JP2013121932A - Method of purifying olefin, which removes acetylene compound contained in olefin - Google Patents
Method of purifying olefin, which removes acetylene compound contained in olefin Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 67
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- -1 acetylene compound Chemical class 0.000 title claims description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 64
- 239000012535 impurity Substances 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 29
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000746 purification Methods 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 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
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、オレフィン原料の精製方法に関し、詳しくは、オレフィン中に含有されるアセチレン系化合物の不純物を特別の吸着剤により除去する、オレフィンの精製方法に係るものである。 The present invention relates to a method for purifying an olefin raw material, and particularly relates to a method for purifying an olefin in which impurities of an acetylene compound contained in the olefin are removed by a special adsorbent.
近年、石油化学工業の基礎原料として利用されるオレフィンにおいて、特に、ポリオレフィン製造用原料として、オレフィンの需要が急速に高まっている。
一般に工業用原料としてのエチレンやプロピレンは、それぞれ炭化水素の熱分解や重質油の接触分解生成物から得られるＣ３留分の分離等によって製造されている。
しかしながら、このようにして得られる、高分子化学工業用原料としての、工業用オレフィン中には通常、アセチレン、メチルアセチレン等のいわゆる、アセチレン系化合物を始めジエン化合物等の多種の不純物が少量含有されている。これら不純物、特にアセチレン系化合物はオレフィンの重合において、触媒を被毒する作用があり、触媒効率の低下といった問題を引き起こす。そのため、これら不純物を除去するための検討が以前より行われてきた。
In recent years, demand for olefins is rapidly increasing as olefins used as basic raw materials for the petrochemical industry, particularly as raw materials for producing polyolefins.
In general, ethylene and propylene as industrial raw materials are produced by thermal decomposition of hydrocarbons, separation of C3 fraction obtained from catalytic cracking products of heavy oil, and the like.
However, the olefin for industrial use as a raw material for the polymer chemical industry thus obtained usually contains a small amount of various impurities such as diene compounds such as acetylene compounds such as acetylene and methylacetylene. ing. These impurities, particularly acetylene compounds, have an action of poisoning the catalyst in the polymerization of olefins, causing problems such as a reduction in catalyst efficiency. Therefore, studies for removing these impurities have been made for some time.
一般的に、混合ガス中に不純物として含まれる微量な有害成分を選択的に除去する方法としては、大別すると、物理吸着による方法（「物理的除去法」という）と、化学反応により除去する方法（「化学的除去法」という）とに分けられる。
工業用オレフィンにおける不純物の除去方法としては、具体的には、以下のような除去方法が提案されている。
Generally, methods for selectively removing a trace amount of harmful components contained as impurities in a mixed gas can be broadly divided into a physical adsorption method (referred to as “physical removal method”) and a chemical reaction. It is divided into a method (referred to as “chemical removal method”).
Specifically, the following removal methods have been proposed as methods for removing impurities in industrial olefins.
先ず、オレフィン中のアセチレン系化合物を除去する、化学的除去法である一般的な方法として、例えば、特許文献１〜３に開示されたような、アルミナ担体に担持されたパラジウム触媒により、選択的に水素化反応し除去する方法が挙げられる。
また、その方法を応用した精製方法として、最初にＣ２及びＣ３オレフィン系ガスを別々の供給流に分離することなく、気相過程において同時にアセチレン類及びジオレフィン類不純物を選択的に水素化する、アセチレン系及びジオレフィン系不純物を含むＣ２及びＣ３オレフィン系供給流の選択的水素化方法が開示されている（特許文献４参照）。
しかしながら、いずれの方法においても高価な貴金属元素であるＰｄを使用することから、工業的規模で使用するには経済的に問題があった。そればかりでなく、オレフィン供給流中に水素ガス（Ｈ２）を導入し化学的除去（水添反応）することからＨ２の供給ラインが必要となり、また、未反応のＨ２がオレフィン流に残存する問題もあった。
First, as a general method that is a chemical removal method for removing an acetylenic compound from an olefin, for example, selective by a palladium catalyst supported on an alumina carrier as disclosed in Patent Documents 1 to 3. And a method of removing by hydrogenation.
Also, as a purification method applying the method, without first separating the C2 and C3 olefinic gases into separate feed streams, the acetylenes and diolefins impurities are selectively hydrogenated simultaneously in the gas phase process. A method for selective hydrogenation of C2 and C3 olefinic feed streams containing acetylenic and diolefinic impurities is disclosed (see Patent Document 4).
However, since Pd which is an expensive noble metal element is used in any method, there is an economical problem in using it on an industrial scale. In addition, since hydrogen gas (H 2 ) is introduced into the olefin feed stream and chemically removed (hydrogenation reaction), an H 2 supply line is required, and unreacted H 2 is converted into the olefin stream. There was also a problem that persisted.
