JPH0259808B2 - - Google Patents
Info
- Publication number
- JPH0259808B2 JPH0259808B2 JP59247935A JP24793584A JPH0259808B2 JP H0259808 B2 JPH0259808 B2 JP H0259808B2 JP 59247935 A JP59247935 A JP 59247935A JP 24793584 A JP24793584 A JP 24793584A JP H0259808 B2 JPH0259808 B2 JP H0259808B2
- Authority
- JP
- Japan
- Prior art keywords
- adsorption
- adsorption tower
- gas
- adsorbent
- raw material
- 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.)
- Expired - Lifetime
Links
- 238000001179 sorption measurement Methods 0.000 claims description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 238000010926 purge Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000005749 Copper compound Substances 0.000 claims description 8
- 150000001880 copper compounds Chemical class 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 34
- 150000001336 alkenes Chemical class 0.000 description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 6
- -1 ethylene, propylene, butylene, pentene Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
産業上の利用分野
本発明は吸着分離方法によつてオレフイン類を
含む原料ガスよりオレフイン系炭化水素、特にエ
チレン、プロピレン、ブチレン、ペンテンなど
（以下エチレン等という）を回収する方法に関す
るものである。
エチレン等のオレフイン系炭化水素類が石油化
学製品であるエタノール、エチレンオキサイド、
アセトアルデヒド、塩化ビニル、スチレン、酢酸
ビニル、エチレングリコール、低密度リニアーポ
リエチレン、プロパノール、プロピレンオキサイ
ド、アセトン、ポリプロピレン、ブタノール、ブ
タジエン、ポリブデン、ブチルゴム等の原料とし
て有用なものであることは周知の通りである。
従来の技術
従来のオレフイン類の一般的な製造法について
簡単に説明すると、先ず原料ナフサとスチームを
混合して、熱分解炉に送入し、ナフサの熱分解を
行ない、次に生成ガスを直ちに水との熱交換及び
重質油の注入によつて120℃付近まで急冷し、液
化したC5以上の炭化水素成分を分離する。次に
この非液化ガスは圧縮して不純物を除去した後、
エチレンやプロピレンなどの冷媒を用いて液化
し、蒸留によつてエチレン、Ｐ−Ｐ留分、C4留
分、残ガス、エタンなどの留分に分離する。
以上説明したように、ナフサの熱分解ガス中か
らオレフイン類などの有用成分を分離、精製する
時の基本原理は低温加圧蒸留（深冷分離法）であ
る。この方法は原料ガスを冷却液化し−100℃〜
−200℃で分留するものである。
発明が解決しようとする問題点
しかしながら、上記の方法においては、原料ガ
ス中に水分や二酸化炭素が存在すると、これらが
低温管システム内で固化して閉塞事故を起すので
前処理によりこれらを十分に除去しなければなら
ないという問題がある。
更に前記した従来の方法には、複雑な冷凍及び
熱回収システムの使用が必要であり、しかも装置
に特殊な金属材料などの高級材料を使用すること
が必要なために装置が高価となり、また冷凍用コ
ンプレツサーの使用が必要などのために運転経費
も高いなどの問題がある。
本発明者等は前記した従来のオレフイン類の製
造方法における問題点を解決すべく検討を重ねた
結果、オレフインを含む原料ガスからオレフイン
