JPH083099B2 - Low polymerization method of light olefin. - Google Patents
Low polymerization method of light olefin.Info
- Publication number
- JPH083099B2 JPH083099B2 JP61241920A JP24192086A JPH083099B2 JP H083099 B2 JPH083099 B2 JP H083099B2 JP 61241920 A JP61241920 A JP 61241920A JP 24192086 A JP24192086 A JP 24192086A JP H083099 B2 JPH083099 B2 JP H083099B2
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- JP
- Japan
- Prior art keywords
- butene
- catalyst
- conversion rate
- type zeolite
- low polymerization
- Prior art date
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はナフサ及びガスオイル等の水蒸気分解及び接
触分解等の種々の方法で入手される炭素数２−５の低級
オレフイン又はこれらの混合物を液相重合反応によりガ
ソリン、灯油、溶剤、石油化学原料に変換し、低級オレ
フイン系炭化水素又はこれらの混合物の有効利用、高付
価価値化を行なう方法に関するものである。The present invention relates to a liquid phase of a lower olefin having 2 to 5 carbon atoms or a mixture thereof, which is obtained by various methods such as steam cracking and catalytic cracking of naphtha and gas oil. The present invention relates to a method for converting a gasoline, kerosene, a solvent, a petrochemical raw material by a polymerization reaction to effectively use a lower olefin hydrocarbon or a mixture thereof and to increase a valuation value.
従来技術 ゼオライトを触媒として液相で低級オレフインを低重
合させる方法は既に出願されている。例えば、米国特許
第4254295号明細書（Mobil oil）には、炭素数２ないし
12のオレフイン系炭化水素をZSM−12型ゼオライト触媒
を液相で選択的にオリゴマリゼーシヨンを行う方法が開
示してある。2. Description of the Related Art A method for low-polymerizing lower olefins in a liquid phase using zeolite as a catalyst has already been filed. For example, U.S. Pat. No. 4,254,295 (Mobil oil) has 2 to 5 carbon atoms.
A method for selectively performing oligomerization of 12 olefin hydrocarbons in a liquid phase using a ZSM-12 type zeolite catalyst is disclosed.
特開昭60−208931号明細書（シエブロンリサーチカン
パニー）には炭素数２ないし20のオレフイン系炭化水素
をZSM−５型ゼオライト触媒などの細孔寸法が中程度の
水素型ニツケル含有シリカ質分子篩を触媒として液相で
オリゴマリゼーシヨンを行う方法が開示してある。Japanese Unexamined Patent Publication (Kokai) No. 60-208931 (Sieblon Research Company) discloses an olefin-based hydrocarbon having 2 to 20 carbon atoms, such as ZSM-5 type zeolite catalyst, which is a hydrogen type nickel-containing silica molecular sieve having a medium pore size. Disclosed is a method of performing oligomerization in a liquid phase by using as a catalyst.
特開昭57−108023号明細書（東亜燃料工業）には水素
型モルデナイト（15＜Si/Al＜250）を触媒として液相で
イソブテンを選択的に低重合する方法が開示されてい
る。JP-A-57-108023 (Toa Fuel Industry Co., Ltd.) discloses a method for selectively low-polymerizing isobutene in a liquid phase using hydrogen type mordenite (15 <Si / Al <250) as a catalyst.
これらの特許に開示されている方法はこれらが本発明
で用いられているフオージヤサイト型ゼオライトとは異
なつた触媒を使用している点で相違している。The methods disclosed in these patents differ in that they use a different catalyst than the phosjasite-type zeolite used in the present invention.
なぜならば、第１表に示すように本発明で用いられて
いるフオージヤサイト型ゼオライトはこれらの特許に開
示されているゼオライトは粉末Ｘ線回析図形（この値は
Ｘ線回析のチヤートより読み取られた２θよりブラツグ
の式を用いて計算した格子面間隔）が異なるからであ
る。This is because, as shown in Table 1, the porphyriasite-type zeolite used in the present invention is the powder X-ray diffraction pattern (this value is obtained from the X-ray diffraction chart). This is because the lattice plane spacing calculated using the Bragg equation is different from the read 2θ.
問題点を解決するための手段 本発明は、触媒として原子比Si/Al1.0〜20の細孔径7.
4Åを有する酸素12員環フオージヤサイト型ゼオライト
を用い、炭素数２ないし５の低級オレフイン系炭化水素
およびこれらの混合物を反応温度20℃ないし200℃にて
該低級炭化水素の少なくとも１部が液状になる圧力下で
反応させることを特徴とする軽質オレフインの低重合方
法に関するものである。 Means for Solving the Problems The present invention is a catalyst having a pore size of atomic ratio Si / Al 1.0 to 20 7.