その他の、物理的除去法による、オレフィン中のアセチレン系化合物を除去する方法としては、例えば、炭素数２〜８のオレフィンと、同じ若しくは同様な炭素含量を有するアセチレン系不純物と、任意の飽和炭化水素ガスとを含むガス混合物を、ＢＥＴガス吸着方法で測定して１０〜２，０００ｍ２／ｇの範囲内の表面積を有し、その上部にクロム、鉄、コバルト、ニッケル、ルテニウム、パラジウム及び白金から成る群から選択された少なくとも１種類の金属元素の、吸着剤の総重量に基づいて０．０１〜４０％が分散した、アルミナ、シリカ、活性炭、粘土及びゼオライトから成る群から選択された担体物質を主として含む吸着剤の粒状床に通して、床内の本質的に分子状水素を含まない雰囲気の存在下で、吸着剤による、含有されるアセチレン系汚染物の選択的かつ可逆的な吸着及び／又は錯体形成を行わせて、それによって予め定められたレベル未満のアセチレン系不純物を含有する精製流出物を得る工程と；その後に、結果としての吸着剤床を分子状水素を含む還元性ガスの存在下で再生して、吸着剤から含有されるアセチレン系不純物を放出させる工程とを含む精製方法が開示されている（特許文献５参照）。
しかしながら、本手法においてもＰｄなどの高価な貴金属元素を使用する方法も含まれ、分子状水素の供給も必要であって、工業的規模で使用するには経済的に問題があった。
Other methods for removing acetylene compounds in olefins by physical removal methods include, for example, olefins having 2 to 8 carbon atoms, acetylene impurities having the same or similar carbon content, and any saturated carbonization. A gas mixture containing hydrogen gas has a surface area in the range of 10 to 2,000 m 2 / g as measured by the BET gas adsorption method, and chromium, iron, cobalt, nickel, ruthenium, palladium and platinum on the top thereof A support selected from the group consisting of alumina, silica, activated carbon, clay and zeolite, wherein 0.01 to 40% is dispersed based on the total weight of the adsorbent of at least one metal element selected from the group consisting of Passed through a granular bed of adsorbent containing primarily material, contained by the adsorbent in the presence of an essentially molecular hydrogen free atmosphere in the bed. Allowing the selective and reversible adsorption and / or complexation of acetylenic contaminants to thereby obtain a purified effluent containing acetylenic impurities below a predetermined level; and as a result And a step of regenerating the adsorbent bed in the presence of a reducing gas containing molecular hydrogen to release the acetylenic impurities contained from the adsorbent (see Patent Document 5). .
However, this method also includes a method using an expensive noble metal element such as Pd, and it is necessary to supply molecular hydrogen, which is economically problematic for use on an industrial scale.
一方、銅及び亜鉛を含む触媒での不飽和炭化水素の水素化方法であって、有効成分が、未還元の形で、１０〜９５質量％の、酸化銅（ＩＩ）として計算される酸化銅（ＣｕＯ）と、５〜９０質量％の酸化亜鉛（ＺｎＯ）と、必要により０．１〜５０質量％の二酸化ジルコニウム（ＺｒＯ２）と、必要により０．１〜５０質量％のＡｌ２Ｏ３とから本質的になる触媒を使用することを特徴とする水素化方法が開示されている（特許文献６参照）。
また、アルミナ等の酸化物担体上の触媒を使用した、アルキン等の不飽和化合物を含む炭化水素流中の不飽和化合物を選択的に水素化する方法も開示されている（特許文献７参照）。
これらの手法においては、Ｐｄなどの高価な貴金属元素は使用しないものの、Ｈ２の供給は必要であるため、その供給設備が必要で、オレフィン流中にＨ２が残存する問題は解決されていない。
On the other hand, a method for hydrogenating unsaturated hydrocarbons with a catalyst containing copper and zinc, the active ingredient being in an unreduced form, 10 to 95% by mass, calculated as copper (II) oxide. and (CuO), and 5 to 90 wt% of zinc oxide (ZnO), and 0.1 to 50 wt% of zirconium dioxide (ZrO 2) if necessary, as required from 0.1 to 50 wt% Al 2 O 3 A hydrogenation method characterized by using a catalyst consisting essentially of the following is disclosed (see Patent Document 6).
Also disclosed is a method of selectively hydrogenating unsaturated compounds in a hydrocarbon stream containing unsaturated compounds such as alkynes using a catalyst on an oxide carrier such as alumina (see Patent Document 7). .
In these methods, although expensive noble metal elements such as Pd are not used, supply of H 2 is necessary, so that supply equipment is necessary, and the problem that H 2 remains in the olefin stream has not been solved. .
従来においては、種々の方法により製造された工業用オレフィン原料中には、通常、アセチレン、メチルアセチレン等の不純物のアセチレン系化合物が含有されている。この工業用オレフィンを、ポリマー製造用の原料モノマーとして使用するためには、含有されているアセチレン系化合物を１ｐｐｍよりも下の濃度レベル、時には０．１ｐｐｍよりも下のレベルにまで除去して、重合用触媒の被毒を防止する必要があるところ、背景技術として前述したように、従来のアセチレン系不純物の除去方法は、高価な触媒金属を使用したり、また、水素ガスの使用のために水素ガス供給ラインを必要とし、水素ガスが精製オレフィンに残存する問題があった。
そこで、本発明は、オレフィン原料からアセチレン系不純物を除去する際に、高価な触媒貴金属を使用せず、水素ガス供給が不要で、水素ガスの残存がないことにより、経済的で、簡易かつオレフィン精製を効率的に行える、オレフィン原料におけるアセチレン系不純物の除去精製方法を開発することを、発明が解決すべき課題とするものである。
Conventionally, industrial olefin raw materials produced by various methods usually contain acetylenic compounds of impurities such as acetylene and methylacetylene. In order to use this industrial olefin as a raw material monomer for polymer production, the contained acetylenic compound is removed to a concentration level below 1 ppm, sometimes to a level below 0.1 ppm, Where it is necessary to prevent poisoning of the polymerization catalyst, as described above as the background art, the conventional method for removing acetylenic impurities uses an expensive catalyst metal or because of the use of hydrogen gas. A hydrogen gas supply line was required, and there was a problem that hydrogen gas remained in the purified olefin.
Therefore, the present invention eliminates the need for expensive catalytic noble metal when removing acetylenic impurities from the olefin raw material, does not require supply of hydrogen gas, and does not leave hydrogen gas. It is an object of the present invention to develop a method for removing and purifying acetylene impurities from an olefin raw material that can be efficiently purified.