を選択的に吸着する銅化合物−活性炭から成る吸
着剤を使用してエチレン、プロピレンなどのオレ
フイン系炭化水素類を効率よく分離する方法を見
出した。
問題点を解決するための手段及びその作用効果
本発明に従つたオレフイン系炭化水素類の精製
分離方法はオレフイン類を含む原料ガスから、吸
着分離方法によりオレフイン系炭化水素類を回収
する方法において、銅化合物−活性炭系吸着剤を
充填した２つ以上の吸着塔を用い、
(1) 原料ガスを吸着塔に流して、オレフイン系炭
化水素類を吸着させる吸着工程、
(2) 吸着工程の終了した吸着塔へ製品ガスを導入
して、難吸着成分をパージするパージ工程及び
(3) 吸着塔内を減圧又は加熱することによつて吸
着剤に吸着されているオレフイン系炭化水素を
脱着回収する回収工程を、２つ以上の吸着塔に
おいて繰り返し実施することを特徴とした方法
に関するものである。
本発明における前記行程(1)は吸着塔内に原料ガ
スを流通させることによつて、オレフイン類を吸
着塔に吸着させる吸着工程である。この吸着工程
では吸着塔内の圧力を常圧で運転することにより
十分な効果が得られるが、加圧状態で操作するこ
とも可能であり、この場合は吸着量が増加したり
高温ガスでも処理できるなどの利点がある。加圧
状態で運転する場合においても高い吸着圧は必要
ではなく10Kg／cm2以下、好ましくは、２〜５Kg／
cm2の吸着圧で十分である。
原料ガスの吸着塔内への流入は吸着塔出口にお
いてオレフイン成分が検出されはじめる時点から
吸着塔入口における濃度に達する時点までの間の
任意の時点まで行なう。又、吸着操作時の温度は
常圧下の場合で−40〜90℃、好ましくは０〜60℃
であり、加圧下では−10℃〜120℃、好ましくは
20℃〜80℃である。
前記工程(2)は吸着工程が終了した吸着塔内に製
品ガスを導入して塔内の空隙に残留する難吸着成
分をパージする工程である。かかる工程(2)の実施
により有用成分であるオレフイン系炭化水素類の
回収純度が向上するという利点が得られ、この工
程は本発明において必須の工程である。製品ガス
の導入の終点は例えば吸着塔出口のガス分析を実
施して有用成分濃度を検知して定めることができ
る。
前記工程(3)はパージ工程が終つた吸着塔を減圧
又は加熱することにより、吸着剤に吸着されてい
るオレフイン類を脱着させ、空隙に残留するパー
ジガスと共に回収する工程である。減圧によつて
脱着を行なう場合は、例えば真空ポンプにより塔
内を100torr以下に減圧して運転するのが好まし
い。また加熱による場合は塔内温度40〜250℃好
ましくは60〜180℃に加熱して運転するのが好ま
しい。
本発明で使用する銅化合物−活性炭吸着剤は銅
（）のハライド塩もしくは酸化銅（）又は銅
（）のハライド塩、カルボン酸塩、硫酸塩、塩
基性塩もしくはアンミン錯塩或いは酸化銅（）
などの銅化合物を適当な溶媒に溶解または懸濁
し、これに活性炭を加えて十分に撹拌した後、液
相を減圧留去などの方法で除去することにより得
ることができる。
吸着剤に用いられる活性炭には特に限定はない
が、形状的には成形炭及び破砕炭からなる粒状炭
及び粉末炭もしくは繊維状のものが好ましい。か
かる活性炭の原料としては、木材、ヤシ殼、石炭
石油系ピツチ及び合成繊維などが用いることがで
きる。本発明に用いる吸着剤中の活性炭と銅化合
物との重量比（活性炭／銅化合物）は一般には
0.5〜60.0、好ましくは2.0〜10.0とする。
以下、本発明の具体的について図面を参照して
説明する。第１図は２塔の吸着塔からなり、減圧
脱着によつて原料ガスからオレフイン類を吸着回
収する装置図である。吸着塔Ａ及びＢにはオレフ
イン類を選択的に吸着する銅化合物−活性炭系吸
着剤を充填する。
かかる装置の運転について説明すると、先ずバ
ルブ１，３及び５を開き、吸着塔Ａ内に原料ガス
を流通させ、オレフインガスを吸着剤に吸着させ
る。この際バルブ２，４，６，７及び８は閉じた
状態である。吸着工程終了後バルブ１を閉じ、吸
着塔Ａ内の空隙に残留する難吸着性ガスをパージ
するため、バルブ２を開き製品ガスを吸着塔Ａ内
に導入し非吸着性成分をパージする。
パージ工程終了後はバルブ２，３及び５を閉
じ、バルブ７を開き、吸着されたオレフインガス
及び空隙内に残留するパージガスを真空ポンプに
よつて吸引して回収する。
吸着塔Ａでの回収工程の間に、吸着塔Ｂでは吸
着工程及びパージ工程を実施する。即ち吸着塔Ａ
内のオレフインガスを真空ポンプで吸引回収する
間、バルブ１，４及び６を開き、吸着塔Ｂ内に原
料ガスを流通させ、オレフインガスを吸着させ
