JP3522824B2 - Solid acid catalyst for paraffin isomerization and method for paraffin isomerization using the same - Google Patents
Solid acid catalyst for paraffin isomerization and method for paraffin isomerization using the sameInfo
- Publication number
- JP3522824B2 JP3522824B2 JP07810594A JP7810594A JP3522824B2 JP 3522824 B2 JP3522824 B2 JP 3522824B2 JP 07810594 A JP07810594 A JP 07810594A JP 7810594 A JP7810594 A JP 7810594A JP 3522824 B2 JP3522824 B2 JP 3522824B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- isomerization
- paraffin
- reaction
- solid acid
- 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 - Fee Related
Links
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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は石油精製、石油化学工業
で使用されるパラフィンの異性化用固体酸触媒およびパ
ラフィンの異性化方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid acid catalyst for paraffin isomerization used in petroleum refining and petrochemical industry, and a paraffin isomerization method.
【０００２】[0002]
【従来技術】石油精製、石油化学工業において、多数の
パラフィンの関与する転化反応が行われている。その例
としては、接触分解、接触改質、水素化分解、異性化、
アルキル化などが挙げられる。特に、パラフィンの異性
化、アルキル化反応を行うパラフィン転化用触媒として
は、強い酸性を有する酸触媒が必要である。従来、これ
らの反応には硫酸、フッ化水素、塩化アルミニウム、三
塩化アンチモンなどの酸触媒が使用されている。しか
し、これらの触媒は金属を腐食させるため、高価な耐食
材料の使用、防食処理の必要がある。また、近年の環境
規制の強化に伴い、廃触媒の処理は高いコストを必要と
するとともに、厳しく規制される方向にある。更に、こ
れらの触媒は反応物との分離が困難であるという問題点
があった。In the petroleum refining and petrochemical industries, conversion reactions involving many paraffins are carried out. Examples are catalytic cracking, catalytic reforming, hydrocracking, isomerization,
Examples include alkylation. In particular, as a paraffin conversion catalyst for isomerizing and alkylating paraffin, an acid catalyst having strong acidity is required. Conventionally, acid catalysts such as sulfuric acid, hydrogen fluoride, aluminum chloride and antimony trichloride have been used for these reactions. However, since these catalysts corrode metals, it is necessary to use expensive anticorrosive materials and perform anticorrosion treatment. In addition, with the recent strengthening of environmental regulations, the treatment of waste catalysts requires high cost and tends to be strictly regulated. Further, these catalysts have a problem that it is difficult to separate them from the reactants.
【０００３】また、パラフィンの異性化においては、Ｐ
ｔなどの貴金属を担持した固体酸をハロゲンを含有する
化合物で処理した触媒を用いて、水素共存下に異性化を
行う方法が用いられるが、この触媒は水によってきわめ
て容易に失活するため、原料の水分除去に多大なコスト
がかかるという問題点がある。また特開平５−５８９２
１号公報にはヘテロポリ酸のアルカリ金属塩と第VIII族
金属からなる触媒を用いて、エチレンと芳香族化合物を
反応させてブチル基置換芳香族化合物の製造方法が記載
されている。しかしながら、パラフィンの転化反応につ
いては全く言及していない。In the isomerization of paraffin, P
A method in which a solid acid carrying a noble metal such as t is treated with a compound containing a halogen is used to perform isomerization in the presence of hydrogen is used. However, this catalyst is extremely easily deactivated by water. There is a problem that it takes a lot of cost to remove water from the raw material. In addition, JP-A-5-5892
Japanese Unexamined Patent Publication (Kokai) No. 1 describes a method for producing a butyl group-substituted aromatic compound by reacting ethylene with an aromatic compound using a catalyst composed of an alkali metal salt of heteropolyacid and a Group VIII metal. However, no reference is made to the paraffin conversion reaction.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の従来
の問題点を解決して、腐食性がなく、反応物との分離が
容易で、さらに酸触媒反応に高活性なパラフィンの異性
化用固体酸触媒を提供することを目的とする。[SUMMARY OF THE INVENTION The present invention is to solve the conventional problems described above, no corrosive, easy separation of the reactants, highly active isomerization of paraffin more acid-catalyzed reaction < The object is to provide a solid acid catalyst for oxidization.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記の問題
点を解決するために鋭意研究した結果、特定な成分から
なる触媒、特に特定の組成からなる触媒が腐食性がな
く、反応物との分離が容易で、さらにパラフィンの異性
化用固体酸触媒反応に高活性であることを見出し、本発
明を完成した。Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to solve the above-mentioned problems, a catalyst composed of a specific component, particularly a catalyst composed of a specific composition is not corrosive and a reaction product The present invention has been completed based on the finding that it can be easily separated from the above and is highly active in the solid acid catalytic reaction for isomerization of paraffin.
【０００６】すなわち、本発明は、ヘテロポリ酸の酸性
塩と第VIII族金属とを必須成分とすることを特徴とする
パラフィンの異性化用固体酸触媒を提供する。That is, the present invention provides a solid acid catalyst for isomerization of paraffin, which comprises an acidic salt of heteropolyacid and a Group VIII metal as essential components.
【０００７】[0007]
【０００８】さらに、本発明は、ヘテロポリ酸の酸性塩
と第VIII族金属とを必須成分とする固体酸触媒及び水素
の存在下で、パラフィンの異性化を行うことを特徴とす
るパラフィンの異性化方法を提供する。Furthermore, the present invention is characterized in that paraffin isomerization is carried out in the presence of hydrogen and a solid acid catalyst containing an acidic salt of a heteropoly acid and a Group VIII metal as essential components and hydrogen. Provide a way.
