JP2006291036A - Adsorptive desulfurization of hydrocarbon oil - Google Patents
Adsorptive desulfurization of hydrocarbon oil Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 49
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 49
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 17
- 230000023556 desulfurization Effects 0.000 title claims abstract description 17
- 230000000274 adsorptive effect Effects 0.000 title claims abstract description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003463 adsorbent Substances 0.000 claims abstract description 31
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001657 ferrierite group Inorganic materials 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 description 49
- 239000011593 sulfur Substances 0.000 description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 47
- 239000003921 oil Substances 0.000 description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 34
- 239000010457 zeolite Substances 0.000 description 34
- 229910021536 Zeolite Inorganic materials 0.000 description 33
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 13
- 239000003502 gasoline Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 239000012013 faujasite Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002795 fluorescence method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 molecular receive Chemical compound 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、二硫化炭素を含有する炭化水素油を吸着剤により脱硫する方法に関する。 The present invention relates to a method for desulfurizing a hydrocarbon oil containing carbon disulfide with an adsorbent.
２１世紀の自動車及びその燃料においては環境問題への対応が大きな課題であり、地球温暖化ガスであるＣＯ２排出削減とＮＯｘ等のいわゆる自動車排出ガス削減との両方の観点から、燃料の硫黄分低減が益々求められている。具体的には、ガソリンの硫黄分は、近い将来サルファー・フリー（硫黄分１０ｐｐｍ以下）に規制され、さらに低硫黄分、すなわちゼロ・サルファー（硫黄分１ｐｐｍ以下）の燃料油も求められている。また、オンボード改質方式燃料電池自動車等の燃料電池の普及によっては、さらに低硫黄の石油系液体燃料油が求められる可能性も有り、超低硫黄化のための脱硫技術が盛んに研究されている。一方、石油化学分野においても、微量の硫黄分が触媒反応などに影響を及ぼすことなどから、硫黄分の効率的除去が求められている。 In the automotive and fuel in the 21st century is a major challenge to respond to environmental problems, both in terms of a so-called vehicle emissions reductions CO 2 emissions reduction and NOx and the like are greenhouse gases, sulfur fuel Reduction is increasingly required. Specifically, the sulfur content of gasoline will be regulated to sulfur-free (sulfur content of 10 ppm or less) in the near future, and fuel oil having a low sulfur content, that is, zero sulfur (sulfur content of 1 ppm or less) is also required. Also, with the widespread use of fuel cells such as on-board reforming fuel cell vehicles, there is a possibility that low-sulfur petroleum-based liquid fuel oil may be required, and desulfurization technology for ultra-low sulfur has been actively researched. ing. On the other hand, in the petrochemical field, efficient removal of sulfur is required because a small amount of sulfur affects the catalytic reaction.
従来、主に用いられてきた脱硫技術である水素化脱硫方法をそのまま用い、ガソリンなどの燃料油に残存する硫黄化合物を除去して硫黄分１０ｐｐｍ以下、さらには１ｐｐｍ以下にすることは、水素化脱硫が高温・高圧の反応であるため、エネルギー消費が大きく、また、膨大な触媒量と水素消費量などにより、多大なコストアップとなる。また、ガソリンについては、オレフィン分まで水素化されてしまうためにオクタン価のロスが大きい。 Conventionally, the hydrodesulfurization method, which is a desulfurization technique that has been mainly used, is used as it is, and sulfur compounds remaining in fuel oil such as gasoline are removed to make the sulfur content 10 ppm or less, and further 1 ppm or less. Since desulfurization is a high-temperature and high-pressure reaction, energy consumption is large, and the cost is greatly increased due to the huge amount of catalyst and hydrogen consumption. In addition, gasoline has a large octane loss because it is hydrogenated to the olefin content.
このように炭化水素油の低硫黄化のためには、２〜５００ｐｐｍ程度の硫黄分を含む炭化水素油を、エネルギー消費が少なく、簡便な設備・低い運転コストで脱硫する技術が必要とされている。吸着による脱硫方法は、水素を用いない緩やかな条件下で脱硫を行うため、加熱、加圧のためのエネルギーを省くことができ、簡便な設備・低い運転コストで、かつオクタン価の減少が少ないというメリットがある。 Thus, in order to reduce the sulfur content of hydrocarbon oils, a technology for desulfurizing hydrocarbon oils containing a sulfur content of about 2 to 500 ppm with low energy consumption, simple equipment and low operating costs is required. Yes. The desulfurization method by adsorption performs desulfurization under mild conditions that do not use hydrogen, saving energy for heating and pressurization, simple equipment, low operating costs, and low decrease in octane number. There are benefits.