る。ついでバルブ１を閉じ、バルブ２を開いて製
品ガスを吸着塔Ｂ内に流通させ、塔内に残留する
難吸着性ガスをパージする。パージ工程終了後は
バルブ２，４及び６を閉じ、同時にバルブ８を開
き吸着塔Ｂ内のオレフインガスを吸引回収する。
吸着塔Ｂの回収工程が開始すると同時に、回収工
程を終えた吸着塔Ａは吸着工程へと移行する。以
上のように吸着塔Ａ及びＢを交互に吸着−パージ
−回収の工程順で運転することによりオレフイン
ガスの吸脱着を連続的に行ない、オレフイン系炭
化水素類を高純度でしかも効率的に精製分離する
ことができる。なお、上記説明は吸着塔工程の場
合について説明したが、これを３塔以上設けて実
施することもできることはいうまでもない。
更に、本発明に従えば、前記方法によつて回収
したオレフインガスを同様の吸着システムに少な
くとも一回以上流通させることにより製品ガス中
のオレフイン純度を更に一層向上させることがで
きるが、かかる態様も本発明の技術的範囲に属す
るものである。
実施例
以下に本発明の実施例を説明するが、本発明の
範囲をこれらの実施例に限定するものでないこと
はいうまでもない。
実施例 １
５容量の加熱減圧蒸留装置の反応釜に賦活処
理を施したヤシ殼を原料とした活性炭（４〜10メ
ツシユ破砕品）２Kgを装填し、真空ポンプを用い
て減圧（3torr）脱気を行なつた。一方、同時に
付帯溶解層を用いて6NHCI3に塩化銅（）
0.3Kgを窒素ガス雰囲気下で撹拌溶解して塩化銅
塩酸溶液を調製した。次に調製した塩化銅溶液を
脱気した反応釜に注入し、更に３時間反応釜内を
減圧下（5torr）に保つた後、温度160℃に加熱し
て水及び塩化水素を除去して黒色粒状の活性炭−
塩化銅吸着剤を得た。
次にこの吸着剤を用いてオレフイン系炭化水素
類を含む混合ガス（C2H4＝33.5％、C2H6＝33.2
％、CH4＝33.3％）の精製を試みた。
精製は前記した第１図に示した２塔式吸脱着装
置を用い、表−１に記載した吸着−パージ−脱着
のサイクルに基づいて実施した。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for recovering olefinic hydrocarbons, particularly ethylene, propylene, butylene, pentene, etc. (hereinafter referred to as ethylene etc.) from a raw material gas containing olefins by an adsorption separation method. Olefinic hydrocarbons such as ethylene are petrochemical products such as ethanol, ethylene oxide,
It is well known that it is useful as a raw material for acetaldehyde, vinyl chloride, styrene, vinyl acetate, ethylene glycol, low density linear polyethylene, propanol, propylene oxide, acetone, polypropylene, butanol, butadiene, polybutene, butyl rubber, etc. . PRIOR TECHNOLOGY To briefly explain the conventional general manufacturing method of olefins, first, the raw material naphtha and steam are mixed and sent to a pyrolysis furnace to pyrolyze the naphtha, and then the generated gas is immediately released. It is rapidly cooled to around 120℃ by heat exchange with water and injection of heavy oil, and the liquefied hydrocarbon components of C5 or higher are separated. This non-liquefied gas is then compressed to remove impurities.