【０００９】以下本発明の構成を詳細に説明する。本発
明の固体酸触媒の成分であるヘテロポリ酸の酸性塩とは
ヘテロポリ酸の水素イオンの一部を他の陽イオンで置き
換えたものである。ヘテロポリ酸とは２種以上の無機酸
素酸が縮合した酸の総称である。本発明において用いら
れるヘテロポリ酸は、特定の構造に限定されるものでは
ないが、一般式（１）で表されるヘテロポリ酸が好まし
い。The structure of the present invention will be described in detail below. The acid salt of heteropoly acid, which is a component of the solid acid catalyst of the present invention, is obtained by replacing a part of hydrogen ions of heteropoly acid with another cation. Heteropoly acid is a general term for acids in which two or more types of inorganic oxygen acids are condensed. The heteropolyacid used in the present invention is not limited to a particular structure, but a heteropolyacid represented by the general formula (1) is preferable.
【００１０】
Ｈ(80-m-12n)［ＸＹ12Ｏ40］ （１）
ここでＸはヘテロ原子とよばれ、例えばＰ、Ａｓ、Ｓ
ｉ、Ｇｅが挙げられる。Ｙはポリ原子とよばれ、例えば
Ｍｏ、Ｗ、Ｎｂ、Ｖなどの遷移金属が挙げられる。これ
らは組み合わせて用いることができる。ｍ、ｎはそれぞ
れＸ、Ｙの価数である。一般式（１）で表されるヘテロ
ポリ酸のなかで、ヘテロ原子はＰ、Ｓｉが好ましく、ポ
リ原子はＭｏ、Ｗが好ましい。さらに好ましくはＨ3Ｐ
Ｗ12Ｏ40、Ｈ3ＰＭｏ12Ｏ40であり、特にＨ3ＰＷ12Ｏ40
ガ好ましい。H (80-m-12n) [XY 12 O 40 ] (1) Here, X is called a hetero atom, for example, P, As, S
i and Ge are mentioned. Y is called a poly atom, and examples thereof include transition metals such as Mo, W, Nb, and V. These can be used in combination. m and n are the valences of X and Y, respectively. Among the heteropolyacids represented by the general formula (1), P and Si are preferable as the hetero atom, and Mo and W are preferable as the poly atom. More preferably H 3 P
W 12 O 40 and H 3 PMo 12 O 40 , especially H 3 PW 12 O 40
Moth preferred.
【００１１】ヘテロポリ酸の水素イオンの一部を置き換
える他の陽イオンはアルカリ金属イオンおよびアンモニ
ウムイオンが好ましい。この中で、Ｒｂ+、Ｃｓ+ 又はＮ
Ｈ４ +が好ましく、特にＣｓ+が好ましい。Other cations that replace some of the hydrogen ions of the heteropolyacid are preferably alkali metal ions and ammonium ions. Among these, Rb + , Cs + or N
H 4 + is preferable, and Cs + is particularly preferable.
【００１２】 触媒を調製するにはこれらの陽イオンの
塩をヘテロポリ酸と反応させる。調製に用いるこれらの
塩は、炭酸塩、硝酸塩、硫酸塩、塩化物、酢酸塩、シュ
ウ酸塩が好ましく、特に炭酸塩が好ましい。To prepare the catalyst, salts of these cations are reacted with a heteropolyacid. These salt used in preparation, carbonates, nitrates, sulfates, chlorides, acetates, oxalates preferably the carbonate especially preferred.
【００１３】本発明で用いるヘテロポリ酸の酸性塩の組
成は下記一般式（２）で表されるものが好ましい。The composition of the acid salt of heteropolyacid used in the present invention is preferably represented by the following general formula (2).
【００１４】[0014]
【化２】
(式中Ｌはアルカリ金属イオン、アルカリ土類金属イオ
ン、アンモニウムイオン、Ｘはヘテロ原子、Ｙはポリ原
子、ｌ、ｍ、ｎはそれぞれＬ、Ｘ、Ｙの価数、ｋはＬの
個数で、０を超え、（８０−ｍ−１２ｎ）／ｌ未満個で
ある）[Chemical 2] (Wherein L is an alkali metal ion, alkaline earth metal ion, ammonium ion, X is a hetero atom, Y is a poly atom, l, m and n are valences of L, X and Y, respectively, and k is a number of L. , More than 0 and less than (80-m-12n) / l)
【００１５】また、本発明で用いるヘテロポリ酸の酢酸
塩の組成はヘテロ原子がＰ又はＳｉ、ポリ原子がＷ及び
／又はＭｏであるものがさらに好ましい。The composition of the acetate salt of the heteropolyacid used in the present invention is more preferably such that the heteroatom is P or Si and the polyatom is W and / or Mo.
【００１６】ヘテロ原子がＰの場合、下記一般式（３）
で表されるものが好ましい。
ＡxＨ(3-x)ＰＹ12Ｏ40 （３）
（式中Ａはアルカリ金属イオン、アンモニウムイオン、
ＹはＷ及び／又はＭｏ、ｘはＡの個数である）
上記一般式（３）において、好ましくはｘが２．０５〜
２．９５、さらに好ましくは２．１〜２．９、特に好ま
しくは２．２〜２．８である。ｘが２．０５未満である
と、活性が低く、また通常好ましくない副反応である水
素化分解が優先して起こる。ｘが２．９５を超えると、
通常好ましくない副反応である水素化分解が優先して起
こる。When the hetero atom is P, the following general formula (3)
What is represented by is preferable. A x H (3-x) PY 12 O 40 (3) (where A is an alkali metal ion, ammonium ion,
Y is W and / or Mo, and x is the number of A) In the general formula (3), x is preferably 2.05 to
2.95, more preferably 2.1 to 2.9, and particularly preferably 2.2 to 2.8. When x is less than 2.05, the activity is low, and hydrogenolysis which is a usually unfavorable side reaction occurs preferentially. When x exceeds 2.95,
Hydrocracking, which is usually an undesirable side reaction, takes place preferentially.