例えば、ナフサ、灯油、軽油、さらに重質な油の熱分解によって得られる炭化水素油には、硫黄化合物として二硫化炭素が含まれることがある。炭化水素油に含まれる二硫化炭素を上述した吸着によって脱硫する方法として、活性炭、モレキュラーレシーブ、シリカゲル、樹脂を用いるものが知られている（特許文献１及び２）。これらの特許文献には、二硫化炭素を含む炭化水素油を、陰イオン交換樹脂と接触させることで除去することが示されている。しかし、その従来技術の記載には、活性炭、モレキュラーレシーブ、シリカゲルにて除去できることが示されているが、モレキュラーレシーブの具体的な種類まで明示するものではない。
ガソリンや石油化学の原料となる炭化水素油中に含まれる二硫化炭素を１０ｐｐｍ以下、さらには１ｐｐｍ以下にゼオライトにより効率的に吸着脱硫する方法は、確立されていない点が多い。
そこで、本発明は、特定の吸着剤を用いて、ユーティリティやエネルギーの消費が少なく、二硫化炭素を含有する炭化水素油から硫黄分を効率よく除去する炭化水素油の吸着脱硫方法を提供することを課題とする。
A method for efficiently adsorbing and desulfurizing carbon disulfide contained in hydrocarbon oil, which is a raw material for gasoline and petrochemicals, to 10 ppm or less, and further to 1 ppm or less, has not been established.
Accordingly, the present invention provides a method for adsorptive desulfurization of hydrocarbon oil that uses a specific adsorbent and has low utility and energy consumption and efficiently removes sulfur from hydrocarbon oil containing carbon disulfide. Is an issue.
本発明者らは、上記課題を解決するために鋭意研究を進めた結果、二硫化炭素を含有する炭化水素油に対して、吸着剤として特定のゼオライトを用いることにより、効率的な吸着脱硫が可能であることを見出し、本発明に想到した。 As a result of diligent research to solve the above-mentioned problems, the present inventors have achieved efficient adsorptive desulfurization by using a specific zeolite as an adsorbent for hydrocarbon oil containing carbon disulfide. The inventors have found that this is possible and have come up with the present invention.
すなわち、本発明による炭化水素油の吸着脱硫方法は、二硫化炭素を含む炭化水素油を、フェリエライト及び／又はモルデナイトを主成分とする吸着剤と接触させることからなる炭化水素油の吸着脱硫方法である。 That is, the hydrocarbon oil adsorptive desulfurization method according to the present invention is a hydrocarbon oil adsorptive desulfurization method comprising contacting a hydrocarbon oil containing carbon disulfide with an adsorbent mainly composed of ferrierite and / or mordenite. It is.
本発明においては、常温付近にて液相状態の、二硫化炭素を含む炭化水素油を、特定の吸着剤と接触させることにより効率よく吸着脱硫することができる。このため、炭化水素油を加熱、加圧することなく、水素を消費することもないため、エネルギー消費が少なく、環境への負荷を低減した方法で、炭化水素油を脱硫することができる。 In the present invention, hydrocarbon desulfurization containing carbon disulfide in a liquid phase near normal temperature can be efficiently adsorbed and desulfurized by contacting with a specific adsorbent. For this reason, since hydrocarbon oil is not heated and pressurized and hydrogen is not consumed, hydrocarbon oil can be desulfurized by a method that consumes less energy and reduces the burden on the environment.
本発明による炭化水素油の吸着脱硫方法の対象となる炭化水素油は、二硫化炭素を含むものであれば特に限定されるものではないが、二硫化炭素を、０．１ｐｐｍ以上含むものが好ましく、より好ましくは０．１〜５００ｐｐｍ、特に好ましくは０．１〜２００ｐｐｍ含むものである。また、吸着の効率を良くする上では、全硫黄化合物に対する二硫化炭素の重量割合が、例えば５０％以上、好ましくは７０％以上含む原料炭化水素油が好ましい。ここで、硫黄濃度は、炭化水素油に対する、有機硫黄化合物に含まれる硫黄原子の重量割合で定義され、例えば、紫外蛍光法、微量電量滴定酸化法、蛍光Ｘ線法、化学発光法などにより測定できる。 The hydrocarbon oil to be subjected to the hydrocarbon oil adsorptive desulfurization method according to the present invention is not particularly limited as long as it contains carbon disulfide, but preferably contains 0.1 ppm or more of carbon disulfide. More preferably, it contains 0.1 to 500 ppm, particularly preferably 0.1 to 200 ppm. Moreover, in order to improve the efficiency of adsorption, a raw material hydrocarbon oil containing, for example, 50% or more, preferably 70% or more of the weight ratio of carbon disulfide to the total sulfur compound is preferable. Here, the sulfur concentration is defined by the weight ratio of the sulfur atom contained in the organic sulfur compound to the hydrocarbon oil, and measured by, for example, the ultraviolet fluorescence method, the microcoulometric titration method, the fluorescent X-ray method, the chemiluminescence method, etc. it can.