It is liquefied using a refrigerant such as ethylene or propylene, and separated into ethylene, PP fraction, C4 fraction, residual gas, ethane, and other fractions by distillation. As explained above, the basic principle for separating and purifying useful components such as olefins from naphtha pyrolysis gas is low temperature pressurized distillation (cryogenic separation method). This method cools the raw material gas and liquefies it to -100℃~
It is fractionated at -200℃. Problems to be Solved by the Invention However, in the above method, if moisture or carbon dioxide exists in the raw material gas, these will solidify in the cryogenic tube system and cause a blockage accident. There is a problem that must be removed. Furthermore, the conventional methods described above require the use of complex refrigeration and heat recovery systems, require the use of high-grade materials such as special metal materials in the equipment, making the equipment expensive, and There are problems such as high operating costs due to the need to use a commercial compressor. As a result of repeated studies to solve the problems in the conventional method for producing olefins, the present inventors used an adsorbent consisting of a copper compound and activated carbon that selectively adsorbs olefins from a raw material gas containing olefins. We discovered a method to efficiently separate olefinic hydrocarbons such as ethylene and propylene. Means for Solving the Problems and Their Effects A method for purifying and separating olefinic hydrocarbons according to the present invention is a method for recovering olefinic hydrocarbons from a raw material gas containing olefins by an adsorption separation method. Using two or more adsorption towers filled with a copper compound-activated carbon adsorbent, (1) an adsorption step in which the raw material gas is passed through the adsorption tower to adsorb olefinic hydrocarbons; (2) an adsorption step in which the adsorption step is completed; A purge step in which the product gas is introduced into the adsorption tower to purge difficult-to-adsorb components; and (3) recovery in which the olefinic hydrocarbons adsorbed on the adsorbent are desorbed and recovered by reducing the pressure or heating the inside of the adsorption tower. The present invention relates to a method characterized in that the steps are repeatedly carried out in two or more adsorption towers. The step (1) in the present invention is an adsorption step in which olefins are adsorbed in an adsorption tower by flowing a raw material gas through the adsorption tower. In this adsorption process, sufficient effects can be obtained by operating the adsorption tower at normal pressure, but it is also possible to operate it under pressure, which increases the amount of adsorption and makes it possible to process even high-temperature gas. There are advantages such as being able to Even when operating in a pressurized state, high adsorption pressure is not necessary and is less than 10Kg/ cm2 , preferably 2 to 5Kg/cm2.
An adsorption pressure of cm 2 is sufficient. The raw material gas is allowed to flow into the adsorption tower at any point between the time when the olefin component begins to be detected at the outlet of the adsorption tower and the time when the concentration reaches the concentration at the entrance of the adsorption tower. Also, the temperature during adsorption operation is -40 to 90°C under normal pressure, preferably 0 to 60°C.
and -10°C to 120°C under pressure, preferably
The temperature is between 20°C and 80°C. The step (2) is a step of introducing the product gas into the adsorption tower after the adsorption step and purging the difficult-to-adsorb components remaining in the voids in the tower. Implementation of step (2) has the advantage of improving the recovery purity of olefinic hydrocarbons, which are useful components, and this step is an essential step in the present invention. The end point of introduction of the product gas can be determined, for example, by performing gas analysis at the outlet of the adsorption tower and detecting the concentration of useful components. The step (3) is a step in which the adsorption tower after the purge step is depressurized or heated to desorb the olefins adsorbed by the adsorbent and recover them together with the purge gas remaining in the voids. When desorption is performed by reducing pressure, it is preferable to operate the column by reducing the pressure inside the column to 100 torr or less using, for example, a vacuum pump. In the case of heating, it is preferable to operate the column at an internal temperature of 40 to 250°C, preferably 60 to 180°C. The copper compound-activated carbon adsorbent used in the present invention is copper () halide salt or copper oxide () or copper () halide salt, carboxylate, sulfate, basic salt or ammine complex salt, or copper () oxide.
It can be obtained by dissolving or suspending a copper compound such as in a suitable solvent, adding activated carbon to the solution, stirring thoroughly, and then removing the liquid phase by a method such as distillation under reduced pressure. The activated carbon used in the adsorbent is not particularly limited, but in terms of shape, granular carbon, powdered carbon, or fibrous carbon consisting of compacted carbon and crushed carbon are preferable. As raw materials for such activated carbon, wood, coconut shell, coal and petroleum pitch, synthetic fibers, etc. can be used. The weight ratio of activated carbon and copper compound (activated carbon/copper compound) in the adsorbent used in the present invention is generally
0.5 to 60.0, preferably 2.0 to 10.0. Hereinafter, specific details of the present invention will be explained with reference to the drawings. FIG. 1 is a diagram of an apparatus that consists of two adsorption towers and adsorbs and recovers olefins from a raw material gas by vacuum desorption. Adsorption towers A and B are filled with a copper compound-activated carbon adsorbent that selectively adsorbs olefins. To explain the operation of such an apparatus, first, valves 1, 3, and 5 are opened to allow the raw material gas to flow through the adsorption tower A, and the olefin gas is adsorbed by the adsorbent. At this time, valves 2, 4, 6, 7, and 8 are in a closed state. After the adsorption process is completed, valve 1 is closed, and in order to purge the poorly adsorbable gas remaining in the voids in adsorption tower A, valve 2 is opened to introduce product gas into adsorption tower A to purge non-adsorbable components. After the purge process is completed, valves 2, 3, and 5 are closed, valve 7 is opened, and the adsorbed olefin gas and the purge gas remaining in the void are sucked and recovered by a vacuum pump. During the recovery process in adsorption tower A, adsorption tower B performs an adsorption process and a purge process. That is, adsorption tower A
While the olefin gas inside is being sucked and recovered by the vacuum pump, valves 1, 4, and 6 are opened to allow the raw material gas to flow through the adsorption tower B, thereby adsorbing the olefin gas. Then, valve 1 is closed and valve 2 is opened to allow the product gas to flow into the adsorption tower B, thereby purging the poorly adsorbable gas remaining in the tower. After the purge process is completed, valves 2, 4, and 6 are closed, and at the same time, valve 8 is opened to suck and recover the olefin gas in the adsorption tower B.
