CN105308009B - The manufacture method of the unsaturated hydro carbons containing metal zeolite catalyst is used - Google Patents

Abstract

A kind of manufacture method of light alkene class in mode of the present invention is characterized in that, be using ethene, propylene as the light alkene class of principal component manufacture method, raw material (O) and oxidizing gas (S) using the saturated hydrocarbons that the boiling point under 1 air pressure is 35~180 DEG C of scopes as principal component is set to be contacted with containing metal zeolite catalyst, it is described to contain the metal (X) in the 8th~10 race of periodic table containing metal zeolite catalyst and have by ten tetrahedral TO₄The mesopore zeolite (Z1) for the ten-ring structure that (T=Si or Al) unit is formed is used as inscape.

Description

The manufacture method of the unsaturated hydro carbons containing metal zeolite catalyst is used

Technical field

The present invention relates to the side for manufacturing unsaturated hydro carbons by the raw material using saturated hydrocarbons as principal component using zeolite catalyst Method.

Background technology

The monocyclic virtue such as the light alkene such as ethene, propylene, butylene and butadiene class and benzene, toluene, ethylbenzene and xylene The fragrant same clan is the important foundation chemical raw material for the backbone to form petro chemical industry.Manufacture the raw material master of these basic chemical feedstocks If the naphtha of the straight run light fraction as crude oil.

In these basic chemical feedstocks, on the light alkene class such as ethene, propylene, butylene and butadiene, following manufacture：Will Belong to the light naphtha of the relatively low component of boiling point in naphtha as raw material, by naphtha cracker complex, steaming Vapour is thermally decomposed (steam cracking) in the case of coexisting with more than 800 DEG C of high temperature.In addition, the thermal decomposition of light naphtha In, in addition to light alkene class, go back the fragrant same clan such as coproduction benzene, toluene, ethylbenzene, xylene.But to these fragrant same clans, The known general manufacture for using cut corresponding using the heavy naphtha with being rich in higher boiling component than light naphtha as raw material Method, this is more efficient manufacture method compared with the method manufactured by light naphtha.From this viewpoint, it may be said that To the decomposition product of light naphtha, it is desirable to reduce aromatic component and improve the ratio of light alkene class as far as possible.

If pay close attention to the Demand trend in recent years of light alkene class, headed by polypropylene, isopropylbenzene, propylene oxide etc. third The demand of ene derivative is expanding.At present, the growth for growing beyond ethylene requirements of propylene demand, it is believed that the propylene from now on It will further speed up with the difference of the demand growth of ethene.

On the other hand, as naphtha principal component rudimentary saturated hydrocarbons, since its reactivity is low, be used as stone brain The decomposition temperature of oil-breaking is, it is necessary to which more than 800 DEG C of high temperature, the decomposition temperature scope that can obtain the yield of good economy performance have Limit.In general, more carrying out naphtha pyrolysis in high temperature, the yield compared to the ethene of propylene is higher, the height more than 800 DEG C Warm area, the propylene/ethylene ratio in product are 0.6~0.7 or so.Within this temperature range, can not significantly change propylene/ Ethylene ratio, accordingly, it can be said that with existing naphtha cracker complex, the selectivity production of propylene is extremely difficult.

In conclusion the product distribution in thermal decomposition depends on decomposition temperature, it is taken as that existing naphtha pyrolysis Device is difficult to the variation for neatly tackling the equilibrium of supply and demand of each component.In addition, centered on the natural gas producing nations such as the Middle East, Rapidly promote raw material conversion, using price compared with naphtha low-down ethane as raw material, second that cost competitiveness is high Alkene is coming into the market.Therefore, the naphtha cracker complex in the Asia headed by the country must not be answered without production adjusting etc. To these situations.In the case where so forcing, the naphtha for looking forward to product can be controlled to be distributed according to supply and demand decomposes work Skill, for this reason, as promising technology, discloses the contact decomposition technique using acid form catalyst (for example, patent document 1).The technology can reduce consumed energy, Jin Erneng compared with belonging to the existing naphtha cracker complex of more energy-dissipating type equipment It is enough to reduce the carbon dioxide (non-patent literature 1) for decomposing and largely discharging with naphtha.

