JPH01245854A - Solid acid catalyst for alkylation reaction - Google Patents
Solid acid catalyst for alkylation reactionInfo
- Publication number
- JPH01245854A JPH01245854A JP63073410A JP7341088A JPH01245854A JP H01245854 A JPH01245854 A JP H01245854A JP 63073410 A JP63073410 A JP 63073410A JP 7341088 A JP7341088 A JP 7341088A JP H01245854 A JPH01245854 A JP H01245854A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- solid acid
- group
- sulfate
- acid catalyst
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 23
- 239000011973 solid acid Substances 0.000 title claims abstract description 13
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 239000001282 iso-butane Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 230000006641 stabilisation Effects 0.000 claims abstract 2
- 238000011105 stabilization Methods 0.000 claims abstract 2
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 abstract description 6
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 abstract description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000029936 alkylation Effects 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- -1 compound metal-compound Chemical class 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 244000175448 Citrus madurensis Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000017317 Fortunella Nutrition 0.000 description 1
- 229910007156 Si(OH)4 Inorganic materials 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material 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
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は第■族の複合金属化合物全担体とする強酸点を
有する新規なインパラフィン、特にイソブタンのオレフ
ィンによるアルキレーション反応用固体酸触媒に関する
ものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a solid acid catalyst for the alkylation reaction of isobutane with a novel imparaffin having strong acid sites, and in particular, isobutane as a whole carrier of a Group Ⅰ complex metal compound. It is something.
イソブタンのオレフィンによるアルキレーション反応は
、軽質炭化水素の重質化反応、すなわち自動車燃料に適
した高オクタン価のガンリン留分への転換技術として、
石油精製業界においては重要な技術でラシ広〈実施され
ている。The alkylation reaction of isobutane with olefins is a technology for converting light hydrocarbons into heavier ones, i.e., the Ganlin fraction with a high octane number suitable for automobile fuel.
In the oil refining industry, it is an important technology that is widely implemented.
アルキレーション反応は一般に、工業的には硫＠めるい
はふつ化水索酸全触媒として用いる方法がほとんどであ
るが、これらの方法は原料もしくは生成物および触媒と
も液体である均一系反応方式であるため、反応生成物と
触媒の分離工程を必要とし、非常に不経済である。まｆ
ｃ１廃酸処理の問題、触媒の取シ扱いの困難さ、毒性あ
るいは腐食性の問題等があシ、必ずしも工業的に十分な
技術とは言い難い。In general, most industrial alkylation reactions use sulfur as a total catalyst, but these methods are homogeneous reactions in which both the raw material or product and the catalyst are liquids. Therefore, a separation step between the reaction product and the catalyst is required, which is very uneconomical. Maf
There are problems with c1 waste acid treatment, difficulty in handling the catalyst, and problems with toxicity or corrosivity, and it is not necessarily an industrially sufficient technology.
前述し几イノパラフィンのオレフィンによるアルキレー
ション反応に使用している液体触媒にみられる問題を解
消するため、過去においてアルキレーション反応に活性
のある固体酸触媒の研究例が一部見られる。In order to solve the aforementioned problems with the liquid catalysts used in the alkylation reaction of inoparaffins with olefins, some research has been done in the past on solid acid catalysts that are active in the alkylation reaction.
例えば特開昭５．１−６３５８６にはルイス酸担持グラ
ファイト含有炭素系、特公昭５７−３６５０には巨大網
目構造の酸型カチオン交換樹脂系、 Ｕ、Ｓ、Ｐ、
３，２５１，９０２ 、４，３７７．７２１．５．６５
５，８１３、特開昭５１−６８５０１には結晶性アルミ
ノシリケートゼ第２イト系、あるいは特公昭５９−６１
８１．５９−４００５６にはジルコニアおよび酸化鉄系
等がお、げられる。For example, JP-A-5.1-63586 discloses a Lewis acid-supported graphite-containing carbon system, JP-A-57-3650 discloses an acid type cation exchange resin system with a giant network structure, U, S, P,
3,251,902, 4,377.721.5.65
5,813, Japanese Patent Publication No. 51-68501 describes crystalline aluminosilicate enzyme second type, or Japanese Patent Publication No. 59-61
81.59-40056 includes zirconia and iron oxide.
