過して脱硫部に供給し、この水素を前記硫黄分の水添脱
硫用水素として用いることを特徴とする原料炭化水素の
脱硫改質装置である。According to the first aspect of the present invention, there is provided a desulfurizing section for desulfurizing and removing sulfur from a raw material hydrocarbon, a steam reforming section for steam reforming the desulfurized hydrocarbon, Comprising, the desulfurization unit and the steam reforming unit are integrated via a partition, and at least a part of the partition,
By being composed of an inorganic hydrogen separation membrane that transmits hydrogen,
Hydrogen generated in the steam reforming section is transmitted through an inorganic hydrogen separation membrane and supplied to a desulfurization section, and the hydrogen is used as hydrogen for hydrodesulfurization of the sulfur component. Device.
【００１１】また、請求項２に記載の発明は、（イ）脱
硫された炭化水素に水または水蒸気を添加して、水蒸気
改質部に供給し、該水蒸気改質部内で改質触媒と接触さ
せてメタン改質することで、メタンリッチガスを製造す
る水蒸気改質工程と、（ロ）少なくとも一部が無機水素
分離膜である隔壁を中間に介在させて、隣接する前記水
蒸気改質工程の水蒸気改質部と一体化された脱硫部内に
原料炭化水素を供給し、これにより該原料炭化水素を、
前記脱硫部に充填された水添触媒および脱硫剤に順次接
触させ、かつ前記水蒸気改質部内から前記無機水素分離
膜を透過して前記脱硫部内に達した水素を、水添脱硫用
水素として用いることで、原料炭化水素中の硫黄分を硫
化水素に改質したのち、前記脱硫剤により脱硫する脱硫
工程と、（ハ）脱硫・改質されたメタンリッチガスを脱
炭酸処理する脱炭酸工程と、（ニ）脱炭酸処理されたメ
タンリッチガス中にＬＰＧを添加することにより、高カ
ロリーな都市ガスを製造する工程、とを備えたことを特
徴とする原料炭化水素の脱硫改質方法である。[0011] The invention according to claim 2 is characterized in that (a) water or steam is added to the desulfurized hydrocarbon and is supplied to a steam reforming section, where it contacts a reforming catalyst in the steam reforming section. And methane reforming to produce a methane-rich gas, and (b) steam in the adjacent steam reforming step with a partition wall at least partly an inorganic hydrogen separation membrane interposed therebetween. The raw material hydrocarbon is supplied into the desulfurization unit integrated with the reforming unit, whereby the raw material hydrocarbon is
The hydrogen that has been sequentially contacted with the hydrogenation catalyst and the desulfurizing agent filled in the desulfurization unit and that has passed through the inorganic hydrogen separation membrane from the steam reforming unit and reached the desulfurization unit is used as hydrogen for hydrodesulfurization. Thus, after reforming the sulfur content in the raw material hydrocarbon to hydrogen sulfide, a desulfurization step of desulfurizing with the desulfurizing agent, and (c) a decarboxylation step of decarboxylation of the desulfurized and reformed methane-rich gas, (D) a step of producing a high-calorie city gas by adding LPG to the decarbonated methane-rich gas.
【００１２】さらに、請求項３に記載の発明は、原料炭
化水素中の硫黄分を脱硫して除去する脱硫部と、脱硫さ
れた炭化水素を水蒸気改質する水蒸気改質部と、該水蒸
気改質部で発生した高濃度水素含有ガスから高純度水素
を分離回収する高純度水素回収部、とを備え、前記脱硫
部、前記水蒸気改質部および前記高純度水素回収部は、
それぞれ隔壁を介して一体化され、かつ該各隔壁の少な
くとも一部は、水素を透過する無機水素分離膜により構
成され、また前記水蒸気改質部で発生した水素を前記無
機水素分離膜に透過して前記脱硫部に供給し、これを前
記原料炭化水素中の硫黄分の水添脱硫用水素として用い
る一方、前記高純度水素回収部では、前記水蒸気改質部
の水素を前記無機水素分離膜に透過して高純度水素を分
離回収することを特徴とする原料炭化水素の脱硫改質装
置である。Further, the invention according to claim 3 is characterized in that a desulfurization section for desulfurizing and removing sulfur from the raw material hydrocarbon, a steam reforming section for steam reforming the desulfurized hydrocarbon, and the steam reforming section. A high-purity hydrogen recovery unit that separates and recovers high-purity hydrogen from the high-concentration hydrogen-containing gas generated in the purification unit, and the desulfurization unit, the steam reforming unit, and the high-purity hydrogen recovery unit include:
Each of the partitions is integrated via a partition, and at least a part of each partition is constituted by an inorganic hydrogen separation membrane that transmits hydrogen, and hydrogen generated in the steam reforming unit is transmitted through the inorganic hydrogen separation membrane. While supplying it to the desulfurization section, and using this as hydrogen for hydrodesulfurization of sulfur in the raw material hydrocarbon, while the high-purity hydrogen recovery section transfers the hydrogen of the steam reforming section to the inorganic hydrogen separation membrane. This is a desulfurization reforming apparatus for raw material hydrocarbons, which separates and recovers high-purity hydrogen through permeation.
【００１３】さらにまた、請求項４に記載の発明は、
（イ）脱硫された炭化水素に水または水蒸気を添加し
て、水蒸気改質部に供給し、該水蒸気改質部内で改質触
媒と接触させて水素改質することで、高濃度水素含有ガ
スを製造する水蒸気改質工程と、（ロ）少なくとも一部
が無機水素分離膜である隔壁を中間に介在させて、隣接
する前記水蒸気改質工程の水蒸気改質部と一体化された
脱硫部内に原料炭化水素を供給し、これにより該原料炭
化水素を、前記脱硫部に充填された水添触媒および脱硫
剤に順次接触させ、しかも前記水蒸気改質部から前記無
機水素分離膜を透過して前記脱硫部内に達した水素を水
添脱硫用水素として用いることで、原料炭化水素中の硫
黄分を硫化水素に改質したのち、前記脱硫剤により脱硫
する脱硫工程と、（ハ）前記高濃度水素含有ガス中に含
まれる水素を、前記高純度水素回収部側の無機水素分離
膜に透過することで高純度水素として回収する高純度水
素回収工程、とを備えたことを特徴とする原料炭化水素
の脱硫改質方法である。[0013] Further, the invention according to claim 4 provides:
(A) High-concentration hydrogen-containing gas is obtained by adding water or steam to the desulfurized hydrocarbon and supplying it to the steam reforming section, and contacting the reforming catalyst in the steam reforming section to perform hydrogen reforming. And (b) in a desulfurization unit integrated with the steam reforming unit of the adjacent steam reforming unit by interposing a partition wall at least a part of which is an inorganic hydrogen separation membrane in the middle. The raw material hydrocarbon is supplied, whereby the raw material hydrocarbon is brought into contact with the hydrogenation catalyst and the desulfurizing agent filled in the desulfurization section sequentially, and furthermore, passes through the inorganic hydrogen separation membrane from the steam reforming section and passes through the inorganic hydrogen separation membrane. A desulfurization step of reforming the sulfur content of the raw material hydrocarbon into hydrogen sulfide by using the hydrogen that has reached the interior of the desulfurization unit as hydrogen for hydrodesulfurization, and then desulfurizing with the desulfurizing agent; Hydrogen contained in the contained gas, High purity hydrogen recovery step of recovering the high purity hydrogen by transmitting the inorganic hydrogen separation membrane pure hydrogen recovery side, a desulfurization method for reforming hydrocarbon feedstock, characterized in that with a capital.