In the contact decomposition technique of the rudimentary saturated hydrocarbons such as disclosed naphtha, mesopore zeolite, wherein particularly ZSM5 Representative MFI zeolites, when generating light alkene class and aromatic compound species with excellent performance.Utilize these skills Art, reaction temperature can be reduced to less than 700 DEG C, and the selectivity of propylene and the ratio of propylene/ethylene can be significantly increased.This Outside, by reducing reaction temperature, the growing amount of the methane relatively low as the value of chemical raw material can also be suppressed.However, these Public technology can not also be known as the technology of the ripe degree to the thermal decomposition alternatively both deposited.

In order to make the contact decomposition technique using the rudimentary saturated hydrocarbons such as the naphtha of zeolite reach can be practical water Put down, it is necessary to significantly extend catalyst life.In addition, catalyst life is common in the reaction process using zeolite catalyst Logical huge problem, especially, reaction condition is harsher, can more cause significantly reducing for catalyst performance.The drop of catalyst performance It is low to cause the yield of purpose product to decline, cause the load increase to refining step etc. to be asked because of the change of product distribution Topic.The main reason for performance of zeolite catalyst reduces, it is believed that be known as thin caused by the carbonaceous accumulation of coke (coke) The Acidity caused by aluminium component disengaging in hole occlusion and the crystallization of zeolites skeleton caused by contact with high-temperature steam etc. Disappearance.

The generation of coke, it is believed that be under harsh reaction condition, pass through the polymerization of such as light alkene, cyclisation, virtue Caused by side reaction as fragrant race carries out in proper order.On the other hand, zeolite catalyst is characterized in that, is had from knot The clear and definite pore of size of crystal structure, the acid site in pore carry out the reaction of shape selective.Therefore, it is particularly, if Using the zeolite catalyst without big pores more than 12 yuan of rings, then due to space in terms of limitation, in pore, can cause The gradualness side reaction of coke generation is also restrained.However, in zeolite, in the pore appearance of the limitation from pore shape Face, also there are acid site in certain proportion, it is believed that thus because of the progress of non-selective reaction the generation of coke can be caused (non- Patent document 2).It is the reaction that carries out at high temperature to be decomposed due to the contact of the lower hydrocarbons such as naphtha, thus such because of coking The problem of performance reduction of zeolite catalyst caused by (U ー キ Application グ) is serious, in terms of practicality, suppresses the skill of coking Art becomes key point.

In the contact converting reaction process of the saturated hydrocarbons carried out at high temperature, it is however generally that, catalyst due to coking, its Activity reduces, but known by adding oxidizing gas in the feed, can inhibit coke generation, extends catalyst life.As Oxidizing gas, uses vapor, carbonic acid gas etc..

For example, the propylene manufacture (non-patent literature 3) of dehydrogenating propane reaction is being carried out using Pt catalyst, is being catalyzed using Fe Agent is carried out in the techniques such as the styrene manufacture (non-patent literature 4) of ethylbenzene dehydrogenation reaction, and water is used by adding in the feed Steam.Vapor plays the effect as oxidizing gas under the high temperature conditions, it is believed that in catalyst layer, except key reaction Outside, promote the removal of coke and precursors of coke produced by steam reforming reaction, suppress coking.

On the other hand, it is known that zeolite catalyst is generally contacted with steam under the high temperature conditions, therefore is absorbed in permanent work Property deterioration.The permanent activity deterioration is to combine hydrolysis, Al components by the Al-O-Si in zeolitic frameworks under the high temperature conditions Depart from, Acidity disappears and produces.Therefore, in order to use vapor conduct in the pyroreaction technique for use zeolite catalyst Oxidizing gas is, it is necessary to the zeolite catalyst for the processing for being improved steam patience using applying.