しかし、これらの固体酸触媒は生成物のアルキレート収
率が低い、アルキレートのオクタン価が低い、オレフィ
ンの重合反応が併発する、あるいは活性劣化が大きい等
の理由から未だ実用化には至っていない。However, these solid acid catalysts have not yet been put into practical use due to reasons such as low alkylate yield, low octane number of alkylate, co-occurrence of olefin polymerization reaction, or large deterioration of activity.
これらのことから、アルキレーション活性の大きい、か
つその生成物のオクタン価の高い、また触媒寿命の長い
固体酸触媒の出現がまたれている。These factors have led to the emergence of solid acid catalysts with high alkylation activity, high octane numbers of their products, and long catalyst life.
本発明者らは前記従来技術の問題点を解決する九め鋭意
検討した結果、アルキレーション活性および選択性に優
れ九固体酸触媒を見出し、本発明を完成するに到達した
ものである。The inventors of the present invention have made extensive studies to solve the problems of the prior art, and as a result have found nine solid acid catalysts with excellent alkylation activity and selectivity, and have completed the present invention.
すなわち、本発明は周期律表■族金属の少なくとも２種
以上の金属の複合金属水酸化物もしくは複合金属酸化物
からなる担体に、硫酸根もしくはＷｃ＠根の前駆物質を
含有させ、焼成安定化してなるイソブタンのオレフィン
によるアルキレーション反応用固体酸触媒でらす、該触
媒はイソブタンのオレフィンによるアルキレーション反
応に高活性を示し、該アルキレーション反応生成物のう
ちオクタン価の高い炭化水素であるトリメチルペンタン
（ＴＭＰ ） の選択性に優れているという特長を有
する。That is, the present invention provides a support made of a composite metal hydroxide or a composite metal oxide of at least two or more metals of group Ⅰ of the periodic table, containing a precursor of a sulfate group or a Wc@ group, and stabilizing it by firing. The solid acid catalyst for the alkylation reaction of isobutane with olefins is highly active, and among the alkylation reaction products, trimethylpentane, a hydrocarbon with a high octane number, is (TMP) is characterized by excellent selectivity.
本発明で用いる担体の■族金属の複合水酸化物もしくは
複合酸化物は、チタン（’ｒｉ）、ジルコニウム（Ｚｒ
）、ケイ素（Ｓｌ）およびスズ（ａｎ）から選択される
少なくとも２種以上の複合水酸化物もしくは複合酸化物
を指す。これらの複合水酸化物もしくは複合酸化物は■
族金属塩の水浴液へのアンモニア水等のアルカリ添加に
よって沈殿する複合水酸化物、もしくは熱分解によって
生成する複合酸化物等、通常用いられる方法によって得
られる。The composite hydroxides or composite oxides of group Ⅰ metals as carriers used in the present invention are titanium ('ri), zirconium (Zr
), silicon (Sl), and tin (an). These composite hydroxides or composite oxides are ■
A complex hydroxide precipitated by adding an alkali such as aqueous ammonia to a water bath solution of a group metal salt, or a complex oxide produced by thermal decomposition, etc. can be obtained by a commonly used method.
硫酸根もしくは硫酸根の前駆物質とは、硫酸（ＨｇＳＯ
４）、硫酸アンモニウム（（ＮＨ４）ｚｓＯａ ：ｌ、
亜硫酸アンモニウムＣ（ＮＨ４）ｚｓｏ＠ 〕、硫酸水
素アンモニウム（（ＮＨ４）Ｈ８０４）、塩化スル７リ
ル（８０ｉＣ＆）等を指すが、好ましくは硫酸、硫酸ア
ンモニウムおよび塩化スル７リルが適している。この硫
酸根を含有させる方法については、−例をあげれば、乾
燥した■族金属の複合水酸化物もしくは複合酸化物をそ
の１〜１０重量倍の（ＬＯ１〜１０モル濃度、好ましく
は１１１〜５モルｇ１度の硫酸根含有水溶液に浸漬もし
くは流下等により、接触させて処理する方法があげられ
る。The sulfate group or the precursor of the sulfate group is sulfuric acid (HgSO
4), ammonium sulfate ((NH4)zsOa: l,
It refers to ammonium sulfite C(NH4)zso@], ammonium hydrogen sulfate ((NH4)H804), sul7lyl chloride (80iC&), etc., and preferably sulfuric acid, ammonium sulfate, and sul7lyl chloride are suitable. Regarding the method of incorporating this sulfate group, for example, a dried composite hydroxide or composite oxide of a group Ⅰ metal is added at a concentration of 1 to 10 times its weight (LO 1 to 10 molar concentration, preferably 111 to 5 Examples include a method of contacting with an aqueous solution containing sulfuric acid radicals of 1 mol g by immersion or flowing down.