原料の炭化水素油は、二硫化炭素を含有する炭化水素油であれば、特に制限されるものではないが、具体的には、製油所などで一般的に生産されるＬＰＧ留分、ガソリン留分、ナフサ留分などに相当する基材が好ましい。ガソリン留分は、一般に炭素数４〜１１の炭化水素を主体とし、密度（１５℃）０.７８３ｇ/ｃｍ３以下、１０％留出温度が２４℃以上、９０％留出温度が１８０℃以下である。ナフサ留分は、ガソリン留分の構成成分（ホールナフサ、軽質ナフサ、重質ナフサ、又はそれらの水素化脱硫ナフサ）あるいはガソリン基材を製造する接触改質の原料（脱硫重質ナフサ）となる成分などの総称であり、沸点範囲がガソリン留分と殆ど同じ範囲か、ガソリン留分の沸点範囲に包含されるものである。ガソリン留分と同じ意味で用いられることも多い。ＬＰＧ留分は、プロパン、プロピレン、ブタン、ブチレンなどを主成分とする燃料ガス及び工業用原料ガスである。通常は、加圧下の球状タンクに液相の状態で貯蔵されるか、大気圧に近い状態で、液相で低温貯蔵される。
また、原料の炭化水素油は、製油所などで生産されるものには限らず、石油化学から生産される同様な留分でも構わない。好ましい炭化水素油として、重質油を熱分解、又は接触分解して得られた炭化水素をさらに分留して、二硫化炭素を比較的多く含有するナフサ留分、特にはその軽質ナフサ留分が使用できる。
The hydrocarbon oil as a raw material is not particularly limited as long as it is a hydrocarbon oil containing carbon disulfide. Specifically, specifically, an LPG fraction and a gasoline fraction that are generally produced in refineries and the like are used. Substrates corresponding to naphtha fractions and the like are preferred. The gasoline fraction is mainly composed of hydrocarbons having 4 to 11 carbon atoms, with a density (15 ° C.) of 0.783 g / cm 3 or less, a 10% distillation temperature of 24 ° C. or more, and a 90% distillation temperature of 180 ° C. or less. It is. The naphtha fraction is a constituent of gasoline fraction (hole naphtha, light naphtha, heavy naphtha, or hydrodesulfurized naphtha thereof) or a raw material for catalytic reforming (desulfurized heavy naphtha) for producing a gasoline base. It is a general term for components and the like, and the boiling point range is almost the same as that of the gasoline fraction, or is included in the boiling point range of the gasoline fraction. Often used interchangeably with gasoline fraction. The LPG fraction is a fuel gas mainly composed of propane, propylene, butane, butylene, and industrial raw material gas. Usually, it is stored in a spherical state under pressure in a liquid phase or is stored in a liquid phase at a low temperature in a state close to atmospheric pressure.
Further, the hydrocarbon oil as a raw material is not limited to one produced in a refinery or the like, but may be a similar fraction produced from petrochemical. As a preferred hydrocarbon oil, a hydrocarbon obtained by pyrolysis or catalytic cracking of heavy oil is further fractionated to obtain a naphtha fraction containing a relatively large amount of carbon disulfide, particularly its light naphtha fraction. Can be used.
また、原料の炭化水素油は、全硫黄分に占める二硫化炭素の割合を多くさせるための操作、例えば蒸留分離、抽出、ソーダ洗浄などを経た炭化水素油でもよい。例えば、重質油熱分解装置からの炭化水素油を蒸留分離して得られる沸点範囲が３４℃以上４２℃以下の軽質留分や、重質油熱分解装置からの沸点範囲が２４℃以上４２℃以下の炭化水素油に含まれる二硫化炭素以外の硫黄化合物を、例えばフォージャサイト型ゼオライトなどの吸着処理などにより除去し、含まれる硫黄化合物の主成分を二硫化炭素とした炭化水素油が挙げられる。 The hydrocarbon oil as the raw material may be a hydrocarbon oil that has undergone operations for increasing the proportion of carbon disulfide in the total sulfur content, such as distillation separation, extraction, and soda washing. For example, a light fraction having a boiling point range of 34 ° C. or more and 42 ° C. or less obtained by distillation separation of hydrocarbon oil from a heavy oil pyrolysis device, or a boiling point range of 24 ° C. or more and 42 ° C. from a heavy oil pyrolysis device. A hydrocarbon oil in which a sulfur compound other than carbon disulfide contained in a hydrocarbon oil at ℃ or less is removed by, for example, adsorption treatment such as faujasite type zeolite, and the main component of the contained sulfur compound is carbon disulfide. Can be mentioned.