【００１７】ヘテロ原子がＳｉの場合、下記一般式
（４）で表されるものが好ましい。
ＡxＨ(4-x)ＳｉＹ12Ｏ40 （４）
（式中Ａはアルカリ金属イオン、アンモニウムイオン、
ＹはＷ及び／又はＭｏ、ｘはＡの個数である）
上記一般式（４）において、好ましくはｘが２．０５〜
３．９５、さらに好ましくは３．１〜３．９である。When the hetero atom is Si, those represented by the following general formula (4) are preferable. A x H (4-x) SiY 12 O 40 (4) (where A is an alkali metal ion, ammonium ion,
Y is W and / or Mo, and x is the number of A.) In the above general formula (4), x is preferably 2.05 to
3.95, and more preferably 3.1 to 3.9.
【００１８】本発明で用いられる第VIII族金属とは、周
期律表第VIII族金属である。この中で、Ｒｕ，Ｒｈ、Ｐ
ｄ、Ｏｓ、Ｉｒ又はＰｔが好ましく、Ｐｄ又はＰｔが特
に好ましい。触媒を調製する際には、これらの塩を用い
るが、通常入手可能な任意の塩を用いることができる。
たとえば、ハロゲン化物、硝酸塩、硫酸塩、酢酸塩、シ
アン化物、アセチルアセトナート、アンミン錯体、カル
ボニル錯体などが好ましい。さらに具体的には、塩化白
金、ヨウ化白金、塩化白金酸、塩化白金酸カリウム、Ｐ
ｔ（ＮＨ3）4Ｃｌ2、酢酸パラジウム、塩化パラジウ
ム、硝酸パラジウム、パラジウムアセチルアセトナー
ト、酢酸ロジウム、塩化ロジウム、硝酸ロジウム、塩化
ルテニウム、塩化オスミウム、塩化イリジウムが好まし
く挙げられる。本発明において、第VIII族金属の含有量
は、好ましくは全触媒量に対して０．０５〜３０重量％
であり、さらに好ましくは０．２〜１０重量％であり、
さらに特に好ましくは０．５〜５重量％である。The Group VIII metal used in the present invention is a Group VIII metal of the periodic table. Among these, Ru, Rh, P
d, Os, Ir or Pt are preferred, with Pd or Pt being especially preferred. These salts are used when preparing the catalyst, but any commonly available salt can be used.
For example, halides, nitrates, sulfates, acetates, cyanides, acetylacetonates, ammine complexes, carbonyl complexes and the like are preferable. More specifically, platinum chloride, platinum iodide, chloroplatinic acid, potassium chloroplatinate, P
Preferable examples include t (NH 3 ) 4 Cl 2 , palladium acetate, palladium chloride, palladium nitrate, palladium acetylacetonate, rhodium acetate, rhodium chloride, rhodium nitrate, ruthenium chloride, osmium chloride and iridium chloride. In the present invention, the content of the Group VIII metal is preferably 0.05 to 30% by weight based on the total catalyst amount.
And more preferably 0.2 to 10% by weight,
More preferably, it is 0.5 to 5% by weight.
【００１９】本発明のヘテロポリ酸の酸性塩と第VIII族
金属からなる触媒を調製する方法にはとくに制限はない
が、第VIII族金属の塩とヘテロポリ酸を接触させた後、
アルカリ金属塩又はアンモニウム塩で中和して酸性塩と
する方法が好ましい。ヘテロポリ酸酸性塩を調製した後
に第VIII族金属を担持すると、活性が低下する傾向があ
る。There is no particular limitation on the method for preparing the catalyst of the present invention, which comprises an acid salt of a heteropolyacid and a Group VIII metal. After contacting the salt of the Group VIII metal with the heteropolyacid,
A method of neutralizing with an alkali metal salt or an ammonium salt to obtain an acidic salt is preferable. When a Group VIII metal is supported after the heteropolyacid acid salt is prepared, the activity tends to decrease.
【００２０】本発明の触媒は、そのまま単独で触媒とし
て用いても良く、担体に担持して用いても良い。担体と
しては任意の担体を用いることができる。例えばシリ
カ、アルミナなどの金属酸化物、シリカ・アルミナなど
の金属複合酸化物、ゼオライト、活性炭などである。こ
の中でシリカ、アルミナ、チタニア、ジルコニア、活性
炭が好ましく、シリカが特に好ましい。The catalyst of the present invention may be used alone as a catalyst, or may be used by supporting it on a carrier. Any carrier can be used as the carrier. Examples thereof include metal oxides such as silica and alumina, metal composite oxides such as silica / alumina, zeolite, and activated carbon. Among these, silica, alumina, titania, zirconia, and activated carbon are preferable, and silica is particularly preferable.
【００２１】本発明の触媒は、酸化雰囲気での前処理を
行うことが望ましい。酸化雰囲気での前処理の例として
は、酸素ガス中の処理、空気中の処理が挙げられる。酸
化雰囲気での前処理を行うことにより、活性が向上し、
またパラフィンの異性化反応等の選択性が向上する。酸
化雰囲気での前処理の前後で、窒素、不活性ガス中での
処理を行っても差し支えない。水素ガス中での処理等の
還元雰囲気での前処理は、酸化雰囲気での前処理の前に
行うことが望ましい。還元雰囲気での前処理を酸化雰囲
気での前処理の後に行うと、酸化雰囲気での前処理での
前処理の効果が減少する傾向がある。The catalyst of the present invention is preferably pretreated in an oxidizing atmosphere. Examples of pretreatment in an oxidizing atmosphere include treatment in oxygen gas and treatment in air. Pretreatment in an oxidizing atmosphere improves activity,
In addition, the selectivity of paraffin isomerization reaction is improved. The treatment in nitrogen or an inert gas may be performed before and after the pretreatment in an oxidizing atmosphere. Pretreatment in a reducing atmosphere, such as treatment in hydrogen gas, is preferably performed before pretreatment in an oxidizing atmosphere. If the pretreatment in the reducing atmosphere is performed after the pretreatment in the oxidizing atmosphere, the effect of the pretreatment in the pretreatment in the oxidizing atmosphere tends to decrease.