また６本発明触媒は、硫酸根もしくは硫酸根前駆物質を
混合する前に５０〜５５０℃、好ましくは１００〜４０
０℃の温度で１〜２４時間空気焼成を行なっても構わな
いが、本発明によれば硫酸根もしくは硫酸根前駆物質に
よる処理を行なつ九後は４００５８００Ｃ１好ましくは
４５０〜７００℃で１５〜１０時間焼成安定化すること
が必要である。In addition, the catalyst of the present invention is heated to 50 to 550°C, preferably 100 to 40°C, before mixing the sulfate group or sulfate group precursor.
Air calcination may be carried out at a temperature of 0°C for 1 to 24 hours, but according to the present invention, after treatment with sulfate radicals or sulfate radical precursors, 4005800C1 is preferably used at 450 to 700°C for 15 to 10 hours. It is necessary to stabilize the firing time.
上記製造方法で製造された触媒は、反応条件下にインパ
ラフイ／をオレフィンと共に接触さセルことによシ、優
れたアルキレーション反応活性を有する。アルキレーシ
ョン反応に適当なイソメ２フインとしては、イソブタン
（１−Ｃ４Ｈｘｏ）が好ましく、オレフィンとしては２
〜６個の炭素数を有するもの、好ましくは２〜４個の炭
素数を有するオレフィン、すなわちエチレン（Ｃ１Ｈ４
）、プロピレン（ＣｓＨｓ）ｖ ブテン（ＣａＨａ ）
が適している。The catalyst produced by the above production method has excellent alkylation reaction activity, especially when the catalyst is contacted with an olefin under reaction conditions. Isobutane (1-C4Hxo) is preferred as the isome-2 fin suitable for the alkylation reaction, and as the olefin,
~6 carbon atoms, preferably olefins with 2 to 4 carbon atoms, i.e. ethylene (C1H4
), propylene (CsHs) v butene (CaHa)
is suitable.
本発明の触媒を使用するアルキレーション反応の適当な
反応条件は、原料および反応方式に依存する。反応は液
相において行なうのが好ましく、したがって反応圧力は
１へ６０バールが適当である。Suitable reaction conditions for alkylation reactions using the catalysts of the present invention depend on the raw materials and reaction mode. The reaction is preferably carried out in the liquid phase, so reaction pressures of 1 to 60 bar are suitable.
また、反応温度は−４０〜２００℃好ましくは−２０−
−１２０℃が適している。供給する原料のイソブタン／
オレフィン比は１ ／ １ ＝ ２００／１（ｗｔ／
ｗｔ ） が適当でらシ、オレフィン濃度が高くなシ
過ぎるとオレフィンの重合が多くな広本来の目的とする
アルキレーション反応を阻害するおそれがおる〇
このようにして得られた反応生成物のアルキレートは、
Ｃ１成分、特にトリメチルペンタンへの選択性に著しく
優れているＯ
本発明を以下の実施例にてさらに詳細に説明する。一
実施例１
市販オキシ塩化ジルコニウム（Ｚｒ０Ｃｔ２・８Ｈ，Ｏ
）２に９と四塩化チタン（Ｔｉｃｋ） １．１８ｋｇを
純水１５ｔＫ溶解させ、攪拌しながらアンモニア水ｆｔ
ｐＨ１０になるまで徐々に滴下し、生成した水酸化ジル
コニウム・水酸化チタン［Ｚｒ（ＯＨ）ｉ ・Ｔｉ（Ｏ
Ｈ）４］複合水酸化物を一昼夜熟成後、ろ過、洗浄、真
空乾燥（１１０℃）して白色粉末的１５００ｆを得た。In addition, the reaction temperature is -40 to 200°C, preferably -20-
-120°C is suitable. Isobutane, the raw material to be supplied/
The olefin ratio is 1/1 = 200/1 (wt/
wt) is appropriate, but if the olefin concentration is too high, there is a risk of inhibiting the alkylation reaction, which is the original purpose of olefin polymerization. Chelate is
The present invention will be explained in more detail with reference to the following examples. Example 1 Commercially available zirconium oxychloride (Zr0Ct2.8H,O
) Dissolve 9 and 1.18 kg of titanium tetrachloride (Tick) in 15 tK of pure water, and add ft of ammonia water while stirring.