本発明の吸着剤は、フェリエライト、モルデナイト又はこれらの混合物を主成分とする吸着剤を用いる。フェリエライト及び／又はモルデナイトの含有量は、６０重量％以上、特には７０重量％以上であり、これら以外の成分が実質的に含まれていないことが好ましい。すなわちフェリエライト及びモルデナイト以外の成分の含有量は５重量％以下であることが好ましく、特には１重量％以下であることが好ましい。 The adsorbent of the present invention uses an adsorbent mainly composed of ferrierite, mordenite, or a mixture thereof. The content of ferrierite and / or mordenite is 60% by weight or more, particularly 70% by weight or more, and it is preferable that other components are not substantially contained. That is, the content of components other than ferrierite and mordenite is preferably 5% by weight or less, and particularly preferably 1% by weight or less.
本発明に使用される吸着剤は、フェリエライト、モルデナイト及びそれらの混合物を主成分とするものである。フェリエライト、モルデナイトは、それぞれフェリエライト（ＦＥＲ）構造、モルデナイト（ＭＯＲ）構造を有するゼオライトである。ゼオライトは、一般式：ｘＭ２／ｎＯ・Ａｌ２Ｏ３・ｙＳｉＯ２・ｚＨ２Ｏ（ここで、ｎは陽イオンＭの価数、ｘは１以下の数、ｙは２以上の数、ｚは０以上の数）で表される結晶性含水アルミノシリケートである。ゼオライトの構造は、International Zeolite Association（ＩＺＡ）のStructure Commisionのホームページhttp://www.iza-structure.org/などに詳しく示されているが、Ｓｉを中心とするＳｉＯ４又はＡｌを中心とするＡｌＯ４の四面体構造が三次元的に規則正しく配列した構造である。ＡｌＯ４の四面体構造は負に帯電しているので、アルカリ金属やアルカリ土類金属等の電荷補償陽イオンを細孔や空洞内に保持している。電荷補償陽イオンは、プロトン等の別の陽イオンと容易に交換することが可能である。 The adsorbent used in the present invention is mainly composed of ferrierite, mordenite, and a mixture thereof. Ferrierite and mordenite are zeolites having a ferrierite (FER) structure and a mordenite (MOR) structure, respectively. Zeolite has the general formula: xM 2 / n O · Al 2 O 3 · ySiO 2 · zH 2 O (where n is the valence of the cation M, x is a number of 1 or less, y is a number of 2 or more, z is a crystalline hydrous aluminosilicate represented by a number of 0 or more. The structure of the zeolite is shown in detail on the Structure Commision website http://www.iza-structure.org/ of the International Zeolite Association (IZA), but it is centered on SiO 4 or Al centered on Si. This is a structure in which the tetrahedral structure of AlO 4 is regularly arranged in three dimensions. Since the tetrahedral structure of AlO 4 is negatively charged, charge compensating cations such as alkali metals and alkaline earth metals are held in the pores and cavities. The charge compensating cation can be easily exchanged for another cation such as a proton.
フェリエライト（ＦＥＲ）は、その骨格構造の構成単位が５員環、６員環及び８員環である。ミクロ細孔は一次元構造であり、入口は１０員環及び８員環で形成された楕円形で、結晶系は斜方晶である。フェリエライト型の天然ゼオライトであるフェリエライト石は、分子式（Ｍｇ２，Ｎａ２）２９・Ａｌ６Ｓｉ３０Ｏ７２・１８Ｈ２Ｏなどで表わされ、ミクロ細孔径が１０員環で４.２×５.４Åの一次元構造と８員環で３.５×４.８Åの一次元構造の二つのチャンネルをもち、両者は連結している。単位胞の大きさは１９.１５６×１４.１２７×７.４８９Åである。本発明では、陽イオンＭは特に限定されないものの、Ｋが主成分のＫフェリエライトが好ましい。 Ferrierite (FER) has a 5-membered ring, a 6-membered ring, and an 8-membered ring as structural units of the skeleton structure. The micropore has a one-dimensional structure, the entrance is an ellipse formed of a 10-membered ring and an 8-membered ring, and the crystal system is orthorhombic. Ferrierite stone, which is a ferrierite-type natural zeolite, is represented by the molecular formula (Mg 2 , Na 2 ) 29 .Al 6 Si 30 O 72 .18H 2 O and the like, and the micropore diameter is 4.2 with a 10-membered ring. It has two channels of a one-dimensional structure of × 5.4 mm and an eight-membered ring and a one-dimensional structure of 3.5 × 4.8 mm, and they are connected. The size of the unit cell is 19.156 × 14.127 × 7.489 cm. In the present invention, the cation M is not particularly limited, but K ferrierite containing K as a main component is preferable.