本発明者らは、上記の発明の課題を解決するために、高価な触媒貴金属を使用しない触媒金属を使用し、かつ水素ガスによる精製方法に依らずに、種々の触媒金属により、オレフィン原料からのアセチレン系不純物の除去精製方法を勘案試行して、特定の吸着剤を採用することにより、本発明の課題を解決し得ることを見い出して、本発明を創出するに至った。 In order to solve the above-described problems of the invention, the present inventors use a catalyst metal that does not use an expensive catalyst noble metal and do not depend on a purification method using hydrogen gas, but can use various catalyst metals to form an olefin raw material. In consideration of this acetylene-based impurity removal and purification method, it was found that the problem of the present invention can be solved by adopting a specific adsorbent, and the present invention was created.
すなわち、本発明は、上記公知技術及びその問題点を鑑みてなされたものであり、エチレン、プロピレンをポリマー製造用の原料モノマーとして使用するために、これらの原料モノマーにおいて、重合用の触媒を被毒させるアセチレン系化合物を重合用触媒に悪影響を及ぼさない程度の含有量にまで低減する簡便かつ効率的な方法であり、更にモノマー中にＨ２等のポリマー分子量に影響を与える物質が混入しない利点を有する。 That is, the present invention has been made in view of the above-mentioned known technology and its problems. In order to use ethylene and propylene as raw material monomers for polymer production, these raw material monomers are coated with a polymerization catalyst. This is a simple and efficient method for reducing the content of acetylene compounds to be poisoned to a level that does not adversely affect the polymerization catalyst, and the advantage that no substances that affect the polymer molecular weight such as H 2 are mixed in the monomer. Have
本発明では、発明の主要な要件として、活性アルミナとゼオライトの混合物からなるハイブリッド系吸着剤（以下単に、「ハイブリッド系吸着剤」ともいう）を用いることで、触媒被毒の原因となるオレフィン、特にエチレン、プロピレン中の、不純物としてのアセチレン系化合物を従来よりも効率的かつ確実に除去することが可能となる。
よって、本発明の第一の発明（基本発明；請求項１）は、アセチレン系化合物を不純物として含むオレフィンを、活性アルミナとゼオライトの混合物からなるハイブリッド系吸着剤と接触させ、アセチレン系化合物を除去することを特徴とする、オレフィンの精製方法、となる。
In the present invention, as a main requirement of the invention, by using a hybrid adsorbent composed of a mixture of activated alumina and zeolite (hereinafter also simply referred to as “hybrid adsorbent”), an olefin that causes catalyst poisoning, In particular, acetylene compounds as impurities in ethylene and propylene can be removed more efficiently and reliably than in the past.
Therefore, in the first invention of the present invention (basic invention; claim 1), an olefin containing an acetylene compound as an impurity is brought into contact with a hybrid adsorbent comprising a mixture of activated alumina and zeolite to remove the acetylene compound. The process for purifying olefins is characterized by the following.
なお、活性アルミナとゼオライトの混合物からなるハイブリッド系吸着剤は、従来から知られた吸着剤であるが、炭化水素の精製には、Ｃ４留分のブテン系の炭化水素からエーテル類やアルコール類等の含酸素化合物を除去する方法に使用されているのみであり（特開２０１０−０９５４９４，特開２０１０−０９５４９５）、従来の特許文献などを精査しても、オレフィン原料からのアセチレン系不純物の除去精製を行う、上記した本発明の要件（発明の特定事項）は見い出せない。そして、本発明は、後記の実施例により実証されているとおり、アセチレン系不純物が検出限界以下（０．１ｐｐｍ以下）までに除去され得る。 A hybrid adsorbent composed of a mixture of activated alumina and zeolite is a conventionally known adsorbent, but for purification of hydrocarbons, ethers, alcohols, etc. from butene-based hydrocarbons of the C4 fraction are used. It is only used in the method of removing oxygen-containing compounds (Japanese Patent Application Laid-Open No. 2010-095494, Japanese Patent Application Laid-Open No. 2010-095495), and even if the conventional patent documents are scrutinized, the removal of acetylenic impurities from the olefin raw material The above-mentioned requirements (specific matters of the invention) for carrying out the purification cannot be found. And this invention can remove an acetylene type impurity below a detection limit (0.1 ppm or less) as demonstrated by the below-mentioned Example.
段落００１１に前記した、本発明の基本発明に付随する実施の態様発明（従属請求項の各発明）としては、第二の発明として、ハイブリッド系吸着剤を１００〜６５０℃の温度で前処理することを特徴とする、第一の発明におけるオレフィンの精製方法であり、第三の発明として、活性アルミナの平均細孔径が１〜１００ｎｍであり、ゼオライトの平均細孔径が０.２〜１ｎｍであることを特徴とする、第一又は第二の発明におけるオレフィンの精製方法であり、第四の発明として、ハイブリッド吸着剤との接触温度が０〜１００℃であることを特徴とする、第一〜第三の発明におけるオレフィンの精製方法であり、第五の発明として、ハイブリッド系吸着剤との接触処理を二段以上の多段にすることを特徴とする、第一〜第四の発明におけるオレフィンの精製方法である。 As the second aspect of the invention of each of the embodiments described in paragraph 0011 (the inventions of the dependent claims), the hybrid adsorbent is pretreated at a temperature of 100 to 650 ° C. In the olefin purification method according to the first invention, the activated alumina has an average pore diameter of 1 to 100 nm, and the zeolite has an average pore diameter of 0.2 to 1 nm. A method for purifying olefins according to the first or second invention, wherein the contact temperature with the hybrid adsorbent is 0 to 100 ° C. as the fourth invention. In the olefin purification method according to the third aspect of the invention, as a fifth aspect of the invention, the contact treatment with the hybrid type adsorbent is made into a multistage of two or more stages. This is a method for purifying olefins.