【００１４】そして、請求項５に記載の発明は、原料炭
化水素中の硫黄分を脱硫して除去する脱硫部と、脱硫さ
れた炭化水素を水蒸気改質する水蒸気改質部と、該水蒸
気改質部で発生した高濃度水素含有ガスから高純度水素
を分離回収する高純度水素回収部、とを備え、前記脱硫
部、前記水蒸気改質部および前記高純度水素回収部を一
体化し、前記脱硫部および前記高純度水素回収部と、前
記水蒸気改質部とは、少なくとも一部が無機水素分離膜
で形成された第１の隔壁により区画され、しかも該第１
の隔壁により区画された空間は、第２の隔壁を介して、
前記脱硫部側と、前記高純度水素回収部側とに仕切られ
ていることを特徴とする原料炭化水素の脱硫改質装置で
ある。Further, the invention according to claim 5 comprises a desulfurization section for desulfurizing and removing sulfur in the raw material hydrocarbon, a steam reforming section for steam reforming the desulfurized hydrocarbon, and the steam reforming section. A high-purity hydrogen recovery unit that separates and recovers high-purity hydrogen from the high-concentration hydrogen-containing gas generated in the purification unit, and integrates the desulfurization unit, the steam reforming unit, and the high-purity hydrogen recovery unit, And the high-purity hydrogen recovery section and the steam reforming section are defined by a first partition wall at least partially formed of an inorganic hydrogen separation membrane.
The space partitioned by the partition of the second through the second partition,
A desulfurization reforming apparatus for raw material hydrocarbons, which is partitioned into the desulfurization section and the high-purity hydrogen recovery section.
【００１５】[0015]
【発明の実施の形態】発明の実施の形態を図面に基づい
て説明する。図１は本発明の一実施の形態に係る原料炭
化水素の脱硫改質装置の系統図であり、図２は他の実施
の形態に係る原料炭化水素の脱硫改質装置の系統図であ
り、図３はさらに別の実施の形態に係る原料炭化水素の
脱硫改質装置の系統図である。Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a system diagram of a raw material hydrocarbon desulfurization reforming apparatus according to one embodiment of the present invention, and FIG. 2 is a system diagram of a raw material hydrocarbon desulfurization reforming apparatus according to another embodiment. FIG. 3 is a system diagram of an apparatus for desulfurizing and reforming a raw hydrocarbon according to still another embodiment.
【００１６】図１において、１０は原料炭化水素の脱硫
改質装置である。以下、この原料炭化水素の脱硫改質装
置１０の構成を説明する。原料炭化水素としては、ナフ
サ、灯油、ＬＰＧなどが採用される。１１は円筒状の脱
硫改質塔であり、この脱硫改質塔１１内には、脱硫され
た炭化水素を水蒸気改質する塔外周部側の水蒸気改質部
１２と、この水蒸気改質部１２の中央部内に、管状の隔
壁を介して収納されて、原料炭化水素中の硫黄分を脱硫
する塔内周部側の脱硫部１３とが配設されている。この
際、隔壁は、少なくともその一部が水素を透過する無機
水素分離膜１６により構成されている。なお、円筒状の
脱硫改質塔１１に代えて箱型の設備ケースとし、この設
備ケース内を、無機水素分離膜１６を有する平坦な隔壁
によって、水蒸気改質部１２と脱硫部１３とに仕切った
ものでもよい。ただし、パラジウム系などの高価な無機
水素分離膜１６は、この例のように円筒状の塔の方が膜
面積を大きくとることができるため好ましい。In FIG. 1, reference numeral 10 denotes an apparatus for desulfurizing and reforming a raw hydrocarbon. Hereinafter, the configuration of the desulfurization reforming apparatus 10 for raw material hydrocarbons will be described. As the raw material hydrocarbon, naphtha, kerosene, LPG and the like are employed. Reference numeral 11 denotes a cylindrical desulfurization reforming tower. Inside the desulfurization reforming tower 11, a steam reforming section 12 on the outer peripheral side of the tower for steam reforming the desulfurized hydrocarbon, and a steam reforming section 12 And a desulfurization unit 13 that is housed through a tubular partition wall and that is located on the inner peripheral side of the tower and that desulfurizes sulfur in the raw material hydrocarbons. At this time, the partition is constituted by an inorganic hydrogen separation membrane 16 at least part of which is permeable to hydrogen. Note that a box-shaped equipment case is used instead of the cylindrical desulfurization reforming tower 11, and the inside of the equipment case is partitioned into a steam reforming section 12 and a desulfurization section 13 by a flat partition having an inorganic hydrogen separation membrane 16. May be used. However, an expensive inorganic hydrogen separation membrane 16 such as a palladium-based one is preferable in a cylindrical column as in this example because the membrane area can be increased.
【００１７】脱硫改質塔１１の下部には、水蒸気改質部
１２の一部を構成する水蒸気の導入室１２ａが形成さ
れ、また脱硫改質塔１１の上部には、無機水素分離膜１
６の非透過ガスであるメタンリッチガスを、高分子膜や
ＰＳＡなどによって脱炭酸する脱炭酸工程１９（後述）
に排出する排出口１８が形成されている。前記導入室１
２ａの周側板には、スーパヒータ（図外）により加熱さ
れた水蒸気を導入する水蒸気供給口１７が設けられてい
る。水蒸気改質部１２での改質温度は、３００〜４００
℃である。３００℃未満では、転化率が低いという不都
合が生じる。一方、４００℃を超えると、メタン選択率
が下がるという不都合が生じる。A steam introduction chamber 12a constituting a part of the steam reforming section 12 is formed below the desulfurization reforming tower 11, and an inorganic hydrogen separation membrane 1 is formed above the desulfurization reforming tower 11.
Decarboxylation step 19 (described later) for decarbonation of methane-rich gas, which is a non-permeate gas, by a polymer membrane, PSA, etc.
A discharge port 18 for discharging the liquid to the outside is formed. The introduction room 1
A steam supply port 17 for introducing steam heated by a super heater (not shown) is provided in the peripheral side plate 2a. The reforming temperature in the steam reforming section 12 is 300 to 400
° C. If the temperature is lower than 300 ° C., a disadvantage that the conversion is low occurs. On the other hand, when the temperature exceeds 400 ° C., there is a disadvantage that the methane selectivity decreases.
【００１８】水蒸気改質部１２は、脱硫された炭化水素
に水または水蒸気を添加し、さらに改質触媒を接触させ
て水蒸気改質することで、メタンリッチガスを製造す
る。この水蒸気改質部１２には、塔に内設された反応管
内に白金，ルテニウムまたはニッケルなどの元素をアル
ミナ，シリカなどの担体に担持した改質触媒が充填され
ている。なお、改質触媒の工業的使用にはニッケルを担
持したニッケル触媒が廉価であるために多く使用されて
いる。The steam reforming section 12 produces methane-rich gas by adding water or steam to the desulfurized hydrocarbon, and further contacting a reforming catalyst to perform steam reforming. The steam reforming section 12 is filled with a reforming catalyst in which an element such as platinum, ruthenium or nickel is supported on a carrier such as alumina or silica in a reaction tube provided in the tower. In addition, nickel catalysts supporting nickel are widely used in industrial use of reforming catalysts because of their low cost.