モルデナイト(ＭＯＲ)は、その骨格構造の構成単位が４員環、５員環及び８員環である。ミクロ細孔は一次元構造及び三次元構造であり、入口は非平面１２員環及び８員環で形成された楕円形で、結晶系は斜方晶である。天然ゼオライトであるモルデナイトとしては、モルデンフッ石があり、分子式Ｎａ８Ａｌ８Ｓｉ４０Ｏ９６・２４Ｈ２Ｏなどで表わされ、ミクロ細孔径が１２員環で６.５×７.０Åの一次元構造と８員環で２.６×５.７Åの三次元構造の二つのチャンネルをもち、両者は連結している。単位胞の大きさは１８.１×２０.５×７.５Åである。モルデナイトは、合成ゼオライトとしても存在する。本発明では、陽イオンＭは特に限定されないものの、Ｎａモルデナイトが好ましい。 Mordenite (MOR) has 4-, 5- and 8-membered structural units in its skeleton structure. The micropores have a one-dimensional structure and a three-dimensional structure, the entrance is an ellipse formed of a non-planar 12-membered ring and an 8-membered ring, and the crystal system is orthorhombic. The mordenite is a natural zeolite, there are mordenite, expressed in such molecular formula Na 8 Al 8 Si 40 O 96 · 24H 2 O, one-dimensional 6.5 × 7.0 Å in micropore diameter of 12-membered ring The structure and the 8-membered ring have two channels of 2.6 × 5.7 mm three-dimensional structure, and both are connected. The size of the unit cell is 18.1 × 20.5 × 7.5 mm. Mordenite also exists as a synthetic zeolite. In the present invention, the cation M is not particularly limited, but Na mordenite is preferable.
原料の炭化水素油の吸着は、公知の吸着操作で行うことができる。例えば、固定層による吸着（炭化水素油中に一定時間、吸着剤を浸漬後、炭化水素油を抜き取る方式、炭化水素油の流通下において吸着剤の固定層と接触させる方式）、移動層や流動層による吸着、擬似移動層による吸着などで行うことができる。炭化水素油量、吸着剤量、炭化水素油の流通速度、吸着剤との接触時間、温度などの吸着条件の調整することにより、炭化水素油の二硫化炭素濃度を５０ｐｐｍ以下、特に１０ｐｐｍ以下、さらには１ｐｐｍ以下とすることができる。通常、吸着温度は１００℃以下、特に吸着剤の吸着容量が大きくできるより低温が好ましいが、経済的な理由から常温付近が好ましい。また、炭化水素油は、気相、液相のどちらでも構わない。 The adsorption of the raw material hydrocarbon oil can be performed by a known adsorption operation. For example, adsorption by a fixed layer (method of removing hydrocarbon oil after dipping the adsorbent in hydrocarbon oil for a certain period of time, method of contacting with the fixed layer of adsorbent in the flow of hydrocarbon oil), moving bed or fluidization Adsorption by a layer, adsorption by a pseudo moving layer, or the like can be performed. By adjusting the adsorption conditions such as the amount of hydrocarbon oil, the amount of adsorbent, the flow rate of hydrocarbon oil, the contact time with the adsorbent, and the temperature, the carbon disulfide concentration of the hydrocarbon oil is 50 ppm or less, particularly 10 ppm or less, Furthermore, it can be 1 ppm or less. Usually, the adsorption temperature is preferably 100 ° C. or less, and in particular, a lower temperature than the adsorption capacity of the adsorbent can be increased. Further, the hydrocarbon oil may be either a gas phase or a liquid phase.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はそれに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
炭化水素油として、石油系重質油の熱分解装置からのナフサ（硫黄濃度：約２０００ｐｐｍ、窒素濃度：約３０ｐｐｍ）を蒸留分離することによって得られた軽質留分（蒸留性状：１０％留出温度=３５．５℃、９０％留出温度=３８．５℃）を用いた。この軽質留分は全硫黄濃度が２６ｐｐｍであり、主に含まれる硫黄化合物は二硫化炭素であり、それに基づく硫黄濃度は２５ｐｐｍであった。 Light fraction obtained by distilling naphtha (sulfur concentration: about 2000 ppm, nitrogen concentration: about 30 ppm) from a petroleum heavy oil pyrolysis unit as hydrocarbon oil (distillation properties: 10% distillation) Temperature = 35.5 ° C., 90% distillation temperature = 38.5 ° C.). This light fraction had a total sulfur concentration of 26 ppm, the sulfur compound contained mainly was carbon disulfide, and the sulfur concentration based on it was 25 ppm.