So far in the contact decomposition technique of the rudimentary saturated hydrocarbons such as disclosed naphtha, as the common zeolite catalyst of use Technique, it is necessary to so-called more than 600 DEG C harsh of high temperature.However, it is difficult to suppress notable due to that can produce under this condition Coking, therefore vapor is made an addition in raw material, relaxes coking.On the other hand, the contact of the rudimentary saturated hydrocarbons such as naphtha In decomposition reaction technique, catalyst needs that reaction is repeated, is regenerated in long-time service, due to the addition of vapor, urges Agent can be exposed to high-temperature vapor for a long time, therefore easily cause active deterioration.In addition, the manufacture of high-temperature vapor is required The reason for specific energy consumption that energy consumption becomes technique entirety is deteriorated.In conclusion from practicality and Eco-power viewpoint Apparently, it is necessary to suppress as far as possible low the additive amount of vapor.

It is disclosed to use the zeolite catalyst for improving steam patience, vapor is added in the feed, implements naphtha etc. The example that the contact of rudimentary saturated hydrocarbons is decomposed.In patent document 2, the ZSM5 catalyst containing P is used, in patent document 3 Used the ZSM5 catalyst containing P, Ca, La, on n-hexane decomposition reaction, implement 48 it is small when more than continuous operation. However, to any example, from the viewpoint of practicality and economy, it cannot be said that be the continuous operation under reality condition.

In addition, also disclose and add vapor in the feed to carry out the contact of the rudimentary saturated hydrocarbons such as naphtha decomposition The example (patent document 4 and 5, non-patent literature 5) of reaction, but to any example, do not implement the reality considered from practical face Property continuous operation.

It is disclosed in steam reforming reaction, using the zeolite catalyst added with active metal class, is steamed in water Implement the technology of the contact decomposition reaction of the rudimentary saturated hydrocarbons such as naphtha under gas adding conditional.In non-patent literature 6, in steam weight In whole reaction, using with the addition of the ZSM5 of active Ni and Ru as catalyst, to the lightweight under vapor adding conditional Naphtha contacts decomposition reaction, continuous operation when progress 10 is small.However, from practicality and Eco-power viewpoint, it is impossible to Say it is the continuous operation under reality condition.

In non-patent literature 7, the ZSM5 added with active Pd is used in steam reforming reaction as catalyst, Implement naphtha contact under vapor adding conditional to decompose.In the prior art document, in order to improve reactivity, except water steams Beyond gas, methanol is also added in raw material naphtha, implements reaction, but conversion ratio at 635 DEG C of catalyst layer temperature, in maximum When also stop at 52.2%, may not proceed sufficiently decomposition reaction.

In non-patent literature 5, using the ZSM5 added with Mo and Ce as catalyst, implement stone under vapor adding conditional Cerebrol contact is decomposed.However, conversion ratio, also stops at 55.3% in maximum, may not proceed sufficiently decomposition reaction.In addition, Reaction time be as short as 5 it is small when, do not carry out the continuous operation from the actuality from the aspect of practicality.

In the embodiment 11 of patent document 4, as catalyst layer, Pt catalyst is divided into leading portion, will be carried with Pr's ZSM5 catalyst is divided into back segment, implements normal butane contact decomposition reaction under vapor adding conditional.However, the reaction can be predicted In system, Pt catalyst is difficult to efficiently remove the coke and precursors of coke accumulated on ZSM5.

In the same manner as vapor, to carbonic acid gas it is also known that it is with coking inhibition.It is believed that by same with vapor The mechanism of sample, promotes the removal of coke and precursors of coke using dry type reforming reaction, suppresses coking.In addition, to carbonic acid gas, Know in addition to dry type reforming reaction, also promote oxidative dehydrogenation.