【００１９】この水蒸気改質部１２内では、前述したよ
うに脱硫された炭化水素の水蒸気改質が行われる。ここ
での反応を次に示す。 ＣＯ＋３Ｈ2 ←→ＣＨ4 ＋Ｈ2 Ｏ・・・・・（２） ＣＯ＋Ｈ2 Ｏ←→ＣＯ2 ＋Ｈ2 ・・・・・（３）In the steam reforming section 12, steam reforming of the desulfurized hydrocarbon is performed as described above. The reaction here is shown below. CO + 3H 2 ← → CH 4 + H 2 O ····· (2) CO + H 2 O ← → CO 2 + H 2 ····· (3)
【００２０】前記脱硫部１３は、水素化触媒が内部充填
された上流側の水素化触媒層１４と、脱硫剤が充填され
た下流側の脱硫剤層１５とから構成されている。水素化
触媒層１４は、硫黄分を含んだ原料炭化水素を水素化触
媒に接触させることで、この硫黄分を水素化処理して硫
化水素に改質する。水素化触媒としては、ニッケル−モ
リブデンまたはコバルト−モリブデンなどの酸化物、ま
たは硫化物をシリカやアルミナなどの担体に担持したＮ
ｉＭｏｘ触媒またはＣｏＭｏｘ触媒などが挙げられる。
なお、ここでは、ＮｉＭｏｘ触媒が採用されている。低
圧下では、ニッケル−モリブデン触媒が好ましい。ま
た、脱硫剤としては、酸化亜鉛や酸化ニッケルなどが単
独または適宜担体に担持して用いられる。なお、ここで
は、酸化亜鉛が採用されている。The desulfurization section 13 is composed of an upstream hydrogenation catalyst layer 14 in which a hydrogenation catalyst is filled, and a downstream desulfurization agent layer 15 in which a desulfurization agent is filled. The hydrogenation catalyst layer 14 reforms the sulfur content by hydrogenating the sulfur content by bringing the raw hydrocarbon containing sulfur into contact with the hydrogenation catalyst. As the hydrogenation catalyst, an oxide such as nickel-molybdenum or cobalt-molybdenum or a sulfide supported on a carrier such as silica or alumina may be used.
An iMox catalyst or a CoMox catalyst is exemplified.
Here, a NiMox catalyst is employed. Under low pressure, nickel-molybdenum catalysts are preferred. In addition, as the desulfurizing agent, zinc oxide, nickel oxide, or the like is used alone or supported on a suitable carrier. Here, zinc oxide is employed.
【００２１】水素化触媒層１４では、原料炭化水素中の
硫黄分が水素化されて硫化水素が生成する。その反応温
度は３００〜４００℃であるが、無機水素分離膜１６を
透過した水素は反応性に富んでいるため、脱硫反応が促
進される。In the hydrogenation catalyst layer 14, the sulfur content in the raw hydrocarbon is hydrogenated to produce hydrogen sulfide. The reaction temperature is 300 to 400 ° C., but hydrogen permeating through the inorganic hydrogen separation membrane 16 is rich in reactivity, so that the desulfurization reaction is promoted.
【００２２】脱硫剤層１５では、Ｈ2 Ｓ＋ＺｎＯ＝Ｚｎ
Ｓ＋Ｈ2 Ｏの反応が起きる。その反応温度は２５０〜３
５０℃である。なお、このようにして脱硫された炭化水
素は、水蒸気改質部１２に供給される。無機水素分離膜
１６としては、パラジウム膜や、このパラジウムと銀，
銅，ニッケル，コバルトなどとの合金からなるパラジウ
ム合金膜などを、セラミックス製，ガラス製，ステンレ
スなどの各種の金属製の多孔質管体に被覆したものや、
ゼオライト膜などが採用できる。In the desulfurizing agent layer 15, H 2 S + ZnO = Zn
The reaction of S + H 2 O takes place. The reaction temperature is 250-3
50 ° C. The desulfurized hydrocarbon is supplied to the steam reforming section 12. As the inorganic hydrogen separation membrane 16, a palladium membrane, palladium and silver,
A porous tube made of various metals such as ceramics, glass, stainless steel, etc. coated with a palladium alloy film made of an alloy with copper, nickel, cobalt, etc.
A zeolite membrane or the like can be adopted.
【００２３】前記脱炭酸工程１９は、脱硫・改質された
メタンリッチガスを脱炭酸処理する工程である。脱炭酸
方法としては、ポリイミド，セルロースなどの有機系選
択炭酸ガス分離膜などを用いた高分子膜法が採用でき
る。また、この高分子膜法に代えて、ＰＳＡ法や従来の
湿式吸収法などが採用できる。その後、脱炭酸処理され
たメタンリッチガス中に増燃用の液化石油ガスを添加す
ることで、高カロリーな都市ガスが製造される。液化石
油ガスの添加量は適宜決定される。The decarboxylation step 19 is a step of decarboxylation of the desulfurized and reformed methane-rich gas. As a decarboxylation method, a polymer membrane method using an organic selective carbon dioxide separation membrane such as polyimide or cellulose can be employed. Instead of the polymer film method, a PSA method or a conventional wet absorption method can be employed. Thereafter, liquefied petroleum gas for increasing the fuel is added to the decarbonated methane-rich gas to produce a high-calorie city gas. The amount of liquefied petroleum gas added is determined as appropriate.
【００２４】上記構成の原料炭化水素の脱硫改質装置１
０を用いた原料炭化水素の脱硫改質方法について、以下
詳述する。硫黄分を含む原料炭化水素ａを、脱硫部１３
の水素化触媒層１４に供給する。この水素化触媒層１４
では、原料炭化水素ａの組成中に含まれる硫黄分が、水
蒸気改質部１２で生成されて無機水素分離膜１６を透過
した水素（水添脱硫用水素）と反応する。無機水素分離
膜１６の透過時、水素はプロトンに解離して透過するた
め、極めて反応性に富み、脱硫効果が大きい。An apparatus 1 for desulfurizing and reforming a raw hydrocarbon having the above structure
The method for desulfurizing and reforming the raw material hydrocarbon using No. 0 will be described in detail below. The raw material hydrocarbon a containing sulfur is supplied to the desulfurization unit 13
Is supplied to the hydrogenation catalyst layer 14. This hydrogenation catalyst layer 14
Then, the sulfur content in the composition of the raw material hydrocarbon a reacts with the hydrogen (hydrogen desulfurization hydrogen) generated in the steam reforming section 12 and permeating the inorganic hydrogen separation membrane 16. At the time of permeation through the inorganic hydrogen separation membrane 16, hydrogen is dissociated into protons and permeates, so that it is extremely reactive and has a large desulfurization effect.