ゼオライト吸着剤となる東ソー株式会社製Ｋフェリエライト粉末ＨＳＺ−７２０ＫＯＡ（ＳｉＯ２／Ａｌ２Ｏ３比：１８.２ｍｏｌ／ｍｏｌ、Ｋ２Ｏ（乾燥ベース）：５．５ｗｔ％、Ｎａ２Ｏ（乾燥ベース）：１．３ｗｔ％、比表面積：１７０ｍ２／ｇ）を用意した。ゼオライト吸着剤は前処理として４００℃で３時間の加熱処理を行った。上述の軽質留分１０ｇに、ゼオライト１.０ｇを５〜１０℃にて２日浸漬した後、上澄み液を分取した。上澄み液の硫黄濃度をＡＳＴＭ−Ｄ５４５３−９３の紫外蛍光法により準拠して測定した結果、硫黄濃度は１ｐｐｍであり、硫黄は９５％除去された。また、二硫化炭素に基づく硫黄分は０.５ｐｐｍであり、９８％除去された。 K Ferrierite powder HSZ-720KOA (SiO 2 / Al 2 O 3 ratio: 18.2 mol / mol, K 2 O (dry basis): 5.5 wt%, Na 2 O (dry) Base): 1.3 wt%, specific surface area: 170 m 2 / g). The zeolite adsorbent was pretreated at 400 ° C. for 3 hours. After 10 g of zeolite was immersed in 10 g of the light fraction described above at 5 to 10 ° C. for 2 days, the supernatant was collected. As a result of measuring the sulfur concentration of the supernatant liquid according to the ultraviolet fluorescence method of ASTM-D5453-93, the sulfur concentration was 1 ppm, and 95% of the sulfur was removed. The sulfur content based on carbon disulfide was 0.5 ppm, and 98% was removed.
ゼオライト吸着剤として、東ソー株式会社製Ｎａモルデナイト粉末ＨＳＺ−６４２ＮＡＡ（ＳｉＯ２／Ａｌ２Ｏ３比：１８.３ｍｏｌ／ｍｏｌ、比表面積：３６０ｍ２／ｇ）を用いた以外、実施例１と同様に浸漬を行った。ゼオライト吸着剤は前処理として乾燥空気気流下４００℃で３時間の加熱処理を行った。上澄み液の硫黄濃度を測定した結果、硫黄濃度は４ｐｐｍであり、８５％除去された。また、二硫化炭素に基づく硫黄分は３ｐｐｍであり、８８％除去された。 The same as in Example 1 except that Na mordenite powder HSZ-642NAA (SiO 2 / Al 2 O 3 ratio: 18.3 mol / mol, specific surface area: 360 m 2 / g) manufactured by Tosoh Corporation was used as the zeolite adsorbent. Immersion was performed. The zeolite adsorbent was pretreated at 400 ° C. for 3 hours under a dry air stream. As a result of measuring the sulfur concentration of the supernatant, the sulfur concentration was 4 ppm, and 85% was removed. Moreover, the sulfur content based on carbon disulfide was 3 ppm, and 88% was removed.
ゼオライト吸着剤として、フォージャサイト型ゼオライトとしてＮａＸ型ゼオライト（Zeolite, Synthetic, F-9, Powder, through 75um (200mesh)（和光純薬工業(株)製））（比表面積：５２８ｍ２／ｇ）を用いた以外、同様に浸漬を行った。ゼオライト吸着剤は前処理として４００℃で３時間の加熱処理を行った。上澄み液の硫黄濃度を測定した結果より、硫黄濃度は１８ｐｐｍであり、３１％除去された。また、二硫化炭素に基づく硫黄分は１８ｐｐｍであり、２８％除去された。 As a zeolite adsorbent, NaX type zeolite (Zeolite, Synthetic, F-9, Powder, through 75um (200mesh) (manufactured by Wako Pure Chemical Industries, Ltd.)) as a faujasite type zeolite (specific surface area: 528 m 2 / g) Immersion was performed in the same manner except that was used. The zeolite adsorbent was pretreated at 400 ° C. for 3 hours. From the result of measuring the sulfur concentration of the supernatant, the sulfur concentration was 18 ppm, and 31% was removed. Moreover, the sulfur content based on carbon disulfide was 18 ppm, and 28% was removed.
実施例１、２と比較例１との比較より、フェリエライト型ゼオライト、及びモルデナイト型ゼオライトが、炭化水素油に含まれる二硫化炭素の吸着脱硫において、有効であることがわかる。 From comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that ferrierite-type zeolite and mordenite-type zeolite are effective in the adsorption desulfurization of carbon disulfide contained in hydrocarbon oil.