As the technique for adding carbonic acid gas as oxidizing gas and into saturation hydrocarbon feed, it can enumerate and for example utilize first The benzene manufacture of the aromatic seriesization reaction of the rudimentary saturated hydrocarbons such as alkane, ethane, propane, utilizes the rudimentary saturation such as ethane, propane, butane The rudimentary unsaturated hydro carbons of the dehydrogenation reaction of hydro carbons manufactures, using styrene manufacture of ethylbenzene dehydrogenation reaction etc., de- using oxidation The reaction process (non-patent literature 8) of hydrogen reaction.Wherein, on aromatic series manufacturing process, it has been disclosed that added with carbonic acid gas Under the conditions of, suitably use the example (non-patent literature 9 and 10) containing metal zeolite catalyst.On the other hand, stone brain is being utilized The contact decomposition reaction of the rudimentary saturated hydrocarbons such as oil is manufactured in the technique of rudimentary unsaturated hydro carbons, it is necessary to which to suppress excessive dehydrogenation anti- The progress answered, but not yet disclose for the suppression and apply the example of carbonic acid gas addition.

In patent document 2, implement the contact of the rudimentary saturated hydrocarbons such as naphtha point as using the zeolite catalyst containing P The form of technique is solved, carbonic acid gas can be used as content as diluent gas by describing.However, the prior art document In, carbonic acid gas is recited as the gas only for the purpose of diluting raw material, and completely without the meaning used as oxidizing gas Figure, also completely without the coking inhibition contemplated on a catalyst.In addition, in the look-ahead technique document Prior Art, also do not disclose and add Add the embodiment of the contact decomposition reaction of carbonic acid gas, on the contact decomposition technique of the rudimentary saturated hydrocarbons such as naphtha, make us complete It can not expect the effect that catalyst life caused by adding is improved by carbonic acid gas.

In the embodiment of patent document 4, disclose in normal butane contacts decomposition reaction, contain in product by raw material Reaction result as the carbonic acid gas for aoxidizing and generating.However, carbonic acid gas contained in product brings catalyst life Influence it is indefinite, from practicality and it is economical from the viewpoint of, also implement continuous operation not under reality condition.

In general, it is known that the oxidation reaction such as VOC decomposition reactions, purifying vehicle exhaust reaction in reforming reaction, exhaust gas In, by using the high oxygen ion conduction body of the Lattice Oxygen supply capacity such as perofskite type oxide and cerium oxide as carrier, Improve the activity (such as non-patent literature 11~17 etc.) of metallic catalyst.However, the contact of the rudimentary saturated hydrocarbons such as naphtha point In solution reaction, not yet disclose and pay close attention to this series of prior art and be used to improve by the Lattice Oxygen supply capacity of catalyst carrier The example of catalyst life.

In conclusion if the contact decomposition reaction of the rudimentary saturated hydrocarbons such as naphtha is considered, hardly to passing through Oxidizing gas is added in the feed to be studied come the technology for the coking for suppressing to trigger catalyst life to shorten, and can not also say it Practical level is reached.In view of such circumstances, to the contact decomposition reaction of the rudimentary saturated hydrocarbons such as naphtha, expect a kind of Suppress the generation of coke by oxidizing gas and efficiently long-term continuous production light alkene class can contain metal zeolite Catalyst.

[citation]

[patent document]

Patent document 1：Japanese Unexamined Patent Publication 6-192135 publications

Patent document 2：Japanese Unexamined Patent Publication 2012-193127 publications

Patent document 3：Japanese Unexamined Patent Publication 2010-104878 publications

Patent document 4：Japanese Unexamined Patent Publication 11-180902 publications

Patent document 5：Japanese Unexamined Patent Application Publication 2011-523584 publications

[non-patent literature]

Non-patent literature 1：The energy (Energy), volume 31,425-451 pages (2006)

Non-patent literature 2：Japanese chemical engineering magazine (Journal of Chemical Engineering of Japan) volume 42, S162-S167 pages (2009)

Non-patent literature 3：Applied catalysis (Applied Catalysis) A:Generally (General), volume 221,397- Page 419 (2001)

Non-patent literature 4：Catalysis comment (Catalysis Reviews), volume 8,285-305 pages (1974)

Non-patent literature 5：Catalysis bulletin (Catalysis Letters), volume 100,1-6 pages (2005)