【００２５】これにより、硫黄が水素化触媒によって水
素化処理されて硫化水素に改質される。なお、水素化反
応の吸熱分は、水蒸気改質反応の発熱で補われる。その
後、硫化水素は脱硫剤層１５に流入し、ここで脱硫剤に
より固定化され脱硫が行われる。脱硫された炭化水素
は、図外のスーパーヒータから供給された水蒸気に、水
蒸気／原料１．０〜５．０ｋｇ−ｍｏｌ−Ｈ2 Ｏ／ｋｇ
−ｍｏｌ−Ｃ、好ましくは２．０〜３．０ｋｇ−ｍｏｌ
−Ｈ2 Ｏ／ｋｇ−ｍｏｌ−Ｃで添加され、温度を３００
〜４００℃、圧力を常圧〜４０ｋｇ／ｃｍ2 Ｇで水蒸気
改質部１２に、改質部供給ガスとして供給される。この
水蒸気改質部１２の導入室１２ａでは、脱硫後の炭化水
素と水蒸気とが混合され、この混合物は改質触媒と接触
してメタンリッチな改質ガス（メタンリッチガス）ｂに
転換される。Thus, the sulfur is hydrogenated by the hydrogenation catalyst and reformed into hydrogen sulfide. The endothermic component of the hydrogenation reaction is supplemented by the heat generated by the steam reforming reaction. Thereafter, the hydrogen sulfide flows into the desulfurizing agent layer 15, where it is fixed by the desulfurizing agent and desulfurized. The desulfurized hydrocarbon is added to steam supplied from a super heater (not shown), and steam / raw material 1.0 to 5.0 kg-mol-H 2 O / kg
-Mol-C, preferably 2.0 to 3.0 kg-mol
Is added -H 2 O / kg-mol- C, the temperature 300
The gas is supplied to the steam reforming section 12 at a pressure of about 400 ° C. and a normal pressure of about 40 kg / cm 2 G as a reforming section supply gas. In the introduction chamber 12a of the steam reforming section 12, the hydrocarbon after the desulfurization is mixed with the steam, and this mixture comes into contact with the reforming catalyst and is converted into a methane-rich reformed gas (methane-rich gas) b.
【００２６】この改質ガスｂは、水蒸気改質部１２の排
出口１８から排出されて、脱炭酸工程１９へ供給され
る。ここでは、高分子膜法またはＰＳＡ法により、選択
的に炭酸ガスを除去する。この炭酸ガスが除去された脱
炭酸ガスｃに増燃用の液化石油ガスが添加されて、高カ
ロリーな都市ガスｄが製造される。一方、高分子膜法に
よる脱炭酸工程１９の透過側のガスは、燃料ガスｅとし
て排出される。The reformed gas b is discharged from the outlet 18 of the steam reforming section 12 and supplied to the decarbonation step 19. Here, carbon dioxide is selectively removed by a polymer film method or a PSA method. A liquefied petroleum gas for increasing the fuel is added to the decarbonated gas c from which the carbon dioxide gas has been removed to produce a high calorie city gas d. On the other hand, the gas on the permeation side in the decarbonation step 19 by the polymer membrane method is discharged as fuel gas e.
【００２７】なお、各工程中のガスである原料炭化水素
ａ，改質ガス（メタンリッチガス）ｂ，脱炭酸ガスｃ，
都市ガスｄ，燃料ガスｅの成分を表１に示す。The raw material hydrocarbons a, reformed gas (methane-rich gas) b, decarbonated gas c,
Table 1 shows the components of the city gas d and the fuel gas e.
【００２８】[0028]
【表１】 [Table 1]
【００２９】このように、原料炭化水素ａ中の硫黄分の
脱硫部１３と、水蒸気改質部１２とを、少なくとも一部
に無機水素分離膜１６が形成された隔壁により分離し、
これにより水蒸気改質部１２により発生した水素と熱エ
ネルギーを、直接的に脱硫部１３の加熱および水添脱硫
用水素として利用するようにしたので、脱硫改質装置１
０のコンパクト化と、熱エネルギーの効率化とを図るこ
とができる。なお、従来は、各工程が各々分離してお
り、しかも水添脱硫用水素をリサイクルするために、冷
却→昇圧→昇温操作が必要であったが、本発明において
は、水素を脱硫部へ直接供給するために、それらの操作
が不要となる。本脱硫改質装置１０は、メタン改質条件
であり、また水素回収部がないため、高純度水素製造に
は不適当であるが、水素改質条件で製造し、本装置１０
の後工程に高純度水素回収工程を設ければ、可能であ
る。As described above, the desulfurization unit 13 for the sulfur content in the raw material hydrocarbon a and the steam reforming unit 12 are separated by the partition wall on which the inorganic hydrogen separation membrane 16 is formed at least partially.
As a result, the hydrogen and heat energy generated by the steam reforming unit 12 are directly used as hydrogen for heating and hydrodesulfurization of the desulfurization unit 13, so that the desulfurization reformer 1
0 and the efficiency of heat energy can be improved. Conventionally, each process is separated from each other, and furthermore, in order to recycle the hydrogen for hydrodesulfurization, it is necessary to perform a cooling->pressure-> temperature-raising operation. These operations are not required because of direct supply. The desulfurization reforming apparatus 10 is not suitable for high-purity hydrogen production because it is under methane reforming conditions and has no hydrogen recovery unit.
This is possible if a high-purity hydrogen recovery step is provided in the subsequent step.
【００３０】次に、この原料炭化水素の脱硫改質装置１
０の一部を設計変更して、図２に示すように、高純度水
素を回収する脱硫改質装置２０とした例を説明する。こ
の図２に示す他の実施の形態に係る原料炭化水素の脱硫
改質装置２０の特長は、次のとおりである。すなわち、
まず円筒状の改質脱硫塔２１の内部が、脱硫部２４、水
蒸気改質部２５および高純度水素回収部２６の３室に区
画されている。このうち、第１室の脱硫部２４と第２室
の水蒸気改質部２５とは隣接し、これらは少なくとも一
部が、無機水素分離膜２７Ａで形成された隔壁により分
離されている。Next, this raw material hydrocarbon desulfurization reformer 1
An example in which a part of the desulfurization reforming apparatus 20 for recovering high-purity hydrogen as shown in FIG. The features of the raw material hydrocarbon desulfurization reformer 20 according to the other embodiment shown in FIG. 2 are as follows. That is,
First, the inside of the cylindrical reforming desulfurization tower 21 is partitioned into three chambers, a desulfurization section 24, a steam reforming section 25, and a high-purity hydrogen recovery section 26. Among them, the desulfurization section 24 in the first chamber and the steam reforming section 25 in the second chamber are adjacent to each other, and at least a part thereof is separated by a partition wall formed by the inorganic hydrogen separation membrane 27A.