At least a part of the lower hydrocarbon is a liquid at a reaction temperature of 20 ° C to 200 ° C, using a lower olefin hydrocarbon having 2 to 5 carbon atoms and a mixture thereof, using an oxygen 12-membered ring phosjasite type zeolite having 4Å. The present invention relates to a method for low polymerization of light olefin, which is characterized by reacting under a pressure of
本発明で使用した触媒はフオージヤサイト型ゼオライ
トであり、モルデナイト型ゼオライト、Ｌ型ゼオライ
ト、ZSM−５型ゼオライト触媒と比較検討した。The catalyst used in the present invention is a faujasite type zeolite, and was compared and examined with mordenite type zeolite, L type zeolite and ZSM-5 type zeolite catalyst.
その化学組成は第２表に示し、その物性は第３表に示
した。Its chemical composition is shown in Table 2, and its physical properties are shown in Table 3.
本発明では、Na型又はＫ型のゼオライトを硝酸アンモ
ニウム（NH4NO3）水溶液でイオン交換した後、焼成しＨ
型としたものをＨ−Ｙ、Ｈ−Ｌ、Ｈ−ＭおよびＨ−ZSM
−５型ゼオライトとし、更にＨ−Ｙを熱水処理すること
により脱アルミニウムしたものをUS−Ｙとした。 In the present invention, Na-type or K-type zeolite is ion-exchanged with an ammonium nitrate (NH 4 NO 3 ) aqueous solution and then calcined to form H.
Modeled as HY, HL, HM and H-ZSM
-5 type zeolite was used, and HY was dealuminated by hot water treatment to obtain US-Y.
実施例 触 媒 第２表に示す化学組成および第３表に示す物性を有す
るフオージヤサイト型ゼオライト（Ｈ−Ｙ、US−Ｙ）、
モルデナイト型ゼオライト（Ｈ−Ｍ）、Ｌ型ゼオライト
（Ｈ−Ｌ）およびＨ−ZSM−５ゼオライト触媒を用いて
比較した。 Examples Catalysts Phosphorite-type zeolite (HY, US-Y) having the chemical composition shown in Table 2 and the physical properties shown in Table 3,
Comparison was made using mordenite type zeolite (HM), L type zeolite (HL) and H-ZSM-5 zeolite catalyst.
触媒は打錠成型後８〜15メツシユに粉砕して使用し
た。The catalyst was used after crushing into tablets by crushing into 8 to 15 meshes.
反 応 第１図に示す流通式加圧反応装置を使用し、反応管は
内径１インチ（24mm）、使用触媒は反応管に200cc充填
した（充填層の長さ410mm）。Reaction Using the flow-type pressure reactor shown in Fig. 1, the reaction tube had an inner diameter of 1 inch (24 mm), and the catalyst used was 200 cc packed in the reaction tube (packed bed length 410 mm).
反応に先立つて触媒前処理としてN2（200/hv）流通
下、200℃、２時間乾燥後次の組成のFCC分解装置よりの
BBガスを反応させた。Prior to the reaction, as a catalyst pretreatment, it was dried under N 2 (200 / hv) flow for 2 hours at 200 ° C.
BB gas was reacted.
原料ガス組成（wt−％） FCC BBガス プロパン7.0、ｉ−ブテン11.9、1,3ブタジエン痕跡、
プロピレン1.2、１−ブテン9.2、C5−炭化水素1.5、ｉ
−ブタン41.2、ｔ−２ブテン11.7、ｎ−ブタン8.2、Ｃ
−２ブテン8.1、ブテントータ40.9。Raw gas composition (wt-%) FCC BB gas Propane 7.0, i-butene 11.9, traces of 1,3 butadiene,
Propylene 1.2,1- butene 9.2, C 5 - hydrocarbons 1.5, i
-Butane 41.2, t-2 butene 11.7, n-butane 8.2, C
-2 butene 8.1, butenta 40.9.
反応条件は、反応温度30〜140℃、圧力55kg/cm2、LHS
VK 1hr-1であつた。The reaction conditions are reaction temperature 30-140 ° C, pressure 55 kg / cm 2 , LHS.
It was VK 1hr -1 .
各種触媒US−Ｙ、Ｈ−Ｙ、Ｈ−Ｌ、Ｈ−ＭおよびＨ−
ZSM−５によるブテン変換率（％）は第４表に示した。Various catalysts US-Y, HY, HL, HM and H-
The butene conversion rate (%) according to ZSM-5 is shown in Table 4.
生成物の分析 （１）ブテン変換率の計算 反応生成物をガスクロマトグラフイーで分析し、未反
応BBの組成を分析し、各種ブテンの変換率を計算した。 Analysis of products (1) Calculation of butene conversion rate The reaction products were analyzed by gas chromatography, the composition of unreacted BB was analyzed, and the conversion rates of various butenes were calculated.