【００２２】本発明の触媒はパラフィンの転化反応に有
効である。例えば、接触分解、接触改質、水素化分解、
異性化、アルキル化等が挙げられる。特に、パラフィン
の異性化、パラフィンのアルキル化反応に有効である。
本発明で用いるパラフィンとしては炭素数４〜１２のパ
ラフィンが好ましく、特に炭素数４〜８のパラフィンが
好ましい。具体的にはブタン、ペンタン、ヘキサン、ヘ
プタン、オクタンが好ましく用いられる。これらのパラ
フィンは単独で、またはこれらの混合して用いることが
できる。また、これらのパラフィンを５０重量％以上含
む軽質ナフサ留分を用いることができる。特にブタン、
ペンタン及びヘキサンが好ましい。The catalyst of the present invention is effective for the paraffin conversion reaction. For example, catalytic cracking, catalytic reforming, hydrocracking,
Examples include isomerization and alkylation. In particular, it is effective for paraffin isomerization and paraffin alkylation reaction.
As the paraffin used in the present invention, a paraffin having 4 to 12 carbon atoms is preferable, and a paraffin having 4 to 8 carbon atoms is particularly preferable. Specifically, butane, pentane, hexane, heptane and octane are preferably used. These paraffins can be used alone or as a mixture thereof. Further, a light naphtha fraction containing 50% by weight or more of these paraffins can be used. Especially butane,
Pentane and hexane are preferred.
【００２３】次にパラフィンの異性化反応について述べ
る。パラフィンの異性化反応は流通法、回分法のいずれ
かの方法によっても行うことができる。触媒の使用量は
回分法では原料に対して０．１〜１０重量％が好まし
く、特に１〜５重量％が好ましい。反応温度は７０〜４
００℃が好ましく、特に１００〜３５０℃が好ましい。
反応圧力は常圧下でも加圧下でもよい。流通法の場合、
液空間速度（ＬＨＳＶ）は０．１〜１０ｈｒ-1が好まし
く、特に０．３〜４ｈｒ-1が好ましい。また、本発明の
触媒は、水素共存下で反応を行うことが好ましい。水素
共存下で反応を行うことにより、異性化の活性、選択性
が向上し、寿命が長くなる傾向がある。反応ガス中の水
素の濃度は好ましくは０．１〜９９ｖｏｌ％、さらに好
ましくは０．５〜８０ｖｏｌ％、さらに特に好ましくは
１〜６０ｖｏｌ％である。Next, the isomerization reaction of paraffin will be described. The paraffin isomerization reaction can be carried out by either a flow method or a batch method. In the batch method, the amount of the catalyst used is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the raw materials. Reaction temperature is 70-4
00 ° C is preferable, and 100 to 350 ° C is particularly preferable.
The reaction pressure may be normal pressure or increased pressure. In the case of distribution law,
The liquid hourly space velocity (LHSV) is preferably from 0.1 to 10 -1, in particular 0.3～4Hr -1 are preferred. In addition, the catalyst of the present invention preferably performs the reaction in the coexistence of hydrogen. By carrying out the reaction in the presence of hydrogen, isomerization activity and selectivity are improved, and the life tends to be prolonged. The concentration of hydrogen in the reaction gas is preferably 0.1 to 99 vol%, more preferably 0.5 to 80 vol%, and even more preferably 1 to 60 vol%.
【００２４】[0024]
【実施例】以下、実施例および比較例によって本発明を
具体的に説明するが、本発明はこの実施例に限定される
ものではない。
実施例１
Ｈ3ＰＷ12Ｏ40・６Ｈ2Ｏ １０．９６ｇを０．０８ｍｏ
ｌ／ｌの水溶液とし、５０℃で撹拌しながらＰｔ（ＮＨ
3）4Ｃｌ2 ０．３０２４ｇを１０ｍｌの水に溶かした
溶液を徐々に滴下した。３０分おいた後、０．１２５ｍ
ｏｌ／ｌの炭酸セシウム水溶液を徐々に滴下した。室温
で一晩放置後、ロータリーエバポレーターで水を蒸発さ
せ、乾燥してＰｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40を得た。こ
の触媒はＰｔ１．５ｗｔ％であり表面積は１００ｍ2／
ｇであった。固定床流通反応装置を用いてブタン異性化
反応を行った。Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇをリ
アクターにつめ、Ｏ2ガス中１ｈ、Ｎ2ガス中１ｈ、３０
０℃で前処理を行った後、ブタン５ｖｏｌ％、Ｈ2５０
ｖｏｌ％及びＮ2４５ｖｏｌ％の混合ガスを１０ｍｌ／
ｍｉｎの流速で流し、反応温度３００℃、１気圧の条件
で反応させた。反応開始後５ｈの転化率、イソブタン選
択率、イソブタン生成速度を表１に示した。異性化反応
生成物であるイソブタン以外の生成物は、ほとんどメタ
ン、エタン、プロパンであった。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. EXAMPLE 1 H 3 PW 12 O 40 · 6H 2 O 10.96g 0.08mo
1 / l aqueous solution, Pt (NH
3 ) A solution of 0.3024 g of 4 Cl 2 in 10 ml of water was gradually added dropwise. 0.125m after 30 minutes
An ol / l cesium carbonate aqueous solution was gradually added dropwise. After standing overnight at room temperature, water is evaporated in a rotary evaporator and dried to obtain a Pt-Cs 2.5 H 0.5 PW 12 O 40. This catalyst is Pt 1.5 wt% and has a surface area of 100 m 2 /
It was g. The butane isomerization reaction was carried out using a fixed bed flow reactor. 1 g of Pt-Cs 2.5 H 0.5 PW 12 O 40 was packed in a reactor, and 1 hour in O 2 gas, 1 hour in N 2 gas, 30
After pretreatment at 0 ° C., butane 5 vol%, H 2 50
mixed gas of vol% and N 2 45 vol% at 10 ml /
It was made to flow at a flow rate of min, and the reaction was carried out at a reaction temperature of 300 ° C. and 1 atm. Table 1 shows the conversion rate, isobutane selectivity, and isobutane production rate 5 hours after the start of the reaction. Products other than isomerization reaction product isobutane were mostly methane, ethane, and propane.