炭化水素油として、二硫化炭素及びノルマルデカンの試薬を用い、二硫化炭素を含むノルマルデカン(硫黄濃度：５２００ｐｐｍ、二硫化炭素に基づく硫黄濃度：５２００ｐｐｍ)を調製した。
ゼオライト吸着剤となる東ソー株式会社製Ｋフェリエライト粉末ＨＳＺ−７２０ＫＯＡ（ＳｉＯ２／Ａｌ２Ｏ３比：１８.２ｍｏｌ／ｍｏｌ、比表面積：１７０ｍ２／ｇ）を用意した。ゼオライト吸着剤は前処理として４００℃で３時間の加熱処理を行った。上述の油７ｇに、ゼオライト０.５ｇを１０℃にて５日浸漬した後、上澄み液を分取した。
上澄み液の硫黄濃度を測定した結果、全硫黄濃度は３６００ｐｐｍであり、３１％除去された。
As the hydrocarbon oil, normal decane containing carbon disulfide (sulfur concentration: 5200 ppm, sulfur concentration based on carbon disulfide: 5200 ppm) was prepared using carbon disulfide and normal decane reagents.
K ferrierite manufactured by Tosoh Corporation becomes zeolite adsorbent powder HSZ-720KOA (SiO 2 / Al 2 O 3 ratio: 18.2 mol / mol, specific surface area: 170m 2 / g) was prepared. The zeolite adsorbent was pretreated at 400 ° C. for 3 hours. After 0.5 g of zeolite was immersed in 7 g of the oil at 10 ° C. for 5 days, the supernatant liquid was collected.
As a result of measuring the sulfur concentration of the supernatant, the total sulfur concentration was 3600 ppm, and 31% was removed.
ゼオライト吸着剤として、東ソー株式会社製Ｎａモルデナイト粉末ＨＳＺ−６４２ＮＡＡ（ＳｉＯ２／Ａｌ２Ｏ３比：１８.３ｍｏｌ／ｍｏｌ、比表面積：３６０ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。ゼオライト吸着剤は前処理として４００℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、全硫黄濃度は２７００ｐｐｍであり、４８％除去された。
As Zeolite adsorbent, the same as in Example 3, except that Na Mordenite powder HSZ-642NAA (SiO 2 / Al 2 O 3 ratio: 18.3 mol / mol, specific surface area: 360 m 2 / g) manufactured by Tosoh Corporation was used. Immersion was performed. The zeolite adsorbent was pretreated at 400 ° C. for 3 hours.
As a result of measuring the sulfur concentration of the supernatant, the total sulfur concentration was 2700 ppm, and 48% was removed.
ゼオライト吸着剤として、東ソー株式会社製ＫＬ型ゼオライト粉末ＨＳＺ−５００ＫＯＡ（ＳｉＯ２／Ａｌ２Ｏ３比：６.１ｍｏｌ／ｍｏｌ、比表面積：２８０ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。ゼオライト吸着剤は前処理として４００℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、全硫黄濃度は、５２００ｐｐｍであり、硫黄は除去されなかった。
As the zeolite adsorbent, manufactured by Tosoh Corp. KL-type zeolite powder HSZ-500KOA (SiO 2 / Al 2 O 3 ratio: 6.1mol / mol, specific surface area: 280m 2 / g) except for using, as in Example 3 Soaked. The zeolite adsorbent was pretreated at 400 ° C. for 3 hours.
As a result of measuring the sulfur concentration of the supernatant, the total sulfur concentration was 5200 ppm, and sulfur was not removed.
吸着剤として、アルコア社製活性アルミナＦ−２００（比表面積：３５０ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。活性アルミナは前処理として２５０℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、硫黄は除去されなかった。
Dipping was performed in the same manner as in Example 3 except that activated alumina F-200 (specific surface area: 350 m 2 / g) manufactured by Alcoa was used as the adsorbent. The activated alumina was pretreated at 250 ° C. for 3 hours.
As a result of measuring the sulfur concentration of the supernatant liquid, sulfur was not removed.
吸着剤として、Aldrich社製不定形活性炭粉末Darco ＫＢ（比表面積：１,５００ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。活性アルミナは前処理として１５０℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、全硫黄濃度は５０００ｐｐｍであり、殆ど除去されなかった。
Immersion was performed in the same manner as in Example 3 except that Aldrich amorphous activated carbon powder Darco KB (specific surface area: 1,500 m 2 / g) was used as the adsorbent. The activated alumina was heat-treated at 150 ° C. for 3 hours as a pretreatment.
As a result of measuring the sulfur concentration of the supernatant liquid, the total sulfur concentration was 5000 ppm and was hardly removed.