更に、第六の発明として、エチレン又はプロピレン中のアセチレンを除去することを特徴とする、第一〜第五の発明におけるオレフィンの精製方法であり、第七の発明として、精製触媒部分として（イ）モレキュラーシーブ、（ロ）金属酸化物、又は（ハ）活性アルミナによる接触処理を併用することを特徴とする、第一〜第六の発明におけるレフィンの精製方法であり、第八の発明として、予め他の手段にてアセチレン系化合物の濃度を１０ｐｐｍ以下に低下させておくことを特徴とする、第一〜第七の発明におけるオレフィンの精製方法であり、第九の発明として、第一〜第八の発明における、オレフィンの精製方法により精製されたエチレン及び／又はプロピレンを用いることを特徴とする、エチレン及び／又はプロピレンの重合方法である。 Furthermore, as a sixth invention, there is provided an olefin purification method according to the first to fifth inventions characterized in that acetylene in ethylene or propylene is removed. (Ii) a method of refining olefins according to the first to sixth inventions, characterized in that it is used in combination with a molecular sieve, (b) a metal oxide, or (c) activated alumina. The method for purifying olefins according to the first to seventh inventions, wherein the concentration of the acetylene compound is reduced to 10 ppm or less in advance by other means. Ethylene and / or propylene polymerization method characterized by using ethylene and / or propylene purified by olefin purification method in eight inventions A.
本発明は、オレフィン原料からアセチレン系不純物を除去する際に、高価な触媒貴金属を使用せず、水素ガス供給が不要で、水素ガスの残存がないことにより、経済的で、簡易にオレフィン精製を効率的に行える。
具体的には、本発明により、アセチレン系化合物を除去して精製したエチレン、プロピレンは、不純物に弱い重合触媒、例えばメタロセン触媒の重合用モノマーとして用いることが可能であり、ポリエチレン、ポリプロピレン単独重合体やプロピレン・α−オレフィン共重合体、プロピレンブロック共重合体などを触媒の被毒なく、安定した触媒効率で生産することが可能となる。
The present invention eliminates the need for expensive catalytic noble metals when removing acetylenic impurities from olefin raw materials, eliminates the need for hydrogen gas supply, and does not leave any hydrogen gas. It can be done efficiently.
Specifically, according to the present invention, ethylene and propylene purified by removing an acetylene compound can be used as a polymerization monomer for a polymerization catalyst that is weak against impurities, such as a metallocene catalyst. , Propylene / α-olefin copolymers, propylene block copolymers and the like can be produced with stable catalyst efficiency without poisoning of the catalyst.
以下においては、本発明の各請求項に係る、原料オレフィン、ハイブリッド吸着剤、精製処理手法等について、本発明を詳細に説明する。 In the following, the present invention will be described in detail with respect to raw material olefins, hybrid adsorbents, purification treatment techniques and the like according to the claims of the present invention.
〔Ｉ〕原料オレフィン
本発明において原料として使用されるオレフィンは、種々の方法によって製造された、アセチレン系化合物を含有する工業用オレフィンを用いることができるが、特にエチレンプラントのロードアップや重質油の接触分解生成物から得られるＣ２，３留分の分離等によって製造される工業用エチレン、及びＦＣＣプロピレン（ＦＣＣ；Ｆｌｕｉｄ Ｃａｔａｌｙｔｉｃ Ｃｒａｃｋｉｎｇ Ｐｒｏｃｅｓｓ）を用いる場合に好適に適用される。
これら原料オレフィン中に含有されるアセチレン系化合物は、１００ｐｐｍ以下の場合に適用され、特に１０ｐｐｍ以下であることが好ましい。仮に、原料オレフィン中に１００ｐｐｍを超える濃度でアセチレン系化合物が含有されている場合には、予め蒸留やＰＳＡ（Ｐｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐｔｉｏｎ）法などの他の手段にてアセチレン系化合物の濃度を１０ｐｐｍ以下に予め低下させておくことが望ましい。
[I] Raw Olefin As the olefin used as a raw material in the present invention, an industrial olefin containing an acetylene compound produced by various methods can be used. It is suitably applied when using industrial ethylene produced by separation of C2,3 fractions obtained from the catalytic cracking product of, and FCC propylene (FCC; Fluid Catalytic Cracking Process).
The acetylenic compound contained in these raw material olefins is applied in the case of 100 ppm or less, and is preferably 10 ppm or less. If the raw material olefin contains an acetylene compound at a concentration exceeding 100 ppm, the concentration of the acetylene compound is previously reduced to 10 ppm or less by other means such as distillation or PSA (Pressure Swing Adsorption). It is desirable to reduce it.
〔ＩＩ〕ハイブリッド系吸着剤
（１）吸着剤の組成
本発明で用いられるハイブリッド系吸着剤は、活性アルミナ及びゼオライトの混合物からなり、活性アルミナ及びゼオライトの合計１００重量％中、通常、活性アルミナ２０〜８０重量％及びゼオライト８０〜２０重量％、好ましくは活性アルミナ３０〜７０重量％及びゼオライト７０〜３０重量％の混合物からなる。
なお、段落００１２に前記したように、かかるハイブリッド系吸着剤は、従来から知られた吸着剤であり、ハイブリッド系吸着剤は、市販品を用いてもよい。
通常、原料オレフィンはアセチレン系化合物以外の不純物（例えば、Ｈ２Ｏ，ＣＯ、ＣＯＳ等）も含んでいるため、ハイブリッド系吸着剤を充填した吸着カラムの前後に別途、モレキュラーシーブス、活性アルミナ、金属酸化物等を充填した吸着カラムを併用し、それらの不純物を除去することができる。
[II] Hybrid Adsorbent (1) Composition of Adsorbent The hybrid adsorbent used in the present invention is a mixture of activated alumina and zeolite, and is usually activated alumina 20 in a total of 100% by weight of activated alumina and zeolite. -80 wt% and zeolite 80-20 wt%, preferably a mixture of activated alumina 30-70 wt% and zeolite 70-30 wt%.