Non-patent literature 6：Industrial chemistry and engineering chemistry research (Industrial ＆ Engineering Chemistry Research), volume 47,2963-2969 pages (2008)

Non-patent literature 7：Catalysis bulletin (Catalysis Letters), volume 142,60-70 pages (2012)

Non-patent literature 8：The energy and fuel (Energy ＆ Fuels), volume 18,1126-1139 pages (2004)

Non-patent literature 9：It is catalyzed (Journal of Catalysis), volume 182,92-103 pages (1999)

Non-patent literature 10：Using organometallic chemistry (Applied Organometallic Chemistry), the 14th Volume, 778-782 pages (2000)

Non-patent literature 11：Chemical engineering magazine (Chemical Engineering Journal), volume 112,13-22 Page (2005)

Non-patent literature 12：It is catalyzed (Journal of Catalysis), volume 234,496-508 pages (2005)

Non-patent literature 13：Catalysis bulletin (Catalysis Letters), volume 105,239-247 pages (2005)

Non-patent literature 14：Applied catalysis (Applied Catalysis) A:Generally (General), volume 286,23-29 Page (2005)

Non-patent literature 15：Surface Science and catalyticing research (Studies in Surface Science and Catalysis), volume 119,843-848 pages (1998)

Non-patent literature 16：Hazardous material magazine (Journal of Hazardous Materials), 244-245 Volume, 613-620 pages (2013)

Non-patent literature 17：Asia catalysis outline (Catalysis Surveys from Asia), volume 9,63-67 pages (2005)

The content of the invention

[problems to be solved by the invention]

The problem of the present invention is, there is provided a kind of manufacturer for having used the light alkene class containing metal zeolite catalyst Method, it is decomposed by the contacts of the rudimentary saturated hydrocarbons such as naphtha, can be to continuously feed light alkene class for a long time in high yield.

[the method used for solving the problem]

The inventors of the present invention are furtherd investigate in view of the above problems, as a result for the above subject, by using with periodic table 8th~10 race's metal and mesopore zeolite contain metal zeolite catalyst for inscape, rudimentary in the naphtha as raw material etc. Oxidizing gas is added in saturated hydrocarbons and carries out contact decomposition, so that the skill upgrading is to industrial level, so that complete this Invention.

That is, the present invention contains following item.

(1) a kind of manufacture method of light alkene class, be carbon number using ethene, propylene as principal component be 2~4 it is low The manufacture method of level olefines, it is characterised in that make the saturated hydrocarbons in the range of using the boiling point under 1 air pressure as 35~180 DEG C be The raw material (O) and oxidizing gas (S) of principal component are contacted with containing metal zeolite catalyst, described to contain containing metal zeolite catalyst The 8th~10 race's metal (X) of periodic table and by ten tetrahedral TO₄(T represents Si atoms or Al atoms, and O represents oxygen atom) The mesopore zeolite (Z1) for the ten-ring structure that unit is formed is used as inscape.

(2) manufacture method of the light alkene class as described in (1), the oxidizing gas (S) are selected from vapor and carbon One or more of acid gas.

(3) manufacture method of the light alkene class as described in (1) or (2), makes described to contain metal zeolite catalyst and institute Under catalyst temperature when stating raw material (O) and the oxidizing gas (S) contact, i.e., decomposed in the contact of the raw material (O) Under reaction temperature in reaction, in other words, at a temperature of the catalyst layer in contacting decomposition reaction, the oxidizing gas (S) volume (V shared by gas_S) relative to the volume (V shared by the gas of the raw material (O)_O) ratio (V_S/V_O) it is 0.01 ~2 scope.

(4) manufacture method of the light alkene class as any one of (1)~(3), the contact of the raw material (O) are decomposed The reaction temperature of reaction is 500~750 DEG C of scopes.

(5) manufacture method of the light alkene class as any one of (1)~(4), mesopore zeolite (Z1) for MFI type, The mesopore zeolite of MWW types or FER types (Z1 ').