吸着剤として、和光純薬工業社製シリカゲルＷＡＫＯＧＥＬ−Ｇ（比表面積：６８７ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。活性アルミナは前処理として１５０℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、硫黄は除去されなかった。
Dipping was performed in the same manner as in Example 3 except that silica gel WAKOGEL-G (specific surface area: 687 m 2 / g) manufactured by Wako Pure Chemical Industries, Ltd. was used as the adsorbent. The activated alumina was heat-treated at 150 ° C. for 3 hours as a pretreatment.
As a result of measuring the sulfur concentration of the supernatant liquid, sulfur was not removed.
吸着剤として、フォージャサイト型ゼオライトである和光純薬工業社製ＮａＸ型ゼオライト粉末Ｆ−９（ＳｉＯ２／Ａｌ２Ｏ３比：２.５ｍｏｌ／ｍｏｌ、比表面積：５９１ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。活性アルミナは前処理として４００℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、硫黄は除去されなかった。
Use (591m 2 / g SiO 2 / Al 2 O 3 ratio:: 2.5 mol / mol, specific surface area) as adsorbent, faujasite zeolite is a product of Wako Pure Chemical Industries, Ltd. NaX type zeolite powder F-9 Immersion was performed in the same manner as in Example 3 except that. The activated alumina was heat-treated at 400 ° C. for 3 hours as a pretreatment.
As a result of measuring the sulfur concentration of the supernatant liquid, sulfur was not removed.
吸着剤として、フォージャサイト型ゼオライトである東ソー株式会社製ＮａＹ型ゼオライト粉末ＨＳＺ−３２０ＮＡＡ（ＳｉＯ２／Ａｌ２Ｏ３比：５.５ｍｏｌ／ｍｏｌ、比表面積：７００ｍ２／ｇ）を用いた以外、実施例３と同様に浸漬を行った。活性アルミナは前処理として４００℃で３時間の加熱処理を行った。
上澄み液の硫黄濃度を測定した結果、硫黄は除去されなかった。
Except for using NaF type zeolite powder HSZ-320NAA (SiO 2 / Al 2 O 3 ratio: 5.5 mol / mol, specific surface area: 700 m 2 / g) manufactured by Tosoh Corporation, which is a faujasite type zeolite, as the adsorbent. The immersion was performed in the same manner as in Example 3. The activated alumina was heat-treated at 400 ° C. for 3 hours as a pretreatment.
As a result of measuring the sulfur concentration of the supernatant liquid, sulfur was not removed.
実施例３及び実施例４、比較例２〜比較例７の比較より、二硫化炭素を含む炭化水素油の吸着脱硫において、フェリエライト型ゼオライト、及びモルデナイト型ゼオライトが有効であることがわかる。 From the comparison of Example 3 and Example 4 and Comparative Examples 2 to 7, it can be seen that ferrilite-type zeolite and mordenite-type zeolite are effective in the adsorption desulfurization of hydrocarbon oil containing carbon disulfide.
本発明によれば、ガソリンや石油化学の原料となる炭化水素油に含まれる二硫化炭素を、吸着により脱硫することができ、しかも、従来の水素化脱硫と比較して、加熱、加圧のためのエネルギーが少なく、簡便な設備・低い運転コストで脱硫することが可能となる。 According to the present invention, carbon disulfide contained in hydrocarbon oil as a raw material for gasoline and petrochemicals can be desulfurized by adsorption, and compared with conventional hydrodesulfurization, it can be heated and pressurized. Therefore, desulfurization can be performed with a simple facility and low operating cost.
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| JPH04106194A (en) * | 1990-08-27 | 1992-04-08 | Kawasaki Steel Corp | Process for refining coke oven gas |
| JPH07118668A (en) * | 1993-10-20 | 1995-05-09 | Tokyo Gas Co Ltd | Method for removing sulfur compound in sulfur-containing gas |
| JP2002020765A (en) * | 2000-07-04 | 2002-01-23 | Idemitsu Petrochem Co Ltd | Removal of carbon disulfide from hydrocarbons |
| JP2005002317A (en) * | 2003-03-20 | 2005-01-06 | Japan Energy Corp | Desulfurization method of liquid hydrocarbon containing organic sulfur compound |
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| JPH04106194A (en) * | 1990-08-27 | 1992-04-08 | Kawasaki Steel Corp | Process for refining coke oven gas |
| JPH07118668A (en) * | 1993-10-20 | 1995-05-09 | Tokyo Gas Co Ltd | Method for removing sulfur compound in sulfur-containing gas |
| JP2002020765A (en) * | 2000-07-04 | 2002-01-23 | Idemitsu Petrochem Co Ltd | Removal of carbon disulfide from hydrocarbons |
| JP2005002317A (en) * | 2003-03-20 | 2005-01-06 | Japan Energy Corp | Desulfurization method of liquid hydrocarbon containing organic sulfur compound |
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