As described above in paragraph 0012, such a hybrid adsorbent is a conventionally known adsorbent, and a commercially available hybrid adsorbent may be used.
Usually, raw material olefins also contain impurities other than acetylene compounds (for example, H 2 O, CO, COS, etc.). Therefore, molecular sieves, activated alumina, metals are separately provided before and after the adsorption column filled with the hybrid adsorbent. An adsorption column filled with oxide or the like can be used in combination to remove these impurities.
ハイブリッド系吸着剤を構成する活性アルミナとは、水酸化アルミナを結晶性の低い多孔質の酸化アルミニウムに転移させて吸着能力を持たせたものをいい、比表面積及び細孔容積が高く、優れた吸着能力を有する。活性アルミナは、市販品を用いてもよいし、公知の方法により製造してもよい。 The activated alumina that constitutes the hybrid adsorbent is the one obtained by transferring alumina hydroxide to porous aluminum oxide with low crystallinity to give adsorption ability, and has a high specific surface area and high pore volume and is excellent. Has adsorption capacity. The activated alumina may be a commercially available product, or may be produced by a known method.
上記活性アルミナの平均細孔径は通常１〜１００ｎｍ、好ましくは１〜８０ｎｍである。活性アルミナの平均粒径は特に制限はなく、平均細孔径が上記の範囲であると、アセチレン系化合物を含む種々の不純物を効率的に吸着させることができるので好ましい。
好ましい活性アルミナとしては特に制限されるものではないが、γ−アルミナなどが挙げられる。
The average pore diameter of the activated alumina is usually 1 to 100 nm, preferably 1 to 80 nm. The average particle diameter of the activated alumina is not particularly limited, and it is preferable that the average pore diameter is in the above range because various impurities including an acetylene compound can be adsorbed efficiently.
Although it does not restrict | limit especially as a preferable activated alumina, (gamma) -alumina etc. are mentioned.
ハイブリッド系吸着剤を構成するゼオライトは、公知の方法により合成して製造することができる。
上記ゼオライトの平均細孔径は、通常０.２〜１ｎｍ、好ましくは０.５〜１ｎｍである。ゼオライトの平均粒径は特に制限はなく、平均細孔径が上記の範囲であると、アセチレン系化合物を含む種々の不純物を効率的に吸着させることができるので好ましい。
The zeolite constituting the hybrid adsorbent can be synthesized and produced by a known method.
The average pore diameter of the zeolite is usually 0.2 to 1 nm, preferably 0.5 to 1 nm. The average particle diameter of the zeolite is not particularly limited, and it is preferable that the average pore diameter is in the above range because various impurities including an acetylene compound can be adsorbed efficiently.
好ましいゼオライトとしては特に制限されるものではないが、ゼオライトＸ、Ｙ及びＡ等が挙げられ、特に好ましくはゼオライトＸ等が挙げられる。（なお、これらの各種ゼオライトは、ゼオライトの種類としての通称であり周知のものである。）
なお、オレフィン中に水及びアルコールなどの極性を有する不純物が多く含まれていると、これらの不純物がアセチレン系化合物よりも優先してハイブリッド系吸着剤に吸着されるので、ゼオライト（モレキュラーシーブス）やアルミナ等の吸着剤をハイブリッド系吸着剤の前段に併用することもでき、むしろ、そうする方が好ましい。
ハイブリッド系吸着剤と併用される単独のゼオライト及び活性アルミナ吸着剤の平均粒径は特に制限はないが、平均細孔径は上述した範囲のものを使用するのが好ましい。
Although it does not restrict | limit especially as a preferable zeolite, Zeolite X, Y, A, etc. are mentioned, Especially preferably, zeolite X etc. are mentioned. (In addition, these various zeolites are common names as types of zeolite and are well known.)
If the olefin contains a large amount of polar impurities such as water and alcohol, these impurities are preferentially adsorbed to the hybrid adsorbent over the acetylene compound, so that zeolite (molecular sieves) and An adsorbent such as alumina can also be used in front of the hybrid adsorbent, but it is preferable to do so.
The average particle diameter of the single zeolite and the activated alumina adsorbent used in combination with the hybrid adsorbent is not particularly limited, but the average pore diameter is preferably within the above-mentioned range.
平均細孔径の測定法は、窒素吸脱着法による吸着及び脱離等温線の測定等が用いられる。本測定においては、窒素ガスを使用する。細孔分布を調べるときに一般的な吸着ガスとしての特性もよく使用されているためである。
脱離等温線は相対圧を減少させた場合に得られる曲線である。脱離等温線の方が、吸着等温線に比べて、同一の吸着ガス量に対してより低い相対圧力を示し、結果的により低い自由エネルギー状態を示すために、より真の熱力学的安定に近い状態であると一般的に考えられている。
上記分析装置としては、カンタークロム社（オートソーブ）、日本ベル社（ベルソープ）、コールター社（４０オムニソープ）等の一般市販品が使用可能である。細孔分布の計算方法としては、ＢＪＨ法が最も一般的である。
測定方法の一例を以下具体的に示す。温度７７Ｋで、圧力は相対圧Ｐ／Ｐ０（Ｐ０は、大気圧である）が０．０２〜１の範囲で測定する。ＢＪＨ法により、横軸を細孔直径（単位：オングストローム，Å）、縦軸に細孔容積の微分値（単位：ｃｍ３／ｇ）で表現する。測定回数は通常１回で充分である。
As a method for measuring the average pore diameter, measurement of adsorption and desorption isotherms by a nitrogen adsorption / desorption method is used. Nitrogen gas is used in this measurement. This is because the characteristics as a general adsorption gas are often used when examining the pore distribution.
The desorption isotherm is a curve obtained when the relative pressure is decreased. The desorption isotherm is more truly thermodynamically stable than the adsorption isotherm because it exhibits a lower relative pressure for the same amount of adsorbed gas and consequently a lower free energy state. It is generally considered close.