It was gradually added dropwise until the pH reached 10, and the generated zirconium hydroxide/titanium hydroxide [Zr(OH)i ・Ti(O
H) 4] Composite hydroxide was aged for a day and night, filtered, washed, and vacuum dried (110°C) to obtain 1500f as a white powder.
この複合水酸化物ｔ−１モル譲度の硫酸７を中に導入、
過剰の硫酸をろ過した後、乾燥し５５０℃で３時間焼成
して、触媒Ａ （Ｅ３０ａ／ ＺｒＯ２・ＴｉＯ２：（
ＺｒＯｌ ：’ｒ１ｏ＝＝５０ ： ５０モル比ン〕を
得た。Introducing sulfuric acid 7 with a yield of t-1 mol of this composite hydroxide,
After filtering off excess sulfuric acid, it was dried and calcined at 550°C for 3 hours to prepare catalyst A (E30a/ZrO2・TiO2:(
ZrOl:'r1o==50:50 molar ratio] was obtained.
ベンゼン溶媒中でのハメット指示薬を用いた滴定法によ
る酸強度の測定結果全表１に示す。Table 1 shows the measurement results of acid strength by a titration method using a Hammett indicator in a benzene solvent.
実施例２
実施例１と同様な試薬を用いて、 Ｚｒ（ＯＨ）４ ：
Ｔｉ（ＯＨ）４ ＝ ８０ ： ２０ 、 ３０ ：
７０ （モル比）となるような複合水酸化物ｅｙｓ製し
、実施例１と同様な方法にて硫酸処理し、さらに、乾燥
し５５０℃で３時間焼成して、触ｖＥ、Ｂ ｈ触媒Ｃｔ
−得た。また、実施例１で得られた硫酸処理した複合水
酸化物を５００℃、６００℃で３時間焼成して触媒Ｄ１
触媒Ｅを得た。ハメット指示薬金柑いた滴定法による酸
強度の測定結果を表１に示す。Example 2 Using the same reagents as in Example 1, Zr(OH)4:
Ti(OH)4 = 80: 20, 30:
70 (molar ratio), treated with sulfuric acid in the same manner as in Example 1, dried and calcined at 550°C for 3 hours to obtain catalyst Ct.
-I got it. Further, the sulfuric acid-treated composite hydroxide obtained in Example 1 was calcined at 500°C and 600°C for 3 hours to prepare catalyst D1.
Catalyst E was obtained. Table 1 shows the measurement results of acid strength using Hammett indicator kumquat titration method.
実施例３
市販のオキシ塩化ジルコニウム（ＺｒＯＣ／１４・８Ｈ
Ｉ Ｏ）と塩化スズ（５ｎＣ１４） を純水に浴屏させ
ｐＨａＯになるまでアンモニア水を滴下に共沈殿物を生
成させ、熟成、ろ過、洗浄および乾燥してＺｒ（ＯＨ）
４− Ｓｎ（ＯＨ）２ の複合水酸化物を得た。マた、
オキシ塩化ジルコニウムとシリカゾルを純水に溶解させ
、ｐｎａｏになるまでＮＵ３水溶液を滴下して共沈殿物
を生成させ、熟成ろ過、洗浄および乾燥してＺｒ（ＯＨ
）４・Ｓｉ（ＯＨ）４の複合水酸化物を得る。Example 3 Commercially available zirconium oxychloride (ZrOC/14.8H
Zr(OH) and tin chloride (5nC14) are bathed in pure water and aqueous ammonia is added dropwise until pHaO is reached to form a coprecipitate, which is aged, filtered, washed and dried to form Zr(OH).
A composite hydroxide of 4-Sn(OH)2 was obtained. Mother,
Zr(OH
)4.Si(OH)4 composite hydroxide is obtained.
これらのＺｒ（ＯＨ）４・８ｎ（ＯＨ）１ （５０：
５０モル比）、Ｚｒ（ＯＨ）４・８１（ＯＨ）４ （５
０： ５０モル比）を実施例１°と同様な方法で硫酸処
理して、乾燥、焼成（５５０℃、３時間）シ、触媒Ｆ％
Ｇを得た。酸強度の測定結果を表１に示す。These Zr(OH)4.8n(OH)1 (50:
50 molar ratio), Zr(OH)4.81(OH)4 (5
0:50 molar ratio) was treated with sulfuric acid in the same manner as in Example 1, dried and calcined (550°C, 3 hours), and the catalyst F%
I got a G. Table 1 shows the measurement results of acid strength.