それらの計算方法を以下に示す。 The calculation methods are shown below.
変換率（ｎ）＝１−Aa（ｎ）/aA（ｎ） 変換率（Ｔ）＝１−Ａ〔ａ（１）＋ａ（２）＋ａ（３）
＋ａ（４）〕／ ａ〔Ａ（１）＋Ａ（２）＋Ａ（３）＋Ａ（４）〕 変換率（ｎ）：各種ブテンの変換率（％）１＜ｎ＜４ 変換率（Ｔ）：全ブテンの変換率（％） A:原料BB中のｎ−ブタン含量（wt％） a:未反応BB中のｎ−ブタン含量（wt％） Ａ（ｎ）：原料BB中の各種ブテン含量（wt％）１＜ｎ＜
４ ａ（ｎ）：未反応BB中の各種ブテン含量（wt％）１＜ｎ
＜４ 液状生成物の分析 生成物はすべてプロパンガスボンベに捕集し、蒸留に
より未反応BBを除去後、横河ヒユーレツトパツカード製
GC蒸留装置で分析した。Conversion rate (n) = 1-Aa (n) / aA (n) Conversion rate (T) = 1-A [a (1) + a (2) + a (3)
+ A (4)] / a [A (1) + A (2) + A (3) + A (4)] conversion rate (n): conversion rate (%) of various butenes 1 <n <4 conversion rate (T): Total butene conversion rate (%) A: n-butane content in raw BB (wt%) a: n-butane content in unreacted BB (wt%) A (n): various butene contents in raw BB ( wt%) 1 <n <
4 a (n): content of various butenes in unreacted BB (wt%) 1 <n
<4 Analysis of liquid products All the products were collected in a propane gas cylinder and the unreacted BB was removed by distillation, then made by Yokogawa Hiyuretsu Paccard
It was analyzed by a GC distillation apparatus.
使用触媒の種類と全ブテン変換率との関係を第４表に
示した。Table 4 shows the relationship between the type of catalyst used and the total butene conversion rate.
使用触媒の種類と生成ブテンの種類との関係は第５表
に示した。Table 5 shows the relationship between the type of catalyst used and the type of butene produced.
また得られた液状炭化水素分布とブテン変換率との関
係を第２図に示した。図においてIBPは初留温度を示
す。The relationship between the obtained liquid hydrocarbon distribution and the butene conversion rate is shown in FIG. In the figure, IBP is the initial distillation temperature.
結 果 触媒活性の序列と触媒の細孔径の序列は一致し、Ｈ−
Ｙ、US−Ｙ＞Ｈ−Ｌ＞Ｈ−Ｍ＞Ｈ−ZSM−５の順であつ
た。 As a result, the order of the catalytic activity and the order of the pore size of the catalyst are the same.
Y, US-Y>H-L>HM-> H-ZSM-5.
また、各種ブテンの変換率はブテンの種類によつて異
なり、その値は ｉ−ブテン＞１−ブテン＞ｔ−２−ブテン＞Ｃ−２−ブ
テン の順であつた。Further, the conversion rates of various butenes differed depending on the type of butene, and the values were in the order of i-butene>1-butene>t-2-butene> C-2-butene.
これらの中でｉ−ブテン、１−ブテンの変換率はいず
れの触媒においても高い値を示しているが、ｔ−２ブテ
ン、Ｃ−２ブテンは各触媒間で変換率の差が大きかつ
た。Among these, the conversion rates of i-butene and 1-butene were high in all catalysts, but the conversion rates of t-2 butene and C-2 butene were large among the catalysts. .
第２図に示すように、ブテンの変換率が高くなるにつ
れて液状生成物は重くなる傾向にあつた。As shown in FIG. 2, the liquid product tended to become heavier as the butene conversion rate increased.
また、ブテンの変換率が高くなるにつれて重合度が増
加することがわかつた。It was also found that the degree of polymerization increased as the butene conversion rate increased.
発明の効果 （１）酸素12員環フオージヤサイト型ゼオライトが軽質
オレフインの液相低温重合に有効な触媒活性を示した。EFFECTS OF THE INVENTION (1) Oxygen 12-membered ring faujasite-type zeolite showed effective catalytic activity for liquid phase low temperature polymerization of light olefin.
（２）軽質オレフインの変換率が高くなるに従つて液状
炭化水素の重合度が増加することがわかつた。(2) It has been found that the degree of polymerization of liquid hydrocarbon increases as the conversion rate of light olefin increases.
（３）従来法では２−ブテンの変換率は低かつたが、本
発明方法では高い変換率を示した。(3) Although the conversion rate of 2-butene was low in the conventional method, the conversion rate of the present invention was high.