As the analyzer, general commercial products such as Canter Chrome (Autosorb), Nippon Bell (Bellethorpe), Coulter (40 Omni Soap) and the like can be used. The BJH method is the most common method for calculating the pore distribution.
An example of the measurement method is specifically shown below. At a temperature of 77K, the pressure is measured in the range of relative pressure P / P 0 (P 0 is atmospheric pressure) in the range of 0.02-1. By the BJH method, the horizontal axis is represented by the pore diameter (unit: angstrom, Å), and the vertical axis is represented by the differential value of the pore volume (unit: cm 3 / g). One measurement is usually sufficient.
（２）吸着剤の形状
本発明において用いられる吸着剤の形状は、特に制限は無く、ペレット状、粉末状、粒状の他、円滴状、円盤状などに成形されたものでもよい。吸着材の形状は、使用態様に応じて適宜選択すればよく、その大きさも、使用条件に応じて適宜選択できる。
(2) Shape of adsorbent The shape of the adsorbent used in the present invention is not particularly limited, and may be a pellet, powder, granule, a droplet, a disk, or the like. What is necessary is just to select the shape of an adsorbent suitably according to a use aspect, and the magnitude | size can also be suitably selected according to use conditions.
〔ＩＩＩ〕処理条件
（１）ハイブリッド系吸着剤の前処理（活性化処理）
本発明のハイブリッド系吸着剤は前処理として加熱活性化処理されていることが好ましい。
本発明の前処理（活性化処理）温度は、不活性ガス流通下、１００〜６５０℃であり、好ましくは２００〜６００℃、より好ましくは３００〜６００℃、最も好ましくは４００〜６００℃である。前処理温度が高過ぎるとゼオライト結晶の崩れが激しくなり除去効率が低下し、前処理温度が低過ぎると除去効率が低くなる。不活性ガスとしては窒素、アルゴン、ヘリウム等が使用できる。
本発明の前処理（活性化処理）時間は、０．１〜１００時間、好ましくは０．５〜５０時間、より好ましくは１〜２５時間である。
[III] Treatment conditions (1) Pretreatment of hybrid adsorbent (activation treatment)
The hybrid adsorbent of the present invention is preferably heat activated as a pretreatment.
The pretreatment (activation treatment) temperature of the present invention is 100 to 650 ° C., preferably 200 to 600 ° C., more preferably 300 to 600 ° C., and most preferably 400 to 600 ° C. under an inert gas flow. . If the pretreatment temperature is too high, the zeolite crystals are severely collapsed and the removal efficiency is lowered. If the pretreatment temperature is too low, the removal efficiency is lowered. Nitrogen, argon, helium, etc. can be used as the inert gas.
The pretreatment (activation treatment) time of the present invention is 0.1 to 100 hours, preferably 0.5 to 50 hours, more preferably 1 to 25 hours.
（２）オレフィンとハイブリッド系吸着剤の接触温度
本発明の接触温度は、０〜１００℃であり、好ましくは１０〜６０℃であり、より好ましくは２０〜５０℃の範囲である。処理温度が高過ぎると液化オレフィンの場合には気化し処理操作が効率的でなくなる。また、気体オレフィンの場合には副反応が生じる懸念がある。同様に処理温度が低過ぎると除去効率が低くなる。
(2) Contact temperature between olefin and hybrid adsorbent The contact temperature of the present invention is 0 to 100 ° C, preferably 10 to 60 ° C, more preferably 20 to 50 ° C. If the treatment temperature is too high, the liquefied olefin vaporizes and the treatment operation becomes inefficient. In the case of gaseous olefins, there is a concern that side reactions occur. Similarly, if the processing temperature is too low, the removal efficiency is lowered.
（３）オレフィンとハイブリッド系吸着剤の接触時間
本発明の接触時間としては、オレフィン中のアセチレン系化合物濃度、ハイブリッド系吸着剤量、接触温度、接触圧力等により適宜選択される。通常は１分〜１００時間である。
(3) Contact time of olefin and hybrid adsorbent The contact time of the present invention is appropriately selected depending on the concentration of the acetylene compound in the olefin, the amount of the hybrid adsorbent, the contact temperature, the contact pressure, and the like. Usually, it is 1 minute to 100 hours.
（４）オレフィンとハイブリッド系吸着剤の接触圧力
本発明の接触圧力としては、常圧で行なうことができるが、０．２〜５ＭＰａ、好ましくは、０．５〜４ＭＰａの圧力下においても行なうことができる。
(4) Contact pressure between olefin and hybrid adsorbent The contact pressure of the present invention can be carried out at normal pressure, but it is also carried out under a pressure of 0.2 to 5 MPa, preferably 0.5 to 4 MPa. Can do.
（５）オレフィンとハイブリッド系吸着剤の接触方法
本発明の接触方法としては、通常はオレフィンをガス状で流通接触させるが、これに限定されるものではなく、プロピレンの場合には液状で接触させても良い。ハイブリッド系吸着剤の充填態様としては、接触塔の形状に応じて適宜選択すればよく、一般的には固定床が用いられるが、移動床、流動床等として充填することもできる。
(5) Contacting method of olefin and hybrid adsorbent As the contacting method of the present invention, olefin is usually contacted in a gaseous state, but is not limited to this, and in the case of propylene, it is contacted in liquid form. May be. The filling mode of the hybrid adsorbent may be appropriately selected according to the shape of the contact tower, and a fixed bed is generally used, but it can also be packed as a moving bed, a fluidized bed or the like.