(6) manufacture method of the light alkene class as any one of (1)~(5), it is described to contain metal zeolite catalyst Further contain selected from one or more of group being made of the 3rd race's element (Y1) of periodic table and the 15th race's element (Y2) of periodic table Element as inscape, the element (Y2) is the element selected from one or more of P, As, Sb and Bi.

(7) manufacture method of the light alkene class as described in (6), it is described to contain the element containing metal zeolite catalyst (Y2), the element (Y2) is P.

(8) manufacture method of the light alkene class as described in (6) or (7), it is described contain containing metal zeolite catalyst it is described Element (Y1), the element (Y1) are Ce.

(9) manufacture method of the light alkene class as any one of (5)~(8), the mesopore zeolite (Z1) are MFI The mesopore zeolite (Z1 ') of type, MWW types or FER types, is carried with the metal (X) on the mesopore zeolite (Z1 ').

(10) manufacture method of the light alkene class as described in (9), choosing is further held on the mesopore zeolite (Z1 ') The element of one or more of the group of 3 race's elements (Y1) of free period Biao and the 15th race's element (Y2) of periodic table composition, it is described Element (Y2) is the element selected from one or more of P, As, Sb and Bi.

(11) manufacture method of the light alkene class as any one of (6)~(8), the mesopore zeolite (Z1) are The mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, is to be supported at the oxidation of the element (Y1) containing metal zeolite catalyst The metal (X) on thing (Z2) is supported at all different from the mesopore zeolite (Z1 ') and the oxide (Z2) inorganic The metal (X) on solid chemical compound (Z3), the physical mixed body with the mesopore zeolite (Z1 ').

(12) manufacture method of the light alkene class as any one of (6)~(8), the mesopore zeolite (Z1) are The mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, is the oxidation for being supported at the element (Y1) containing metal zeolite catalyst The metal (X) on thing (Z2) is supported at all different from the mesopore zeolite (Z1 ') and the oxide (Z2) inorganic The metal (X) on solid chemical compound (Z3), the physics of the mesopore zeolite (Z1 ') with being carried with the element (Y2) mix It is fit.

(13) manufacture method of the light alkene class as described in (12), Al is further held on the mesopore zeolite (Z1 ').

(14) manufacture method of the light alkene class as described in (13), contains as the element containing metal zeolite catalyst (Y2) as necessary element, the Al that the mesopore zeolite (Z1 ') is held is derived from selected from boehmite, is intended boehmite, oxidation P At least one of aluminium, aluminium salt and amorphous silica-aluminium oxide aluminum contained compound (A).

(15) manufacture method of the light alkene class as described in (14), the aluminum contained compound (A) is boehmite or intends vigorous Any of nurse stone.

(16) manufacture method of the light alkene class as any one of (13)~(15), mesopore zeolite (the Z1 ') institute The Si and the composition of Al contained, by the molar ratio (SiO for being converted into silica and aluminium oxide₂/Al₂O₃) it is calculated as 30~100 model Enclose, also, total scope that 1~10 mass % is calculated as with Al atoms of the Al components containing contained by metal zeolite catalyst.

(17) manufacture method of the light alkene class as any one of (14)~(16), it is described to be catalyzed containing metal zeolite The composition of P and Al contained by agent, 0.1~1.0 scope is calculated as with atomic molar ratio (P/Al).

(18) manufacture method of the light alkene class as any one of (11)~(17), the oxide (Z2) are oxygen Change cerium.

(19) manufacture method of the light alkene class as any one of (11)~(18), the inorganic solid compounds (Z3) it is perovskite compound.

(20) manufacture method of the light alkene class as any one of (6)~(8), the mesopore zeolite (Z1) are The mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, is to be supported at the oxidation of the element (Y1) containing metal zeolite catalyst The metal (X) on thing (Z2) is supported at all different from the mesopore zeolite (Z1 ') and the oxide (Z2) inorganic The metal (X), the physics of the metal (X) held with the mesopore zeolite (Z1 ') on solid chemical compound (Z3) mix It is fit.