【００２５】実施例２
反応ガスをブタン５ｖｏｌ％、Ｈ2ｖｏｌ５％、Ｎ2４５
ｖｏｌ％及びＨｅ４５ｖｏｌ％として、実施例１と同様
にブタンの異性化反応を行った。表１に結果を示した。Example 2 Butane 5 vol%, H 2 vol 5%, N 2 45
An isomerization reaction of butane was performed in the same manner as in Example 1 with vol% and He 45 vol%. The results are shown in Table 1.
【００２６】実施例３
Ｈ3ＰＷ12Ｏ40・６Ｈ2Ｏ １０．８６ｇを０．０８ｍｏ
ｌ／ｌの水溶液とし、５０℃で撹拌しながらＰｄ（ＮＯ
3）2・１．５Ｈ2Ｏ ０．４２３３ｇを５ｍｌの水に溶
かした溶液を徐々に滴下した。３０分おいた後、０．１
２５ｍｏｌ／ｌの炭酸セシウム水溶液を徐々に滴下し
た。室温で一晩放置後、ロータリーエバポレーターで水
を蒸発させ、乾燥してＰｄ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40を
得た。この触媒はＰｄ１．５ｗｔ％であり表面積は１１
３ｍ2／ｇであった。Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１
ｇの代りにＰｄ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇを用い
て、実施例１と同様にブタンの異性化反応を行った。表
１に結果を示した。[0026] Example 3 H 3 PW 12 O 40 · 6H 2 O 10.86g 0.08mo
1 / l of aqueous solution and stirred at 50 ° C with Pd (NO
3) 2 · 1.5H 2 O 0.4233g was gradually added dropwise a solution prepared by dissolving in water of 5 ml. After 30 minutes, 0.1
A 25 mol / l cesium carbonate aqueous solution was gradually added dropwise. After standing overnight at room temperature, water is evaporated in a rotary evaporator and dried to obtain a Pd-Cs 2.5 H 0.5 PW 12 O 40. This catalyst has a Pd of 1.5 wt% and a surface area of 11
It was 3 m 2 / g. Pt-Cs 2.5 H 0.5 PW 12 O 40 1
An isomerization reaction of butane was carried out in the same manner as in Example 1 except that 1 g of Pd-Cs 2.5 H 0.5 PW 12 O 40 was used instead of g. The results are shown in Table 1.
【００２７】実施例４
反応ガスをブタン５ｖｏｌ％、Ｈ2５ｖｏｌ％、Ｎ2４５
ｖｏｌ％及びＨｅ４５ｖｏｌ％として、実施例３と同様
にブタンの異性化反応を行った。表１に結果を示した。Example 4 5 vol% butane, 5 vol% H 2 , 45 N 2
An isomerization reaction of butane was carried out in the same manner as in Example 3 with vol% and He 45 vol%. The results are shown in Table 1.
【００２８】比較例１
Ｈ3ＰＷ12Ｏ40・６Ｈ2Ｏ ８．５６２ｇを０．０８ｍｏ
ｌ／ｌの水溶液とし、５０℃で撹拌しながらＰｔ（ＮＨ
3）4Ｃｌ2 ０．２１１８ｇを５ｍｌの水に溶かした溶
液を徐々に滴下した。室温で一晩放置後、ロータリーエ
バポレーターで水を蒸発させ、乾燥してＰｔ−Ｈ3ＰＷ
12Ｏ40を得た。この触媒はＰｔ１．５ｗｔ％であり表面
積は９．７ｍ2／ｇであった。Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ
12Ｏ40 １ｇの代りにＰｔ−Ｈ3ＰＷ12Ｏ40 １ｇを用
いて、実施例１と同様にブタンの異性化反応を行った。
表１に結果を示した。[0028] 0.08mo Comparative Example 1 H 3 PW 12 O 40 · 6H 2 O 8.562g
1 / l aqueous solution, Pt (NH
3 ) A solution of 0.2118 g of 4 Cl 2 in 5 ml of water was gradually added dropwise. After standing overnight at room temperature, water is evaporated in a rotary evaporator and dried to Pt-H 3 PW
12 O 40 was obtained. This catalyst had Pt of 1.5 wt% and a surface area of 9.7 m 2 / g. Pt-Cs 2.5 H 0.5 PW
Using 12 O 40 1g Pt-H 3 PW 12 O 40 1g instead of, was performed isomerization of butane in the same manner as in Example 1.
The results are shown in Table 1.