実施例４
実施例１と同様な方法で調製し次Ｚｒ（０Ｈ）４・Ｔｉ
（ＯＨ）４複合水酸化物［Ｚｒ（ＯＨ）４・Ｔｉ（ＯＨ
）４ ＝ ５０ ： ５０ モル比］を１５モル濃度の
亜硫酸アンモニウム溶液（（ＮＨａ）ｚｓＯｓ ）
まｔは、塩化スルフリルに浸漬し、過剰分をろ過した後
、乾燥し、５５０℃で３時間焼成し触媒Ｈ，Ｉを得た。Example 4 Zr(0H)4.Ti was prepared in the same manner as in Example 1.
(OH)4 composite hydroxide [Zr(OH)4・Ti(OH
)4 = 50:50 molar ratio] to a 15 molar ammonium sulfite solution ((NHa)zsOs)
The catalyst was immersed in sulfuryl chloride, the excess was filtered, dried, and calcined at 550° C. for 3 hours to obtain catalysts H and I.
酸強度の測定結果を表１に示す。Table 1 shows the measurement results of acid strength.
比較例１
オキシ塩化ジルコニウム水溶液にアンモニア水を滴下し
て得たＺｒ（ＯＨ）４を１モル蹟度の硫酸中に導入し、
ろ過、乾燥後、５５０℃で焼成し触媒Ｊｆｔ得た。酸強
度の測定結果全表１に示す。Comparative Example 1 Zr(OH)4 obtained by dropping aqueous ammonia into an aqueous zirconium oxychloride solution was introduced into 1 molar sulfuric acid,
After filtering and drying, it was calcined at 550°C to obtain a catalyst Jft. The measurement results of acid strength are shown in Table 1.
比較例２
実施例１と同様な方法で調製したＺｒ（ＯＨ）４・Ｔｉ
（ＯＨ）４複合水酸化物を５５０℃で３時間焼成し次触
媒Ｋを得た。酸強度測定結果を表１に示す。Comparative Example 2 Zr(OH)4・Ti prepared in the same manner as Example 1
The (OH)4 composite hydroxide was calcined at 550°C for 3 hours to obtain the next catalyst K. Table 1 shows the acid strength measurement results.
表１Ｌカ、硫酸根または硫酸根の前駆物質を含有した２
゛種以上のｌｖ族金属の複合水酸化物もしくは複合酸化
物を焼成安定化することに工っで得られる触媒は酸度関
数（Ｈｅ）が−１２，７エク強い酸強度を有する固体酸
触媒となっていることがわかる。Table 1L mosquitoes, 2 containing sulfate radicals or sulfate radical precursors
゛The catalyst obtained by firing and stabilizing the composite hydroxide or composite oxide of more than one type of lv group metal is a solid acid catalyst with an acidity function (He) of -12.7 Eq and strong acid strength. You can see that it is happening.
〔実験例１〕
実施例１〜４、比較例１．２の手法にて調製し友触媒Ａ
〜触媒ｘｌ使用して、固定床、加圧液相流通式でアルキ
レーション反応を行った。[Experimental Example 1] Friend catalyst A prepared by the method of Examples 1 to 4 and Comparative Example 1.2
~ Catalyst xl was used to carry out the alkylation reaction in a fixed bed, pressurized liquid phase flow system.
反応方法は、まず所定量の乾燥した触媒全１６−２８メ
ツシユに成型してリアクターに充填した。前処理として
、空気を４００℃、３ｈ供給後窒素に切シ換え、所定温
度、所定圧力に設定する。次に窒素の供給をストップし
、所定比に混合したイソブタン（１−Ｃ，）とシス−２
−ブテン（Ｃ１８−２−Ｃ４″″）の原料液を触媒上に
所定流量にて供給する。リアクター出口液組成の分析は
辰ナンプラーを用いることにより随時ガスクロマトグラ
フにて分析し、出口リアクター組成を経時的に求めた。In the reaction method, first, a predetermined amount of dried catalyst was molded into a 16-28 mesh and filled into a reactor. As a pretreatment, air was supplied at 400° C. for 3 hours, then switched to nitrogen, and set at a predetermined temperature and pressure. Next, the nitrogen supply was stopped, and isobutane (1-C,) and cis-2 were mixed at a predetermined ratio.