(21) manufacture method of the light alkene class as described in (20), further holds on the mesopore zeolite (Z1 ') Element selected from one or more of the element (Y1) and the element (Y2).

(22) manufacture method of the light alkene class as described in (10), further holds on the mesopore zeolite (Z1 ') Al。

(23) manufacture method of the light alkene class as any one of (1)~(22), the metal (X) be selected from Metal in Ru, Rh, Ir, Ni, Pd and Pt.

[invention effect]

According to the present invention, in the contact decomposition reaction of the rudimentary saturated hydrocarbons such as naphtha, can connect for a long time with high yield Light alkene class is manufactured continuously.

Embodiment

Hereinafter, describe a kind of method by the rudimentary saturated hydrocarbons manufacture light alkene class such as naphtha in detail, it use Contain metal zeolite catalyst involved by embodiment.

The manufacture method of light alkene class involved by embodiment is as follows：Contain metal zeolite catalyst using above-mentioned, make Raw material using saturated hydrocarbons that the boiling point under 1 air pressure is 35~180 DEG C of scopes as principal component produces contact decomposition reaction, manufacture with Ethene, the light alkene class that propylene is principal component.Here, " light alkene " refers to the alkene that carbon number is 2~4, " principal component " Refer to ethene contained in light alkene, propylene adds up to more than 50 mass %.Hereinafter, successively to raw material (O), oxidisability gas Body (S), mesopore zeolite (Z1), containing metal zeolite catalyst, the modulator approach of the catalyst and reactive mode and other guide It is described in detail.

(raw material)

As using the saturated hydrocarbons that the boiling point under 1 air pressure is 35~180 DEG C of scope To as the raw material of principal component, do not have special Limitation, can enumerate the sturated aliphatic hydrocarbon for being 3~10 using carbon number and ester ring type hydrocarbon as raw material of principal component etc..Specifically, Light naphtha, heavy naphtha, full fraction naphtha, FCC gasoline and pyrolysis gasoline etc. can be enumerated.In addition, petroleum refinement In technique, do not become object by flowing the heavy ends such as the decompression light oil for contacting decomposition progress lighting, Residual oil.It is here, main Component refers to more than the 70 mass % of saturated hydrocarbons for 35~180 DEG C of scopes containing the boiling point under 1 air pressure, in addition can also Contain the heterocyclic compounds such as sulfur-containing compound, nitrogenous compound and oxygenatedchemicals.Particularly, on sulfur-containing compound, one As for, due to its become metallic catalyst poisoning constituents, it is taken as that being to contain the unsuitable component of catalyst to metal.So And the manufacture method of the light alkene class in the present invention does not produce catalyst performance special influence.In contact point described later Xie Shi, in addition to above-mentioned raw materials, as needed can also supply the gases such as the low nitrogen of reactivity and helium to reactor.

(oxidizing gas)

In the contact decomposition reaction of the rudimentary saturated hydrocarbons such as naphtha, as the oxidizing gas with catalyst layer contacts, do not have There is special limitation, specifically, vapor, carbonic acid gas, nitrous oxide, air, oxygen, ozone etc. can be enumerated.Wherein it is possible to especially close Vapor and carbonic acid gas are used suitablely.

(mesopore zeolite (Z1))

Matrix containing metal zeolite catalyst of the mesopore zeolite (Z1) involved by present embodiment, is had by ten four Face build TO₄The zeolite for the ten-ring structure that (T represents Si atoms or Al atoms, and O represents oxygen atom) unit is formed.The zeolite In, preferably fine pore accounts for more than 10% of the full pore from crystallization of zeolites structure for the pore of 0.50~0.65nm scopes Volume, more preferably accounts for more than 20% volume, further preferably accounts for more than 50% volume.In addition, derive from crystallization of zeolites knot The pore of structure represents the pore that fine pore is 0.20~1.0nm scopes.In addition, on the pore from crystallization of zeolites structure Fine pore, is calculated with temperature variation curve (t-plot) method by the Adsorption and desorption isotherms measured by nitrogen adsorption methods.