【００２９】比較例２
Ｈ3ＰＷ12Ｏ40・６Ｈ2Ｏ ８．２０３ｇを０．０８ｍｏ
ｌ／ｌの水溶液とし、５０℃で撹拌しながらＰｄ（ＮＯ
3）2・１．５Ｈ2Ｏ ０．２８６６ｇを５ｍｌの水に溶
かした溶液を徐々に滴下した。室温で一晩放置後、ロー
タリーエバポレーターで水を蒸発させ、乾燥してＰｄ−
Ｈ3ＰＷ12Ｏ40を得た。この触媒はＰｄ１．５ｗｔ％で
あり表面積は８．６ｍ2／ｇであった。Ｐｔ−Ｃｓ2.5Ｈ
0.5ＰＷ12Ｏ40 １ｇの代りにＰｄ−Ｈ3ＰＷ12Ｏ40 １
ｇを用いて、実施例１と同様にブタンの異性化反応を行
った。表１に結果を示した。[0029] 0.08mo Comparative Example 2 H 3 PW 12 O 40 · 6H 2 O 8.203g
1 / l of aqueous solution and stirred at 50 ° C with Pd (NO
3 ) A solution prepared by dissolving 0.2866 g of 2 · 1.5H 2 O in 5 ml of water was gradually added dropwise. After standing overnight at room temperature, water was evaporated on a rotary evaporator and dried to dry Pd-
H 3 PW 12 O 40 was obtained. The catalyst had a Pd of 1.5 wt% and a surface area of 8.6 m 2 / g. Pt-Cs 2.5 H
0.5 PW 12 O 40 1 g instead of Pd-H 3 PW 12 O 40 1
Using g, the butane isomerization reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.
【００３０】比較例３
Ｈ−ＺＳＭ−５（２５Ｈ、日本のモービルキャタリスト
社製）にＰｔ１ｗｔ％を担持した触媒０．５ｇをＰｔ−
Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりに用いて、実施例
１と同様にブタンの異性化反応を行った。表１に結果を
示した。Comparative Example 3 H-ZSM-5 (25H, manufactured by Mobile Catalyst of Japan) was loaded with 0.5 g of a catalyst in which 1 wt% of Pt was supported on Pt-.
An isomerization reaction of butane was carried out in the same manner as in Example 1 except that 1 g of Cs 2.5 H 0.5 PW 12 O 40 was used. The results are shown in Table 1.
【００３１】比較例４
市販の１ｗｔ％Ｐｔ／Ａｌ2Ｏ3（Ｎ．Ｅ．ケムキャット
社製）をＰｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40の代わりに用い
て、実施例１と同様にブタンの異性化反応を行った。表
１に結果を示した。Comparative Example 4 A commercially available 1 wt% Pt / Al 2 O 3 (manufactured by NE Chemcat) was used in place of Pt-Cs 2.5 H 0.5 PW 12 O 40 , butane of butane was obtained in the same manner as in Example 1. An isomerization reaction was performed. The results are shown in Table 1.
【００３２】比較例５
炭酸セシウム水溶液の滴下量のみを変え、実施例１と同
様の方法でＰｔ−Ｃｓ3ＰＷ12Ｏ40を調製した。Ｐｔ−
Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりにＰｔ−Ｃｓ3Ｐ
Ｗ12Ｏ40１ｇ用い、かつ触媒の前処理として、Ｎ2ガス
処理の後、Ｏ2ガス処理が行われた以外は実施例１と同
様にブタン異性化反応を行った。表１に結果を示した。Comparative Example 5 Pt-Cs 3 PW 12 O 40 was prepared in the same manner as in Example 1, except that the amount of the cesium carbonate aqueous solution added was changed. Pt-
Cs 2.5 H 0.5 PW 12 O 40 Pt-Cs 3 P instead of 1 g
A butane isomerization reaction was carried out in the same manner as in Example 1 except that 1 g of W 12 O 40 was used, and as a pretreatment of the catalyst, N 2 gas treatment and then O 2 gas treatment were carried out. The results are shown in Table 1.
【００３３】比較例６
Ｈ3ＰＷ12Ｏ40・６Ｈ2Ｏを０．０８ｍｏｌ／ｌの水溶液
とし、撹拌しながら０．１２５ｍｏｌ／ｌの炭酸セシウ
ム水溶液を徐々に滴下した。一晩放置後、ロータリーエ
バポレーターで水を蒸発させ、乾燥してＣｓ2.5Ｈ0.5Ｐ
Ｗ12Ｏ40を得た。 Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇ
の代わりにＣｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇを用いて、実施
例１と同様にブタン異性化反応を行った。表１に結果を
示した。Comparative Example 6 H 3 PW 12 O 40 · 6H 2 O was made into a 0.08 mol / l aqueous solution, and a 0.125 mol / l cesium carbonate aqueous solution was gradually added dropwise while stirring. After standing overnight, evaporate the water with a rotary evaporator and dry to dryness to Cs 2.5 H 0.5 P
W 12 O 40 was obtained. Pt-Cs 2.5 H 0.5 PW 12 O 40 1 g
Butane isomerization reaction was carried out in the same manner as in Example 1 except that 1 g of Cs 2.5 H 0.5 PW 12 O 40 was used instead of. The results are shown in Table 1.