第１図は流通式加圧反応装置の系統図、 第２図はブテン変換率と液状炭化水素分布との関係を示
す図 である。 第１図において、 １……原料ガスタンク、２……原料供給用ポンプ、３…
…反応管、４……サンプリングノズル、５……コンデン
サー、６……受器、７……ガスメーター、８……反応生
成物捕集用ボンベ 第２図において、 A:H−ZSM−５、B:H−Ｍ、C:H−Ｌ、D:US−Ｙ、E:H−
Ｙ。FIG. 1 is a system diagram of a flow-type pressure reactor, and FIG. 2 is a diagram showing a relationship between butene conversion rate and liquid hydrocarbon distribution. In FIG. 1, 1 ... Raw material gas tank, 2 ... Raw material supply pump, 3 ...
… Reaction tube, 4 …… Sampling nozzle, 5 …… Condenser, 6 …… Receiver, 7 …… Gas meter, 8 …… Cylinder for collecting reaction products In Fig. 2, A: H-ZSM-5, B : HM, C: HL, D: US-Y, E: H-
Y.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩崎 正夫 東京都千代田区丸の内２丁目７番３号 昭 和シエル石油株式会社内 (56)参考文献 特開 昭61−2791（ＪＰ，Ａ) 特開 昭60−208931（ＪＰ，Ａ) 特開 昭59−49290（ＪＰ，Ａ) 特開 昭57−94089（ＪＰ，Ａ) 特開 昭57−108023（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Iwasaki 2-7-3 Marunouchi, Chiyoda-ku, Tokyo Within Showa Shell Petroleum Co., Ltd. (56) Reference JP-A 61-2791 (JP, A) JP JP-A-60-208931 (JP, A) JP-A-59-49290 (JP, A) JP-A-57-94089 (JP, A) JP-A-57-108023 (JP, A)
Claims (1)
4Åを有する酸素12員環フオージヤサイト型ゼオライト
を用い、炭素数２ないし５の低級オレフイン系炭化水素
およびこれらの混合物を反応温度20℃ないし200℃にて
該低級炭化水素の少なくとも１部が液状になる圧力下で
反応させることを特徴とする軽質オレフインの低重合方
法。1. A catalyst having a pore size of atomic ratio Si / Al of 1.0 to 20 7.
At least a part of the lower hydrocarbon is a liquid at a reaction temperature of 20 ° C to 200 ° C, using a lower olefin hydrocarbon having 2 to 5 carbon atoms and a mixture thereof, using an oxygen 12-membered ring phosjasite type zeolite having 4Å. A method for low polymerization of light olefins, which comprises reacting under a pressure that changes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61241920A JPH083099B2 (en) | 1986-10-14 | 1986-10-14 | Low polymerization method of light olefin. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61241920A JPH083099B2 (en) | 1986-10-14 | 1986-10-14 | Low polymerization method of light olefin. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6397692A JPS6397692A (en) | 1988-04-28 |
| JPH083099B2 true JPH083099B2 (en) | 1996-01-17 |
Family
ID=17081521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61241920A Expired - Lifetime JPH083099B2 (en) | 1986-10-14 | 1986-10-14 | Low polymerization method of light olefin. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083099B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4965798B2 (en) * | 2004-07-30 | 2012-07-04 | サウジ ベイシック インダストリーズ コーポレイション | Methylation of toluene |
| FR2894850B1 (en) * | 2005-12-20 | 2008-02-01 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF A CATALYST CONTAINING MODIFIED ZEOLITHE AND USE THEREOF IN OLIGOMERIZATION OF LIGHT OLEFINS |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3038117A1 (en) * | 1980-10-09 | 1982-05-13 | EC Erdölchemie GmbH, 5000 Köln | HYDRATED HYDROCARBON MIXTURES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AND FUELS, CONTAINING THESE HYDROGENATED HYDROCARBON MIXTURES |
| JPS57108023A (en) * | 1980-12-26 | 1982-07-05 | Toa Nenryo Kogyo Kk | Oligomerization catalyst for isobutene |
| US4465884A (en) * | 1982-08-17 | 1984-08-14 | Mobil Oil Corporation | Olefin processing |
| US4538012A (en) * | 1984-02-27 | 1985-08-27 | Chevron Research Company | Oligomerization of liquid olefin over a nickel-containing silicaceous crystalline molecular sieve |
| JPS612791A (en) * | 1984-06-15 | 1986-01-08 | Res Assoc Petroleum Alternat Dev<Rapad> | Preparation of gasoline having high octane number |
-
1986
- 1986-10-14 JP JP61241920A patent/JPH083099B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6397692A (en) | 1988-04-28 |
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