【００３１】また、第１室の脱硫部２４内には、水素化
触媒層２２および脱硫剤層２３が設けられている。一
方、第２室の水蒸気改質部２５内には、水蒸気改質触媒
が充填されている。この第２室の水蒸気改質部２５と第
３室の高純度水素回収部２６とは隣接され、しかも両者
は少なくとも一部が無機水素分離膜２７Ｂである円筒状
の隔壁によって仕切られている。なお、無機水素分離膜
２７Ｂの筒内には触媒などは充填されていない。この脱
硫部２４には、原料炭化水素を水素化触媒層２２と脱硫
剤層２３との順序で供給する原料炭化水素供給口２８が
設けられている。この水蒸気改質部２５には、水蒸気供
給口２９および無機水素分離膜２７Ｂの非透過ガスを排
出する非透過ガス排出口３０が設けられている。さら
に、高純度水素回収部２６には、高純度水素排出口３１
が設けられている。Further, a hydrogenation catalyst layer 22 and a desulfurizing agent layer 23 are provided in the desulfurizing section 24 of the first chamber. On the other hand, the inside of the steam reforming section 25 of the second chamber is filled with a steam reforming catalyst. The steam reforming section 25 in the second chamber and the high-purity hydrogen recovery section 26 in the third chamber are adjacent to each other, and at least a part thereof is partitioned by a cylindrical partition wall which is an inorganic hydrogen separation membrane 27B. Note that the inside of the cylinder of the inorganic hydrogen separation membrane 27B is not filled with a catalyst or the like. The desulfurization section 24 is provided with a raw hydrocarbon supply port 28 for supplying the raw hydrocarbon in the order of the hydrogenation catalyst layer 22 and the desulfurizing agent layer 23. The steam reforming section 25 is provided with a steam supply port 29 and a non-permeate gas discharge port 30 for discharging the non-permeate gas of the inorganic hydrogen separation membrane 27B. Further, the high-purity hydrogen recovery section 26 has a high-purity hydrogen outlet 31.
Is provided.
【００３２】この水蒸気改質部１２における改質温度
は、５００〜６００℃が最適である。アルミナ（Ａｌ2
Ｏ3 ）や酸化マグネシウムを担体とするニッケル触媒の
接媒式水蒸気分解法によるメタンを改質したガスの成分
は、水素７６．６，一酸化炭素１５．５，二酸化炭素
７．５，メタン０．４（容量％），合計１００である。
ここでの反応を次に示す。 ＣＨ4 ＋Ｈ2 Ｏ→３Ｈ2 ＋ＣＯ ・・・（１） ＣＯ＋Ｈ2 Ｏ→ＣＯ2 ＋Ｈ2 ・・・（２）The optimum reforming temperature in the steam reforming section 12 is 500 to 600 ° C. Alumina (Al 2
The components of the gas obtained by reforming methane by a steam-catalyzed cracking method using a nickel catalyst using O 3 ) or magnesium oxide as a carrier include hydrogen 76.6, carbon monoxide 15.5, carbon dioxide 7.5, and methane 0 .4 (volume%), a total of 100.
The reaction here is shown below. CH 4 + H 2 O → 3H 2 + CO (1) CO + H 2 O → CO 2 + H 2 (2)
【００３３】この脱硫改質装置２０を用いた原料炭化水
素の脱硫改質方法は、原料炭化水素ｆを原料炭化水素供
給口２８を通して、まず水素化触媒層２２に供給し、炭
化水素中の硫黄分が水素化反応を起こして硫化水素とな
る。この硫化水素は、下流側の脱硫剤層２３に供給され
て、脱硫剤に固定されて脱硫される。このようにして脱
硫された炭化水素は、その後、図外のスーパーヒータか
ら水蒸気供給口２９より供給された水蒸気中に、水蒸気
／原料１．０〜５．０ｋｇ−ｍｏｌ−Ｈ2 Ｏ／ｋｇ−ｍ
ｏｌ−Ｃ、好ましくは２．０〜３．０ｋｇ−ｍｏｌ−Ｈ
2 Ｏ／ｋｇ−ｍｏｌ−Ｃで添加される。これにより、温
度が５００〜６００℃、圧力が常圧〜４０ｋｇ／ｃｍ2
Ｇ未満で水蒸気改質部２５に供給される。In the desulfurization reforming method for the raw material hydrocarbon using the desulfurization reformer 20, the raw material hydrocarbon f is first supplied to the hydrogenation catalyst layer 22 through the raw material hydrocarbon supply port 28, and the sulfur contained in the hydrocarbon is removed. The components undergo a hydrogenation reaction to become hydrogen sulfide. This hydrogen sulfide is supplied to the desulfurizing agent layer 23 on the downstream side, is fixed to the desulfurizing agent, and is desulfurized. In this way, the desulfurized hydrocarbon is then in a water vapor supplied from the vapor supply port 29 from an unillustrated superheater, steam / feedstock 1.0~5.0kg-mol-H 2 O / kg- m
ol-C, preferably 2.0-3.0 kg-mol-H
It is added at 2 O / kg-mol-C. Thereby, the temperature is 500 to 600 ° C. and the pressure is normal pressure to 40 kg / cm 2.
The gas is supplied to the steam reforming section 25 at less than G.
【００３４】この水蒸気改質部２５では、無機水素分離
膜２７Ｂを利用した上記反応式（１）〜（２）に示すよ
うな水素改質反応が起き、高濃度水素含有ガスが生成さ
れる。その一部の水素が無機水素分離膜２７Ａを透過し
て、水添脱硫用水素として水素化触媒層２２に供給され
る。しかも、水素改質反応において発生した熱は、吸熱
反応であるこの水素化反応に利用される。水蒸気改質部
２５で生成した水素は、無機水素分離膜２７Ｂを透過し
て高純度水素回収部２６に流れ込み、その後、高純度水
素排出口３１から高純度水素ｇとして回収される。一
方、無機水素分離膜２７Ｂの非透過側からは、非透過側
ガス排出口３０から燃料ガスｈとして排出される。な
お、各工程中のガスである原料炭化水素ｆ，高純度水素
ｇ，燃料ガスｈの各成分を表２に示す。In the steam reforming section 25, a hydrogen reforming reaction using the inorganic hydrogen separation membrane 27B as shown in the above reaction formulas (1) and (2) occurs, and a high-concentration hydrogen-containing gas is generated. Part of the hydrogen passes through the inorganic hydrogen separation membrane 27A and is supplied to the hydrogenation catalyst layer 22 as hydrogen for hydrodesulfurization. In addition, the heat generated in the hydrogen reforming reaction is used for this endothermic hydrogenation reaction. The hydrogen generated in the steam reforming section 25 passes through the inorganic hydrogen separation membrane 27B, flows into the high-purity hydrogen recovery section 26, and is thereafter recovered from the high-purity hydrogen outlet 31 as high-purity hydrogen g. On the other hand, from the non-permeate side of the inorganic hydrogen separation membrane 27B, the fuel gas h is discharged from the non-permeate side gas outlet 30. Table 2 shows the components of the raw material hydrocarbon f, the high-purity hydrogen g, and the fuel gas h, which are the gases in each step.
【００３５】[0035]
【表２】 [Table 2]
【００３６】このように、脱硫部２４、水蒸気改質部２
５および高純度水素回収部２６を一体化し、それぞれ無
機水素分離膜２７Ａ，２７Ｂを有する隔壁を介して仕切
ったので、無機水素分離膜２７Ｂを透過した水蒸気改質
部２５からの高純度水素ｇを、高純度水素回収部２６か
ら分離回収することができる。また、無機水素分離膜２
７Ａ，２７Ｂを透過した水素はプロトンに解離するの
で、水素よりも反応性に富むため、脱硫効率が高まる。As described above, the desulfurization unit 24 and the steam reforming unit 2
5 and the high-purity hydrogen recovery unit 26 are integrated and separated via partition walls having inorganic hydrogen separation membranes 27A and 27B, respectively, so that the high-purity hydrogen g from the steam reforming unit 25 that has passed through the inorganic hydrogen separation membrane 27B is removed. From the high-purity hydrogen recovery unit 26. In addition, the inorganic hydrogen separation membrane 2
Hydrogen that has passed through 7A and 27B is dissociated into protons and is more reactive than hydrogen, so that the desulfurization efficiency increases.