- Supplying a raw material liquid of butene (C18-2-C4'') onto the catalyst at a predetermined flow rate. The reactor outlet liquid composition was analyzed by gas chromatography at any time using a vase sampler, and the outlet reactor composition was determined over time.
アルキレーション反応の反応条件は次のとお夛でおる。The reaction conditions for the alkylation reaction are as follows.
反応温度＝Ｄ℃ 反応圧力＝３０ｋｇ／ｃ！ｒ？Ｇ ＷＨ８Ｍ（原料）：１ｏｈ−１ １−％５−２−Ｃ４＝ ： １００Ｗｔ／。Reaction temperature = D°C Reaction pressure = 30kg/c! r? G WH8M (raw material): 1oh-1 1-%5-2-C4=: 100Wt/.
触 媒 量 二 １０９
原料供給後１ｈ後、５０ｈ後の生成物の分析結果を表２
に示す。表２において、転化率、収率および選択率はそ
れぞれ次の数式で定義する０〔実験例２〕
実施例１の手法で真裏した触媒Ａを使用して棟々の反応
条件にて、イノブタンのｃｉａ−２−Ｃ４”によるアル
キレーション反応全行った。反応方法は実験例１で示し
た方法と同様の方法で行った。原料供給３０ｈ後の活性
評価結果を表３に示す◇
〔実験し！１３，１
四塩化テ°タンの水浴液、塩化スズの水酊液にｐＨａｏ
になるまでアンモニア水ｔ １ｍ下して共沈殿物全生成
させ、熟成、ろ過、洗浄及び乾燥してＴｔ（ｏＨ）４・
Ｓｎ（ｏＨ）ｚの複合水改化物を調製し、実施例１と同
様な方法で硫ば処理し、さらに乾燥し、５５０℃で３時
間焼成して触媒りを調製した。Catalyst amount 2 109 Table 2 shows the analysis results of the product 1 h and 50 h after supplying the raw materials.
Shown below. In Table 2, the conversion rate, yield, and selectivity are each defined by the following formulas. All alkylation reactions using cia-2-C4'' were carried out. The reaction method was the same as that shown in Experimental Example 1. The activity evaluation results after 30 hours of raw material supply are shown in Table 3◇ [Experiment! 13,1 Water bath solution of tethane tetrachloride, pHao in water bath solution of tin chloride
Drop 1 m of ammonia water to form a coprecipitate, ripen, filter, wash and dry to give Tt(oH)4.
A composite water modified product of Sn(oH)z was prepared, treated with sulfur in the same manner as in Example 1, further dried, and calcined at 550° C. for 3 hours to prepare a catalyst.
この触媒り全用い実験９１Ｊ １と同様な方法、条件で
アルキレーション反応試験を行なった。An alkylation reaction test was conducted using the same method and conditions as in Experiment 91J 1 using this catalyst.
反応供給１ｈ後の生成物の分析結果は次の通りである。The analysis results of the product 1 hour after the reaction supply are as follows.
オレフィン転化率 １００％
＋
ａＳ収単 １７２％
Ｃ，／Ｃ，選択率 ５６％
ＴＭＰ／Ｃ，Ｊ折率 ６２％
〔発明の効果〕
表２、表３の活性試験結果から、本発明の触［は０８
およびトリメチルペンタン（ＴＭＰ ）の選択性に優れ
かつ長寿命であることから、アルキレーション反応用触
媒として有効でおることが判明した。Olefin conversion rate 100% + aS yield 172% C,/C, selectivity 56% TMP/C, J refraction rate 62% [Effects of the invention] From the activity test results in Tables 2 and 3, it can be seen that the catalyst of the present invention [ is 08
It has been found that it is effective as a catalyst for alkylation reactions because it has excellent selectivity to and trimethylpentane (TMP) and has a long life.