At the same time as the recovery process of adsorption tower B starts, adsorption tower A, which has completed the recovery process, shifts to the adsorption process. As described above, by operating adsorption towers A and B alternately in the process order of adsorption, purge, and recovery, olefin gas can be adsorbed and desorbed continuously, and olefin hydrocarbons can be efficiently purified with high purity. Can be separated. In addition, although the above explanation was given regarding the case of the adsorption tower process, it goes without saying that this can be implemented by providing three or more towers. Furthermore, according to the present invention, the olefin purity in the product gas can be further improved by passing the olefin gas recovered by the above method through a similar adsorption system at least once, but such an embodiment also It belongs to the technical scope of the present invention. Examples Examples of the present invention will be described below, but it goes without saying that the scope of the present invention is not limited to these examples. Example 1 2 kg of activated carbon made from activated coconut shell (crushed product of 4 to 10 meshes) was loaded into the reaction pot of a 5-capacity heated vacuum distillation device, and degassed under reduced pressure (3 torr) using a vacuum pump. I did this. Meanwhile, copper chloride () to 6NHCI3 using an incidental dissolution layer at the same time
A copper chloride hydrochloric acid solution was prepared by stirring and dissolving 0.3 kg in a nitrogen gas atmosphere. Next, the prepared copper chloride solution was poured into the degassed reaction vessel, and after keeping the inside of the reaction vessel under reduced pressure (5 torr) for another 3 hours, it was heated to a temperature of 160°C to remove water and hydrogen chloride and turn black. Granular activated carbon
A copper chloride adsorbent was obtained. Next, using this adsorbent, a mixed gas containing olefinic hydrocarbons (C 2 H 4 = 33.5%, C 2 H 6 = 33.2
%, CH 4 =33.3%). Purification was carried out using the two-column adsorption/desorption apparatus shown in FIG. 1, based on the adsorption-purge-desorption cycle shown in Table 1.
【表】
４ 〃 パージ工程
[Table] 4 Purge process
Claims (1)
フイン系炭化水素を吸着分離方法によつて回収す
る方法において、 銅化合物−活性炭系からなる吸着剤を充填させ
た２つ以上の吸着塔を用い、 (1) 原料ガスを吸着塔に流通させてオレフイン系
炭化水素類を吸着剤に吸着させる吸着行程、 (2) 吸着工程を終了した吸着塔へ製品ガスを導入
して、難吸着性成分をパージするパージ工程及
び (3) 吸着塔内を加熱又は減圧することにより、吸
着剤に吸着されているオレフイン系炭化水素類
を回収する回収行程を２つ以上の吸着塔におい
て繰り返し実施することを特徴とする方法。[Scope of Claims] 1. A method for recovering olefinic hydrocarbons from a raw material gas containing multi-component hydrocarbons by an adsorption separation method, comprising: two or more adsorbents filled with a copper compound-activated carbon system adsorbent; Using an adsorption tower, (1) an adsorption step in which the raw material gas is passed through the adsorption tower to adsorb olefinic hydrocarbons on the adsorbent; (2) a product gas is introduced into the adsorption tower after the adsorption step; A purge step for purging difficult-to-adsorb components and (3) a recovery step for recovering olefinic hydrocarbons adsorbed by the adsorbent by heating or reducing the pressure inside the adsorption tower are repeated in two or more adsorption towers. A method characterized by carrying out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247935A JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247935A JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61126036A JPS61126036A (en) | 1986-06-13 |
| JPH0259808B2 true JPH0259808B2 (en) | 1990-12-13 |
Family