（６）他の吸着剤による補足処理
特にメタロセン触媒などの不純物の影響を受け易い触媒によるオレフィンの重合では、アセチレン系化合物濃度を下げるために、オレフィンを、本発明の活性アルミナとゼオライトの混合物からなるハイブリッド系吸着剤で接触処理することが有用であるが、更に各種の慣用の追加可能な精製触媒部分による接触といえる（イ）モレキュラーシーブ接触、（ロ）金属酸化物接触、及び（ハ）活性アルミナ接触、との併用接触をすることにより、アセチレン系化合物以外のその他多種の不純物を除去することが可能となり有益である。
(6) Supplementary treatment with other adsorbents Particularly in the polymerization of olefins with a catalyst that is easily affected by impurities such as metallocene catalysts, in order to reduce the concentration of acetylene compounds, the olefins are mixed from the activated alumina and zeolite mixture of the present invention. It is useful to perform the contact treatment with the hybrid adsorbent as described above, but it can also be said to be contact by various conventional and usable additional purification catalyst parts (a) molecular sieve contact, (b) metal oxide contact, and (c) By making contact with activated alumina in combination, it is possible to remove various impurities other than acetylene compounds, which is beneficial.
このような、いわゆる併用接触による実施態様の例を示すと以下のとおりになる。
（１）モレキュラーシーブ接触後に、ハイブリッド系吸着剤による併用接触
（２）金属酸化物接触後に、ハイブリッド系吸着剤による併用接触
（３）活性アルミナ接触後に、ハイブリッド系吸着剤による併用接触
（４）ハイブリッド系吸着剤接触後に、金属酸化物又は金属酸化物の複合酸化物による併用接触
（５）金属酸化物又は金属酸化物の複合酸化物による接触後に、ハイブリッド系吸着剤接触、次いで金属酸化物又は金属酸化物の複合酸化物による多段併用接触
An example of such an embodiment using so-called combined contact is as follows.
(1) Combined contact with hybrid adsorbent after molecular sieve contact (2) Combined contact with hybrid adsorbent after metal oxide contact (3) Combined contact with hybrid adsorbent after activated alumina contact (4) Hybrid (5) Hybrid adsorbent contact, followed by metal oxide or metal after contact with metal oxide or metal oxide composite oxide Multi-stage contact with oxide complex oxide
以上のハイブリッド系吸着剤、及び追加可能な精製触媒による接触処理は、オレフィンの性状、品質を考慮して種々の組み合わせの変更及び回数などを、任意に多段に設定できる。というのも、活性アルミナとゼオライトの混合物からなるハイブリッド系吸着剤による接触は、専ら、ハイブリッド系吸着剤の含有量を順次低下させるのに対して、この追加可能な精製触媒はそれ以外の触媒毒のような不純物の含有量を順次低下させることにも有益であり、具体的には、例えば、エチレン、プロピレンを重合に供する場合に、あらゆる触媒毒を無害化することにより、メタロセン触媒の活性を全体的に維持するという点で顕著に有用である。
このように、エチレン、プロピレンを、予めモレキュラーシーブ接触、金属酸化物又は金属酸化物の複合酸化物接触、或いは活性アルミナなどの追加可能な汎用の各種の精製触媒部分と接触後、ハイブリッド系吸着剤により接触する併用接触も有益である。ハイブリッド系吸着剤処理を二段、三段にすることも可能であり、又追加可能な精製触媒部分を任意に多段に併設すること、その接触前後を任意に変えるいずれの態様も本発明の技術範囲に含まれる。
In the contact treatment using the above hybrid adsorbent and an additional purification catalyst, various combinations of changes and the number of times can be arbitrarily set in consideration of the properties and quality of the olefin. This is because contact with a hybrid adsorbent composed of a mixture of activated alumina and zeolite exclusively reduces the content of the hybrid adsorbent in turn, while this additional purification catalyst can be used for other catalyst poisons. In particular, for example, when ethylene or propylene is used for polymerization, the activity of the metallocene catalyst can be reduced by detoxifying any catalyst poison. Remarkably useful in terms of overall maintenance.
In this way, after contacting ethylene and propylene with a molecular sieve contact, a metal oxide or a composite oxide contact of metal oxide, or various general-purpose purification catalyst parts that can be added such as activated alumina, a hybrid adsorbent Combined contact that makes contact with is also beneficial. The hybrid adsorbent treatment can be performed in two or three stages, and an optional purification catalyst portion can be provided in multiple stages, and any aspect that arbitrarily changes the contact before and after the contact can be achieved by the technology of the present invention. Included in the range.
〔ＩＶ〕アセチレン濃度測定
モレキュラーカーボンカラムを用いたＧＣ／ＭＳ分析（ガスクロ／マス分析）にて行う。
[IV] Measurement of acetylene concentration The acetylene concentration is measured by GC / MS analysis (gas chromatography / mass analysis) using a molecular carbon column.
以下、実施例に基づいて本発明を更に具体的に説明するが、本発明の実施例と比較例との対照において、本発明の構成要件の合理性と有意性及び本発明の卓越性を実証するものである。 Hereinafter, the present invention will be described more specifically based on examples, but the rationality and significance of the constituent elements of the present invention and the superiority of the present invention are demonstrated in contrast with the examples of the present invention and comparative examples. To do.
［実施例１］
予めハイブリッド系吸着剤として、平均細孔径１〜１００ｎｍの活性アルミナと平均細孔径０．９ｎｍのゼオライトから成るＡＺ−３００（＃７×１４ １．４−２．８ｍｍφ ＵＯＰ社／ユニオン昭和製）０．５ｇをＵ字管に仕込み、６００℃、Ｈｅガス流通下で前処理を行った。
アセチレンの吸着性はエチレンを吸着材に通す前後の濃度で評価をした。また標準ガスとして、アセチレン４ｐｐｍ含有のエチレンガスを用いた。予め処理したハイブリッド系吸着剤に、２５℃にて５０ｃｃ／ｍｉｎの速度で９０分間エチレンガスを流した。９０分経過時の通過ガスをサンプリングボトルに採取し、Ｈｅ気流下、ｏｎ−ｌｉｎｅでＧＣ／ＭＳへ導入した。ＧＣカラムとしてパックドカラム（ｓｈｉｎｃａｒｂｏｎＳＴ）を用いた。吸着剤通過後のアセチレン濃度を表１に示す。
[Example 1]
As a hybrid adsorbent, AZ-300 (# 7 × 14 1.4-2.8 mmφ UOP / Union Showa) made of activated alumina having an average pore diameter of 1 to 100 nm and zeolite having an average pore diameter of 0.9 nm was previously prepared. .5 g was charged into a U-shaped tube and pre-treated at 600 ° C. under He gas flow.