【００３７】次に、図３に基づいて、この原料炭化水素
の脱硫改質装置２０の一部を設計変更して、同じく高純
度水素を回収する脱硫改質装置３０を説明する。この図
３に示すさらに別の実施の形態に係る原料炭化水素の脱
硫改質装置３０の特長は、次のとおりである。すなわ
ち、水蒸気改質触媒層が形成された水蒸気改質部３２の
脱硫改質塔３１内は、少なくとも壁面の一部が無機水素
分離膜（第１の隔壁）３７で形成され、内部が隔壁（第
２の隔壁）３８で上下に２区画されており、しかも上部
の区画は、内部に水素化触媒層３３および脱硫剤層３４
が形成された脱硫部３５とされ、下部の区画は、高純度
水素回収部３６が設けられている。脱硫部３５には、下
部の水素化触媒層３３と、上部の脱硫剤層３４の順序で
原料炭化水素ｆを供給する原料炭化水素供給ノズル３
９、および脱硫された炭化水素の排出口４０が設けられ
ている。水蒸気改質部３２には、脱硫された炭化水素お
よび水蒸気の混合ガスの供給口４１、および無機水素分
離膜３７の非透過ガス排出口４２、高純度水素回収部３
６には、高純度水素排出口４３が設けられている。Next, a desulfurization reformer 30 for recovering high-purity hydrogen by partially modifying the desulfurization reformer 20 for raw material hydrocarbons will be described with reference to FIG. The features of the raw material hydrocarbon desulfurization reformer 30 according to still another embodiment shown in FIG. 3 are as follows. That is, in the desulfurization reforming tower 31 of the steam reforming section 32 on which the steam reforming catalyst layer is formed, at least a part of the wall surface is formed by the inorganic hydrogen separation membrane (first partition) 37 and the inside is formed by the partition ( A second partition 38 is vertically divided into two sections, and the upper section is provided with a hydrogenation catalyst layer 33 and a desulfurization agent layer 34 therein.
Is formed in the desulfurization section 35, and a lower section is provided with a high-purity hydrogen recovery section 36. In the desulfurization unit 35, the raw hydrocarbon feed nozzle 3 that supplies the raw hydrocarbon f in the order of the lower hydrogenation catalyst layer 33 and the upper desulfurizer layer 34
9 and an outlet 40 for desulfurized hydrocarbons. The steam reforming section 32 has a supply port 41 for a mixed gas of desulfurized hydrocarbon and steam, a non-permeate gas outlet 42 of the inorganic hydrogen separation membrane 37, a high-purity hydrogen recovery section 3
6 is provided with a high-purity hydrogen outlet 43.
【００３８】硫黄分を含んだ原料炭化水素ｆは、原料炭
化水素供給ノズル３９を介して、下層側の水素化触媒層
３３に供給されて硫化水素に改質される。この際、水蒸
気改質部３２より無機水素分離膜３７を透過した水素を
水添用脱硫水素として利用される。その後、上層の脱硫
剤層３４で脱硫され、脱硫された炭化水素は、排出口４
０から排出されて、図外のスーパーヒータから供給され
た水蒸気に混合されて、混合ガスの供給口４１を通して
水蒸気改質部３２に供給される。この水蒸気改質部３２
内での水素改質反応により得られた高濃度含有水素ガス
は、無機水素分離膜３７を透過して、高純度水素回収部
３６へ流れ込み、高純度排出口４３より高純度水素ｇと
して回収される。一方、無機水素分離膜３７の非透過ガ
スは、非透過ガス排出口４２から燃料ガスｈとして排出
される。The raw hydrocarbon f containing sulfur is supplied to the lower hydrogenation catalyst layer 33 via the raw hydrocarbon feed nozzle 39 and reformed into hydrogen sulfide. At this time, the hydrogen that has passed through the inorganic hydrogen separation membrane 37 from the steam reforming section 32 is used as desulfurized hydrogen for hydrogenation. Thereafter, the desulfurized hydrocarbon is desulfurized in the upper desulfurizing agent layer 34,
The mixed gas is discharged from 0, mixed with steam supplied from a super heater (not shown), and supplied to the steam reforming section 32 through a mixed gas supply port 41. This steam reformer 32
The high-concentration-containing hydrogen gas obtained by the hydrogen reforming reaction in the reactor passes through the inorganic hydrogen separation membrane 37, flows into the high-purity hydrogen recovery unit 36, and is recovered as high-purity hydrogen g from the high-purity outlet 43. You. On the other hand, the non-permeate gas of the inorganic hydrogen separation membrane 37 is discharged from the non-permeate gas outlet 42 as the fuel gas h.
【００３９】このように、原料炭化水素の脱硫改質装置
３０においては、脱硫部３５および高純度水素回収部３
６と、水蒸気改質部３２とを、無機水素分離膜３７によ
り仕切り、かつこの無機水素分離膜３７で区画された空
間を、隔壁３８により、脱硫部３５側と、高純度水素回
収部３６側とに仕切ったので、脱硫改質装置をさらにコ
ンパクト化することができる。その他の作用および効果
は、図２に示す他の実施の形態に係る原料炭化水素の脱
硫改質装置２０と同様であるので、説明を省略する。As described above, in the desulfurization reforming apparatus 30 for the raw material hydrocarbon, the desulfurization section 35 and the high-purity hydrogen recovery section 3
6 and the steam reforming section 32 are separated by an inorganic hydrogen separation membrane 37, and the space defined by the inorganic hydrogen separation membrane 37 is divided by a partition 38 into a desulfurization section 35 side and a high-purity hydrogen recovery section 36 side The desulfurization reformer can be made more compact. Other functions and effects are similar to those of the raw material hydrocarbon desulfurization reforming apparatus 20 according to the other embodiment shown in FIG.
【００４０】[0040]
【発明の効果】請求項１〜５の発明にあっては、単一装
置内で、原料炭化水素中の硫黄分の脱硫部と水蒸気改質
部とを、少なくとも一部に無機水素分離膜が形成された
隔壁により分離し、これにより水蒸気改質部で発生した
水素と熱エネルギーを、直接的に脱硫部の加熱および水
添脱硫用水素として利用するようにしたので、脱硫改質
装置のコンパクト化と、熱エネルギーの効率利用化とを
図ることができる。According to the first to fifth aspects of the present invention, in a single device, the desulfurization unit for the sulfur content in the raw material hydrocarbon and the steam reforming unit, and the inorganic hydrogen separation membrane is at least partially provided. Separated by the formed partition walls, and the hydrogen and heat energy generated in the steam reforming section are directly used as hydrogen for heating and hydrodesulfurization of the desulfurization section. And the efficient use of heat energy.