ID=17170741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59247935A Granted JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61126036A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06320214A (en) * | 1993-05-11 | 1994-11-22 | Saikawa:Kk | Continuous wire drawing and rolling method and its apparatus |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH053253Y2 (en) * | 1988-05-11 | 1993-01-26 | ||
| KR100822847B1 (en) | 2007-03-29 | 2008-04-16 | 한국에너지기술연구원 | Olefin separation technology in olefin / paraffin mixture gas |
| US9034185B2 (en) | 2007-03-29 | 2015-05-19 | Korea Institute Of Energy Research | Separation of olefins from olefins/paraffins mixed gas |
| KR100836707B1 (en) * | 2007-04-25 | 2008-06-10 | 한국에너지기술연구원 | High purity butene-1 separation technology in olefin / paraffin mixture gas |
| JP5426179B2 (en) * | 2009-01-15 | 2014-02-26 | 株式会社神戸製鋼所 | Method for separation and purification of hydrocarbons |
| KR101270713B1 (en) | 2010-08-26 | 2013-06-17 | 에스케이 주식회사 | Process for the recovery of ethylene from fcc off-gas |
| KR101470675B1 (en) * | 2010-08-26 | 2014-12-08 | 한국에너지기술연구원 | Displacement desorption process for light olefin separation |
| CN106268645B (en) * | 2016-09-27 | 2019-04-09 | 华南理工大学 | A kind of preparation method of fluorine-doped carbon-based adsorption material that preferentially adsorbs ethane |
| CN109012576A (en) * | 2018-07-02 | 2018-12-18 | 昆明理工大学 | A kind of preparation method and application loading cuprous oxide particle active carbon |
-
1984
- 1984-11-26 JP JP59247935A patent/JPS61126036A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06320214A (en) * | 1993-05-11 | 1994-11-22 | Saikawa:Kk | Continuous wire drawing and rolling method and its apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61126036A (en) | 1986-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR870000758B1 (en) | Argon Separation Method | |
| KR100836707B1 (en) | High purity butene-1 separation technology in olefin / paraffin mixture gas | |
| KR100822847B1 (en) | Olefin separation technology in olefin / paraffin mixture gas | |
| US4025321A (en) | Purification of natural gas streams containing oxygen | |
| CN101346183A (en) | The use of MOFs in pressure swing adsorption | |
| JPS6362522A (en) | Adsorptive separation of gaseous mixture | |
| WO1989006218A1 (en) | Process for separating and recovering carbonic acid gas from gas mixture by adsorption | |
| KR20030040068A (en) | Syngas purification process | |
| KR101470675B1 (en) | Displacement desorption process for light olefin separation | |
| JP3566766B2 (en) | Method for recovering alkenes from flue gas | |
| JPH0259808B2 (en) | ||
| SA111320719B1 (en) | Method and apparatus for recovering ethylene from fluidized catalytic cracking (FCC) off-gas | |
| KR102017863B1 (en) | Cyclic Separation Process of Olefin And Paraffin | |
| AU2008274180B2 (en) | Method and apparatus for separating nitrogen from a mixed nitrogen and methane containing stream by using a metal organic framework | |
| CN115504855B (en) | A method for adsorption separation of low-carbon olefin/alkane mixture and its application | |
| JPS6137970B2 (en) | ||
| JP5426179B2 (en) | Method for separation and purification of hydrocarbons | |
| CN1073422A (en) | Process for separating ethene by catalytic cracking and dry gas adsorption | |
| CN108329962B (en) | Method and device for removing nitrogen in natural gas | |
| EP0216900B1 (en) | Processing of high normal paraffin concentration naphtha feedstocks | |
| KR102033456B1 (en) | Carbon monoxide separation process and its system | |
| JPS61115033A (en) | Purification and separation of olefinic hydrocarbon | |
| KR100849987B1 (en) | Ethylene enrichment technology from fluidized bed catalytic cracking flue gas | |
| JPS6351056B2 (en) | ||
| JP2587334B2 (en) | Method of separating CO gas not containing CH4 |