【００３４】比較例７
オキシ塩化ジルコニウム水溶液にアンモニア水を加え、
沈殿を生じさせた。沈殿をろ過、乾燥後、０．５ｍｏｌ
／ｌの硫酸を注ぎ、乾燥した。これに塩化白金酸水溶液
を含浸し、乾燥、焼成してＰｔ担持硫酸処理ＺｒＯ2触
媒（Ｐｔ−ＳＯ4 2-／ＺｒＯ2と略記する）を得た。Ｐｔ
−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40の代わりにＰｔ−ＳＯ4 2-／
ＺｒＯ2１ｇ用いて、実施例１と同様にブタン異性化反
応を行った。表１に結果を示した。Comparative Example 7 Aqueous ammonia was added to an aqueous zirconium oxychloride solution,
A precipitate formed. After the precipitate is filtered and dried, 0.5 mol
/ L sulfuric acid was poured and dried. This was impregnated with a chloroplatinic acid aqueous solution, dried, and calcined to obtain a Pt-supported sulfuric acid-treated ZrO 2 catalyst (abbreviated as Pt—SO 4 2− / ZrO 2 ). Pt
-Cs 2.5 H 0.5 PW 12 O 40 Instead of Pt-SO 4 2- /
A butane isomerization reaction was carried out in the same manner as in Example 1 using 1 g of ZrO 2 . The results are shown in Table 1.
【００３５】実施例５
固定床高圧流通反応装置を用いてペンタン異性化反応を
行った。実施例１で得たＰｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40
１ｇをリアクターにつめ、Ｏ2ガス中１ｈ、Ｎ2ガス中１
ｈ、３００℃で前処理を行った後、反応温度１７０℃、
全圧２０ｋｇ／ｃｍ2、Ｈ2／ペンタン比３／２、ＷＨＳ
Ｖ４ｈ-1の条件で反応させた。反応開始後５ｈの転化
率、イソペンタン選択率を表２に示した。異性化反応生
成物であるイソペンタン以外の生成物は、ほとんどメタ
ン、エタン、プロパン、ブタンであった。Example 5 A pentane isomerization reaction was carried out using a fixed bed high pressure flow reactor. Pt—Cs 2.5 H 0.5 PW 12 O 40 obtained in Example 1
1g was packed in the reactor, 1h in O 2 gas, 1 in N 2 gas
h after pretreatment at 300 ° C., reaction temperature 170 ° C.,
Total pressure 20kg / cm 2 , H 2 / pentane ratio 3/2, WHS
The reaction was carried out under the condition of V4h -1 . Table 2 shows the conversion and isopentane selectivity 5 hours after the start of the reaction. Products other than isomerization reaction product isopentane were mostly methane, ethane, propane and butane.
【００３６】実施例６
Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりに実施例３
で得たＰｄ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇを用いて実施
例５と同様にペンタン異性化反応を行った。表２に結果
を示した。Example 6 Example 3 was used in place of 1 g of Pt-Cs 2.5 H 0.5 PW 12 O 40.
A pentane isomerization reaction was carried out in the same manner as in Example 5 using 1 g of Pd-Cs 2.5 H 0.5 PW 12 O 40 obtained in. The results are shown in Table 2.
【００３７】実施例７
炭酸セシウム水溶液の滴下量のみを変え、実施例１と同
様の方法でＰｔ−Ｃｓ2.4Ｈ0.6ＰＷ12Ｏ40を調製した。
Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりにＰｔ−Ｃ
ｓ2.4Ｈ0.6ＰＷ12Ｏ40１ｇを用いて、実施例５と同様に
ペンタン異性化反応を行った。表２に結果を示した。Example 7 Pt-Cs 2.4 H 0.6 PW 12 O 40 was prepared in the same manner as in Example 1 except that the amount of the cesium carbonate aqueous solution added was changed.
Pt-Cs 2.5 H 0.5 PW 12 O 40 Pt-C instead of 1 g
A pentane isomerization reaction was carried out in the same manner as in Example 5 using 1 g of s 2.4 H 0.6 PW 12 O 40 . The results are shown in Table 2.
【００３８】実施例８
炭酸セシウム水溶液の滴下量のみを変え、実施例１と同
様の方法でＰｔ−Ｃｓ2.6Ｈ0.4ＰＷ12Ｏ40を調製した。
Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりにＰｔ−Ｃ
ｓ2.6Ｈ0.4ＰＷ12Ｏ40１ｇを用いて、実施例５と同様に
ペンタン異性化反応を行った。表２に結果を示した。Example 8 Pt-Cs 2.6 H 0.4 PW 12 O 40 was prepared in the same manner as in Example 1, except that the amount of the cesium carbonate aqueous solution added was changed.
Pt-Cs 2.5 H 0.5 PW 12 O 40 Pt-C instead of 1 g
A pentane isomerization reaction was carried out in the same manner as in Example 5 using 1 g of s 2.6 H 0.4 PW 12 O 40 . The results are shown in Table 2.
【００３９】比較例８
Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりに比較例５
で得たＰｔ−Ｃｓ3ＰＷ12Ｏ40１ｇを用いて、実施例５
と同様にペンタン異性化反応を行った。表２に結果を示
した。Comparative Example 8 Pt—Cs 2.5 H 0.5 PW 12 O 40 Comparative Example 5 instead of 1 g
In using a Pt-Cs 3 PW 12 O 40 1g obtained, Example 5
The pentane isomerization reaction was carried out in the same manner as in. The results are shown in Table 2.
【００４０】比較例９
Ｐｔ−Ｃｓ2.5Ｈ0.5ＰＷ12Ｏ40１ｇの代わりに比較例７
で得たＰｔ−ＳＯ4 2-／ＺｒＯ2１ｇを用いて、実施例５
と同様にペンタン異性化反応を行った。表２に結果を示
した。Comparative Example 9 Pt—Cs 2.5 H 0.5 PW 12 O 40 Comparative Example 7 instead of 1 g
Example 5 using 1 g of Pt—SO 4 2− / ZrO 2 obtained in
The pentane isomerization reaction was carried out in the same manner as in. The results are shown in Table 2.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【表２】 [Table 2]
【００４３】表１及び表２から明らかなように、本発明
の触媒はパラフィンの転化反応であるブタンおよびペン
タンの異性化反応においてイソブタンおよびイソペンタ
ン選択率が高く、かつ転化率も高い優れた触媒である。As is clear from Tables 1 and 2, the catalyst of the present invention is an excellent catalyst having a high selectivity of isobutane and isopentane in the isomerization reaction of butane and pentane, which is a conversion reaction of paraffin, and a high conversion rate. is there.