Claims (1)
の複合金属水酸化物もしくは複合金属酸化物からなる担
体に、硫酸根もしくは硫酸根の前駆物質を含有させ、焼
成安定化してなることを特徴とするイソブタンのオレフ
ィンによるアルキレーション反応用固体酸触媒。 ２、IV族金属がチタン、ジルコニウム、ケイ素、スズか
ら選択される少なくとも２種以上の金属の複合金属水酸
化物もしくは複合金属酸化物からなる特許請求の範囲第
１項記載の固体酸触媒。 ３、硫酸根もしくは硫酸根の前駆物質が硫酸、硫酸アン
モニウム、亜硫酸アンモニウム、硫酸水素アンモニウム
、塩化スルフリルから選択される少なくとも一種の物質
からなる特許請求の範囲第１項または第２項記載の固体
酸触媒。 ４、焼成安定化を４００〜８００℃の温度で行なう特許
請求の範囲第１項、第２項または第３項記載の固体酸触
媒。[Claims] 1. A carrier consisting of a composite metal hydroxide or composite metal oxide of at least two metals of Group IV of the Periodic Table contains a sulfate group or a precursor of a sulfate group. A solid acid catalyst for the alkylation reaction of isobutane with an olefin, which is stabilized by calcination. 2. The solid acid catalyst according to claim 1, wherein the group IV metal is a composite metal hydroxide or composite metal oxide of at least two or more metals selected from titanium, zirconium, silicon, and tin. 3. The solid acid catalyst according to claim 1 or 2, in which the sulfate group or the precursor of the sulfate group comprises at least one substance selected from sulfuric acid, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, and sulfuryl chloride. . 4. The solid acid catalyst according to claim 1, 2 or 3, wherein the calcination stabilization is carried out at a temperature of 400 to 800°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073410A JP2601866B2 (en) | 1988-03-29 | 1988-03-29 | Solid acid catalyst for alkylation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073410A JP2601866B2 (en) | 1988-03-29 | 1988-03-29 | Solid acid catalyst for alkylation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01245854A true JPH01245854A (en) | 1989-10-02 |
| JP2601866B2 JP2601866B2 (en) | 1997-04-16 |
Family
ID=13517398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63073410A Expired - Fee Related JP2601866B2 (en) | 1988-03-29 | 1988-03-29 | Solid acid catalyst for alkylation reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2601866B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310868A (en) * | 1991-11-27 | 1994-05-10 | Sun Company, Inc. | Processes using solid-acid catalyst compositions |
| US5321197A (en) * | 1991-11-27 | 1994-06-14 | Sun Company, Inc. (R&M) | Processes using solid-acid catalyst composition |
| US5444175A (en) * | 1992-08-20 | 1995-08-22 | Institut Francais Du Petrole | Process for the alkylation of paraffins |
| US5491278A (en) * | 1993-11-12 | 1996-02-13 | Sun Company, Inc. (R&M) | Alkylation process using solid superacid catalyst liquid phase |
| US5493067A (en) * | 1993-11-12 | 1996-02-20 | Sun Company, Inc. (R&M) | Solid superacid alkylation catalyst compositions and alkylation method using the same |
| CN106631655A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alkylation reaction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60132650A (en) * | 1983-12-19 | 1985-07-15 | Agency Of Ind Science & Technol | Catalyst for synthesizing lower olefin and branched hydrocarbon |
| JPS61153141A (en) * | 1984-12-26 | 1986-07-11 | Res Assoc Util Of Light Oil | Production of solid acid catalyst |
-
1988
- 1988-03-29 JP JP63073410A patent/JP2601866B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60132650A (en) * | 1983-12-19 | 1985-07-15 | Agency Of Ind Science & Technol | Catalyst for synthesizing lower olefin and branched hydrocarbon |
| JPS61153141A (en) * | 1984-12-26 | 1986-07-11 | Res Assoc Util Of Light Oil | Production of solid acid catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310868A (en) * | 1991-11-27 | 1994-05-10 | Sun Company, Inc. | Processes using solid-acid catalyst compositions |
| US5321197A (en) * | 1991-11-27 | 1994-06-14 | Sun Company, Inc. (R&M) | Processes using solid-acid catalyst composition |
| US5444175A (en) * | 1992-08-20 | 1995-08-22 | Institut Francais Du Petrole | Process for the alkylation of paraffins |
| US5491278A (en) * | 1993-11-12 | 1996-02-13 | Sun Company, Inc. (R&M) | Alkylation process using solid superacid catalyst liquid phase |
| US5493067A (en) * | 1993-11-12 | 1996-02-20 | Sun Company, Inc. (R&M) | Solid superacid alkylation catalyst compositions and alkylation method using the same |
| CN106631655A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alkylation reaction method |
| CN106631655B (en) * | 2015-10-28 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of alkylation reaction method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2601866B2 (en) | 1997-04-16 |
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