The adsorptivity of acetylene was evaluated by the concentration before and after passing ethylene through the adsorbent. Further, ethylene gas containing 4 ppm of acetylene was used as a standard gas. Ethylene gas was allowed to flow for 90 minutes at a rate of 50 cc / min at 25 ° C. through the pre-treated hybrid adsorbent. The passing gas after 90 minutes was collected in a sampling bottle and introduced into the GC / MS on-line under a He stream. A packed column (shincarbonST) was used as the GC column. Table 1 shows the acetylene concentration after passing through the adsorbent.
［比較例１］
予めパラジウム／アルミナ吸着剤として、ＰｏｌｙＭａｘ２００（３−５ｍｍ Ｓｐｈ．ズード・ケミー製）０．１ｇをＵ字管に仕込み、１５０℃、Ｈｅガス流通下で前処理を行った。また、２０分間エチレンガスを流し、接触温度を４０℃とすること以外は実施例１と同様に行った。
[Comparative Example 1]
As a palladium / alumina adsorbent, 0.1 g of PolyMax 200 (manufactured by 3-5 mm Sph. Zude Chemie) was charged in a U-shaped tube in advance, and pretreatment was performed at 150 ° C. under He gas flow. Moreover, it carried out like Example 1 except flowing ethylene gas for 20 minutes, and making contact temperature 40 degreeC.
［比較例２］
ＰｏｌｙＭａｘ２００を０．５ｇ充填、多量のＨ２（＞１８０ｐｐｍ）による水添反応を行ったこと以外は比較例１と同様に行った。
[Comparative Example 2]
The same procedure as in Comparative Example 1 was performed except that 0.5 g of PolyMax 200 was charged and a hydrogenation reaction with a large amount of H 2 (> 180 ppm) was performed.
表１の結果を見ると、本願の実施例にあっては、エチレン流通量５０ｃｃ／ｍｉｎで９０分間流通継続において、アセチレンが検出限界以下（０．１ｐｐｍ以下）までに除去され、かつ、水添反応に依らないため水素が混入していない。
これに対して、高価なパラジウム／アルミナを用いる比較例１にあっては、水添反応には依らないものの、吸着能力が不十分なため吸着剤接触後もアセチレンが多量に残存していた。また、比較例２にあっては、水添反応により実施例１と同様にアセチレンが検出限界以下（０．１ｐｐｍ以下）までに除去されている。しかし、多量のＨ２を使用することから吸着剤接触後にＨ２が残存していた。
As seen from the results in Table 1, in the examples of the present application, acetylene was removed to below the detection limit (0.1 ppm or less) in the continuous flow for 90 minutes at an ethylene flow rate of 50 cc / min, and hydrogenation was performed. Since it does not depend on the reaction, hydrogen is not mixed.
On the other hand, in Comparative Example 1 using expensive palladium / alumina, although it did not depend on the hydrogenation reaction, a large amount of acetylene remained even after contact with the adsorbent because of insufficient adsorption capacity. In Comparative Example 2, acetylene was removed by the hydrogenation reaction to the detection limit or less (0.1 ppm or less) as in Example 1. However, since a large amount of H 2 was used, H 2 remained after contacting the adsorbent.
本発明のオレフィンの精製方法は、オレフィン、特にエチレン、プロピレン中のアセチレン系化合物の不純物を、経済的に簡便かつ極めて効率的に吸着除去できる。そのため、精製したオレフィンはモノマーとして使用した場合に、重合用触媒、特にメタロセン触媒の被毒が極めて少ないため、飛躍的に安定した触媒効率での生産が可能となる。更に、水添反応に依らないため、オレフィンモノマー中にＨ２が残存することなく、特に、Ｈ２に対して反応性の高いメタロセン触媒での分子量制御性が安定する。
以上の理由から、ポリプロピレン単独重合体、ポリエチレン単独重合体、プロピレン・α−オレフィン共重合体、プロピレン系ブロック共重合体等々の製造や、オレフィンを接触反応原料として用いる有機化合物（例えばフェノールやアクリル酸等々）の製造におけるコストを大幅に低減でき、よって、重合用モノマー材料や接触反応原料としての利用が格段に広がる。
The method for purifying olefins of the present invention can adsorb and remove impurities of olefins, particularly acetylene compounds in ethylene and propylene, economically simply and extremely efficiently. Therefore, when the purified olefin is used as a monomer, the polymerization catalyst, particularly the metallocene catalyst, is extremely less poisoned, so that production with dramatically stable catalyst efficiency becomes possible. Furthermore, since it does not depend on the hydrogenation reaction, H 2 does not remain in the olefin monomer, and in particular, the molecular weight controllability with a metallocene catalyst highly reactive with H 2 is stabilized.
For these reasons, the production of polypropylene homopolymers, polyethylene homopolymers, propylene / α-olefin copolymers, propylene-based block copolymers, etc., and organic compounds using olefins as contact reaction raw materials (for example, phenol and acrylic acid) Etc.), and the use as a monomer material for polymerization and a raw material for contact reaction is greatly expanded.
Claims (9)
A method for polymerizing ethylene and / or propylene, characterized by using ethylene and / or propylene purified by the method for purifying olefins according to any one of claims 1 to 8.
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