【００４１】特に、請求項２の発明にあっては、上記請
求項１〜５の効果に加え、脱硫された炭化水素を水蒸気
改質部内でメタン改質してメタンリッチガスとし、それ
からこのガスを脱炭酸処理したのち、同ガス中に液化石
油ガスを添加するようにしたので、高カロリーな都市ガ
スを製造することができる。In particular, in the invention of claim 2, in addition to the effects of claims 1 to 5, the desulfurized hydrocarbon is reformed with methane in the steam reforming section to form a methane-rich gas. After decarbonation, liquefied petroleum gas is added to the gas, so that high calorie city gas can be produced.
【００４２】また、請求項３，４の発明にあっては、上
記請求項１〜５の効果に加えて、一体化された脱硫部、
水蒸気改質部および高純度水素回収部を、それぞれ無機
水素分離膜を有する隔壁を介して仕切ったので、無機水
素分離膜を透過した水蒸気改質部からの高純度水素を、
高純度水素回収部から分離回収することができる。According to the third and fourth aspects of the present invention, in addition to the effects of the first to fifth aspects, an integrated desulfurization unit,
Since the steam reforming section and the high-purity hydrogen recovery section were separated via partition walls each having an inorganic hydrogen separation membrane, high-purity hydrogen from the steam reforming section that passed through the inorganic hydrogen separation membrane was
It can be separated and recovered from the high-purity hydrogen recovery section.
【００４３】さらに、請求項５の発明にあっては、上記
請求項１〜５の効果に加えて、一体化された脱硫部およ
び高純度水素回収部と、水蒸気改質部とを、無機水素分
離膜を有する第１の隔壁により仕切り、かつこの第１の
隔壁で区画された空間を、第２の隔壁により、脱硫部側
と、高純度水素回収部側とに仕切ったので、脱硫改質装
置をさらにコンパクト化することができる。Further, according to the invention of claim 5, in addition to the effects of claims 1 to 5, the integrated desulfurization unit and high-purity hydrogen recovery unit, and the steam reforming unit may be replaced with inorganic hydrogen. Since the space partitioned by the first partition having the separation membrane and the space partitioned by the first partition is partitioned by the second partition into the desulfurization section side and the high-purity hydrogen recovery section side, the desulfurization reforming is performed. The device can be made more compact.
【図１】本発明の一実施の形態に係る原料炭化水素の脱
硫改質装置の系統図である。FIG. 1 is a system diagram of a raw material hydrocarbon desulfurization reforming apparatus according to one embodiment of the present invention.
【図２】他の実施の形態に係る原料炭化水素の脱硫改質
装置の系統図である。FIG. 2 is a system diagram of a raw material hydrocarbon desulfurization reforming apparatus according to another embodiment.
【図３】さらに別の実施の形態に係る原料炭化水素の脱
硫改質装置の系統図である。FIG. 3 is a system diagram of an apparatus for desulfurizing and reforming a raw hydrocarbon according to still another embodiment.
１０，２０，３０ 原料炭化水素の脱硫改質装置 １３，２４，３５ 脱硫部 １２，２５，３２ 水蒸気改質部 １６，２７Ａ，２７Ｂ 無機水素分離膜 １７ 高純度水素回収部 １９ 脱炭酸工程 ３７ 無機水素分離膜（第２の隔壁） ３８ 隔壁（第２の隔壁） ａ 原料炭化水素 ｂ 改質ガス（メタンリッチガス） ｃ 脱炭酸ガス ｄ 都市ガス ｅ 燃料ガス ｆ 原料炭化水素 ｇ 高純度水素 ｈ 燃料ガス 整理番号 ＰＭＫ７３ 10, 20, 30 Desulfurization reforming unit for raw hydrocarbons 13, 24, 35 Desulfurization unit 12, 25, 32 Steam reforming unit 16, 27A, 27B Inorganic hydrogen separation membrane 17 High-purity hydrogen recovery unit 19 Decarbonation step 37 Inorganic Hydrogen separation membrane (second partition) 38 Partition (second partition) a Source hydrocarbon b Reformed gas (methane-rich gas) c Decarbonation gas d City gas e Fuel gas f Source hydrocarbon g High-purity hydrogen h Fuel gas Reference number PMK73
───────────────────────────────────────────────────── フロントページの続き (72)発明者 谷口 浩之 神奈川県川崎市川崎区大川町２番１号 三 菱化工機株式会社内 Ｆターム(参考） 4H029 BA01 BA02 BA08 BB11 BB12 BD17 BD19 DA03 DA09 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Taniguchi 2-1 Okawa-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term (reference) 4H029 BA01 BA02 BA08 BB11 BB12 BD17 BD19 DA03 DA09
Claims (5)
する脱硫部と、 脱硫された炭化水素を水蒸気改質する水蒸気改質部、と
を備え、 前記脱硫部と前記水蒸気改質部とは隔壁を介して一体化
され、かつ該隔壁の少なくとも一部を、水素を透過する
無機水素分離膜により構成することで、前記水蒸気改質
部で発生した水素を無機水素分離膜に透過して脱硫部に
供給し、この水素を前記硫黄分の水添脱硫用水素として
用いることを特徴とする原料炭化水素の脱硫改質装置。1. A desulfurization unit for desulfurizing and removing sulfur in a raw material hydrocarbon, and a steam reforming unit for steam reforming the desulfurized hydrocarbon, wherein the desulfurization unit and the steam reforming unit are provided. Is integrated via a partition, and at least a part of the partition is constituted by an inorganic hydrogen separation membrane that transmits hydrogen, so that hydrogen generated in the steam reforming unit is transmitted through the inorganic hydrogen separation membrane. Wherein the hydrogen is supplied to a desulfurization section, and the hydrogen is used as hydrogen for the hydrodesulfurization of the sulfur content.
蒸気を添加して、水蒸気改質部に供給し、該水蒸気改質
部内で改質触媒と接触させてメタン改質することで、メ
タンリッチガスを製造する水蒸気改質工程と、 （ロ）少なくとも一部が無機水素分離膜である隔壁を中
間に介在させて、隣接する前記水蒸気改質工程の水蒸気
改質部と一体化された脱硫部内に原料炭化水素を供給
し、これにより該原料炭化水素を、前記脱硫部に充填さ
れた水添触媒および脱硫剤に順次接触させ、かつ前記水
蒸気改質部内から前記無機水素分離膜を透過して前記脱
硫部内に達した水素を、水添脱硫用水素として用いるこ
とで、原料炭化水素中の硫黄分を硫化水素に改質したの
ち、前記脱硫剤により脱硫する脱硫工程と、 （ハ）脱硫・改質されたメタンリッチガスを脱炭酸処理
する脱炭酸工程と、 （ニ）脱炭酸処理されたメタンリッチガス中にＬＰＧを
添加することにより、高カロリーな都市ガスを製造する
工程、とを備えたことを特徴とする原料炭化水素の脱硫
改質方法。2. (a) water or steam is added to the desulfurized hydrocarbon and supplied to a steam reforming section, and is brought into contact with a reforming catalyst in the steam reforming section to perform methane reforming; A steam reforming step for producing a methane-rich gas; and (b) desulfurization integrated with a steam reforming section of the adjacent steam reforming step by interposing a partition wall at least a part of which is an inorganic hydrogen separation membrane therebetween. The raw material hydrocarbon is supplied into the section, whereby the raw material hydrocarbon is sequentially brought into contact with the hydrogenation catalyst and the desulfurizing agent filled in the desulfurization section, and passes through the inorganic hydrogen separation membrane from inside the steam reforming section. Using the hydrogen that has reached the desulfurization unit as hydrogen for hydrodesulfurization to reform the sulfur content in the raw material hydrocarbons into hydrogen sulfide, and then desulfurize with the desulfurizing agent;・ Reformed methane-rich gas A carbon dioxide raw material characterized by comprising: a decarboxylation step of decarbonating carbon dioxide; and (d) a step of producing high-calorie city gas by adding LPG to the methane-rich gas subjected to decarbonation. Hydrogen desulfurization reforming method.