【００４４】[0044]
【発明の効果】本発明の触媒は腐食性がなく、反応物と
の分離が容易で、さらにパラフィンの異性化反応に高活
性な触媒である。Industrial Applicability The catalyst of the present invention is not corrosive, can be easily separated from the reaction product, and is highly active in the paraffin isomerization reaction.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ１０Ｇ 11/02 Ｃ１０Ｇ 35/06 35/06 45/62 45/62 47/14 47/14 49/06 49/06 Ｃ０７Ｂ 61/00 ３００ // Ｃ０７Ｂ 61/00 ３００ Ｂ０１Ｊ 23/64 １０３Ｚ (72)発明者 榎本 敏行 神奈川県横浜市中区千鳥町８番地 日本 石油株式会社中央技術研究所内 (56)参考文献 特開 平５−306240（ＪＰ，Ａ) 特開 平５−255132（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C07B 61/00 C07C 5/27 C27C 9/12 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C10G 11/02 C10G 35/06 35/06 45/62 45/62 47/14 47/14 49/06 49/06 C07B 61 / 00 300 // C07B 61/00 300 B01J 23/64 103Z (72) Inventor Toshiyuki Enomoto 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Petroleum Co., Ltd. Central Research Institute (56) Reference JP-A-5-306240 (JP, A) JP 5-255132 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-38/74 C07B 61/00 C07C 5/27 C27C 9 / 12
Claims (2)
ロポリ酸の酸性塩と第VIII族金属とを必須成分とするこ
とを特徴とするパラフィンの異性化用固体酸触媒。 （式中ＬはＲｂ + 、Ｃｓ + 又はＮＨ ４ + 、Ｘはヘテロ原
子、Ｙはポリ原子、ｌ、ｍ、ｎはそれぞれＬ、Ｘ、Ｙの
価数、ｋはＬの個数で、０を超え、（８０−ｍ−１２
ｎ）／ｌ未満個である） 1. A solid acid for the isomerization of paraffins, which comprises, as essential components, an acid salt of a heteropoly acid having a composition represented by the following general formula (2) and a Group VIII metal. catalyst. (In the formula, L is Rb + , Cs + or NH 4 + , and X is a hetero atom.
Child, Y is a poly atom, l, m and n are L, X and Y, respectively.
Valence, k is the number of L, which exceeds 0 and is (80-m-12
n) / l less than 1)
ポリ酸の酸性塩と第VIII族金属とを必須成分とする固体
酸触媒及び水素の存在下で、パラフィンの異性化を行う
ことを特徴とするパラフィンの異性化方法。 （式中ＬはＲｂ + 、Ｃｓ + 又はＮＨ ４ + 、Ｘはヘテロ原
子、Ｙはポリ原子、ｌ、ｍ、ｎはそれぞれＬ、Ｘ、Ｙの
価数、ｋはＬの個数で、０を超え、（８０−ｍ−１２
ｎ）／ｌ未満個である） 2. A solid acid catalyst comprising an acidic salt of a heteropolyacid having a composition represented by the following general formula (2) and a Group VIII metal as essential components and paraffin in the presence of hydrogen. A method for isomerizing paraffin, which comprises performing isomerization. (In the formula, L is Rb + , Cs + or NH 4 + , and X is a hetero atom.
Child, Y is a poly atom, l, m and n are L, X and Y, respectively.
Valence, k is the number of L, which exceeds 0 and is (80-m-12
n) / l less than 1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07810594A JP3522824B2 (en) | 1993-03-26 | 1994-03-24 | Solid acid catalyst for paraffin isomerization and method for paraffin isomerization using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-92125 | 1993-03-26 | ||
| JP9212593 | 1993-03-26 | ||
| JP07810594A JP3522824B2 (en) | 1993-03-26 | 1994-03-24 | Solid acid catalyst for paraffin isomerization and method for paraffin isomerization using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06327976A JPH06327976A (en) | 1994-11-29 |
| JP3522824B2 true JP3522824B2 (en) | 2004-04-26 |
Family
ID=26419179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07810594A Expired - Fee Related JP3522824B2 (en) | 1993-03-26 | 1994-03-24 | Solid acid catalyst for paraffin isomerization and method for paraffin isomerization using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3522824B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080032886A1 (en) * | 2006-08-03 | 2008-02-07 | Abb Lummus Global, Inc. | Doped solid acid catalyst composition, process of conversion using same and conversion products thereof |
| FR2944716B1 (en) * | 2009-04-28 | 2011-05-27 | Centre Nat Rech Scient | CATALYST AND PROCESS FOR ELECTROCHEMICAL OXIDATION OF METHANE |
| CN103055906B (en) * | 2011-10-18 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of Solid superacid bifunctional catalyst and preparation method thereof |
| CN103059911B (en) * | 2011-10-18 | 2015-03-18 | 中国石油化工股份有限公司 | Isomerization reaction method of straight-chain paraffin |
| CN103059912B (en) * | 2011-10-18 | 2015-02-25 | 中国石油化工股份有限公司 | Isomerization reaction method of straight-chain paraffin |
| CN103055912B (en) * | 2011-10-18 | 2015-07-29 | 中国石油化工股份有限公司 | Solid superacid bifunctional catalyst and preparation method thereof |
-
1994
- 1994-03-24 JP JP07810594A patent/JP3522824B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06327976A (en) | 1994-11-29 |
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