する脱硫部と、 脱硫された炭化水素を水蒸気改質する水蒸気改質部と、 該水蒸気改質部で発生した高濃度水素含有ガスから高純
度水素を分離回収する高純度水素回収部、とを備え、 前記脱硫部、前記水蒸気改質部および前記高純度水素回
収部は、それぞれ隔壁を介して一体化され、かつ該各隔
壁の少なくとも一部は、水素を透過する無機水素分離膜
により構成され、また前記水蒸気改質部で発生した水素
を前記無機水素分離膜に透過して前記脱硫部に供給し、
これを前記原料炭化水素中の硫黄分の水添脱硫用水素と
して用いる一方、前記高純度水素回収部では、前記水蒸
気改質部の水素を前記無機水素分離膜に透過して高純度
水素を分離回収することを特徴とする原料炭化水素の脱
硫改質装置。3. A desulfurization unit for desulfurizing and removing sulfur content in a raw material hydrocarbon, a steam reforming unit for steam reforming the desulfurized hydrocarbon, and a high-concentration hydrogen generated in the steam reforming unit. A high-purity hydrogen recovery unit that separates and recovers high-purity hydrogen from gas, wherein the desulfurization unit, the steam reforming unit, and the high-purity hydrogen recovery unit are each integrated via a partition, and each of the partitions At least a part of is constituted by an inorganic hydrogen separation membrane that permeates hydrogen, and supplies the hydrogen generated in the steam reforming section to the desulfurization section through the inorganic hydrogen separation membrane,
This is used as hydrogen for hydrodesulfurization of sulfur in the raw material hydrocarbon, while the high-purity hydrogen recovery section separates high-purity hydrogen by permeating the hydrogen in the steam reforming section through the inorganic hydrogen separation membrane. A desulfurization reformer for raw hydrocarbons, characterized by being recovered.
蒸気を添加して、水蒸気改質部に供給し、該水蒸気改質
部内で改質触媒と接触させて水素改質することで、高濃
度水素含有ガス を製造する水蒸気改質工程と、 （ロ）少なくとも一部が無機水素分離膜である隔壁を中
間に介在させて、隣接する前記水蒸気改質工程の水蒸気
改質部と一体化された脱硫部内に原料炭化水素を供給
し、これにより該原料炭化水素を、前記脱硫部に充填さ
れた水添触媒および脱硫剤に順次接触させ、しかも前記
水蒸気改質部から前記無機水素分離膜を透過して前記脱
硫部内に達した水素を水添脱硫用水素として用いること
で、原料炭化水素中の硫黄分を硫化水素に改質したの
ち、前記脱硫剤により脱硫する脱硫工程と、 （ハ）前記高濃度水素含有ガス中に含まれる水素を、前
記高純度水素回収部側の無機水素分離膜に透過すること
で高純度水素として回収する高純度水素回収工程、とを
備えたことを特徴とする原料炭化水素の脱硫改質方法。4. (a) Water or steam is added to the desulfurized hydrocarbon and supplied to a steam reforming section, and is brought into contact with a reforming catalyst in the steam reforming section to perform hydrogen reforming. A steam reforming step for producing a high-concentration hydrogen-containing gas; and (b) integrating with a steam reforming section of the adjacent steam reforming step by interposing a partition wall at least partly of which is an inorganic hydrogen separation membrane in the middle. And supplying the raw hydrocarbon to the hydrogenation catalyst and the desulfurizing agent filled in the desulfurization section, and furthermore, the inorganic hydrogen separation membrane from the steam reforming section. A desulfurization step of reforming the sulfur content of the raw material hydrocarbons into hydrogen sulfide by using the hydrogen that has passed through and passed into the desulfurization unit as hydrogen for hydrodesulfurization, and then desulfurizing with the desulfurizing agent; ) Contained in said high-concentration hydrogen-containing gas A high-purity hydrogen recovery step of recovering high-purity hydrogen by permeating the high-purity hydrogen through an inorganic hydrogen separation membrane on the high-purity hydrogen recovery section side. .
する脱硫部と、 脱硫された炭化水素を水蒸気改質する水蒸気改質部と、 該水蒸気改質部で発生した高濃度水素含有ガスから高純
度水素を分離回収する高純度水素回収部、とを備え、 前記脱硫部、前記水蒸気改質部および前記高純度水素回
収部を一体化し、前記脱硫部および前記高純度水素回収
部と、前記水蒸気改質部とは、少なくとも一部が無機水
素分離膜で形成された第１の隔壁により区画され、しか
も該第１の隔壁により区画された空間は、第２の隔壁を
介して、前記脱硫部側と、前記高純度水素回収部側とに
仕切られていることを特徴とする原料炭化水素の脱硫改
質装置。5. A desulfurization section for desulfurizing and removing sulfur from a raw material hydrocarbon, a steam reforming section for steam reforming the desulfurized hydrocarbon, and a high-concentration hydrogen generated in the steam reforming section. A high-purity hydrogen recovery unit that separates and recovers high-purity hydrogen from gas; and the desulfurization unit, the steam reforming unit and the high-purity hydrogen recovery unit are integrated, and the desulfurization unit and the high-purity hydrogen recovery unit are integrated. The steam reforming section is defined by a first partition at least partially formed of an inorganic hydrogen separation membrane, and a space defined by the first partition is formed via a second partition. A desulfurization reforming apparatus for raw hydrocarbons, wherein the apparatus is partitioned into the desulfurization section and the high-purity hydrogen recovery section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10182267A JP2000017276A (en) | 1998-06-29 | 1998-06-29 | Equipment and process for desulfurization and reforming of hydrocarbon feedstock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10182267A JP2000017276A (en) | 1998-06-29 | 1998-06-29 | Equipment and process for desulfurization and reforming of hydrocarbon feedstock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000017276A true JP2000017276A (en) | 2000-01-18 |
Family
ID=16115278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10182267A Withdrawn JP2000017276A (en) | 1998-06-29 | 1998-06-29 | Equipment and process for desulfurization and reforming of hydrocarbon feedstock |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000017276A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003523450A (en) * | 2000-02-17 | 2003-08-05 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Desulfurization |
| US9803148B2 (en) | 2011-07-29 | 2017-10-31 | Saudi Arabian Oil Company | Hydrocracking process with interstage steam stripping |
-
1998
- 1998-06-29 JP JP10182267A patent/JP2000017276A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003523450A (en) * | 2000-02-17 | 2003-08-05 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Desulfurization |
| US9803148B2 (en) | 2011-07-29 | 2017-10-31 | Saudi Arabian Oil Company | Hydrocracking process with interstage steam stripping |
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