The preferred scope of the fine pore of the pore with ten-ring structure of above-mentioned mesopore zeolite (Z1) for 0.50~ 0.65nm, preferred scope are 0.50~0.60nm.It is less than the pore of 0.50nm to fine pore, due to limitation spatially, Be difficult to as the saturated hydrocarbons contained by the naphtha cut of raw material in thin pore diffusion, it is possible to hinder decomposition reaction into OK.In addition, exceed the pore of 0.65nm to fine pore, since system limit spatially is few, it is possible to promote the coke in pore to give birth to Into the progress of reaction.Therefore, fine pore accounts for the full pore from crystallization of zeolites structure for the pore of 0.50~0.65nm scopes Be less than 10% in the case of, can not fully control the contact decomposition reaction of the saturated hydrocarbons such as naphtha.

The crystalline texture of above-mentioned mesopore zeolite (Z1) is preferably MFI type, MWW types or FER types, more preferably MFI type or MWW Type, particularly preferably MFI type.In addition, in following explanation, sometimes by the crystalline texture with MFI type, MWW types or FER types Hole zeolite is known as mesopore zeolite (Z1 ').

The content ratio of element silicon (Si) and aluminium element (Al) contained by above-mentioned mesopore zeolite (Z1), is converted into SiO₂/ Al₂O₃Molar ratio, is preferably 25~1000 scopes, more preferably 25~300 scopes.

Above-mentioned mesopore zeolite (Z1) can be manufactured with always known method, can also use commercially available product.As commercially available product, Such as NH can be enumerated₄ ⁺Type ZSM5 (molecular sieve catalyst international corporation system) etc..

The particle diameter of above-mentioned mesopore zeolite (Z1) is not particularly limited.However, if particle diameter were too small, crystalline reduction Troubling, if excessive on the contrary, the pore length in crystallization becomes long, induces the pore caused by coking and closes Plug.The particle diameter of zeolite is preferably 10nm~5000nm, more preferably 50nm~1000nm.

To above-mentioned mesopore zeolite (Z1), in order to be coated to promote the non-selective reactions such as coke generation be located at pore outer surface Existing acid site, can apply silylation processing as needed.As silylation processing, it is not particularly limited, can be used The known method usually carried out.Specifically, it can enumerate and utilize tetramethoxy-silicane, tetraethoxysilane and aminopropyl-triethoxy The oxyalkyl silanes such as silane；The Silicon Containing Hydrogens such as trimethoxy silane, triethoxysilane, 1,3,5,7- tetramethyl-ring tetrasiloxanes Alkanes；The silazane classes such as three silazane of hexamethyldisilazane and nine methyl；The silicates such as sodium metasilicate and potassium silicate；And six The processing of the halogenated silicon compound class such as ammonium fluosilicate, silicon tetrachloride and trim,ethylchlorosilane etc..

To above-mentioned mesopore zeolite (Z1), in order to control sour amount, dealumination treatment can be applied as needed.As dealumination treatment, It is not particularly limited, the known method usually carried out can be used.Specifically, high temperature steam treatment can be enumerated；Hydrochloric acid, nitric acid and sulphur The mineral acid treatment such as acid；The processing of tetraacethyl diamino-vinyl；Hexafluorosilicic acid salt treatment；And silicon tetrachloride processing etc..

(containing metal zeolite catalyst)

Contain metal zeolite catalyst involved by present embodiment, be containing above-mentioned mesopore zeolite (Z1) and periodic table the 8th Catalyst of~10 race's metals (X) as inscape.Containing metal zeolite catalyst, as long as the metal (X) containing more than one Just show effect, but can also be made of two or more metals (X).Metal (X) is preferably selected from Ru, Rh, Ir, Ni, Pd and Pt In, it is more preferably selected from Ru, Rh, Ir, Pd and Pt, further preferably in Ru, Rh, Pd and Pt.In addition, as by two kinds with On metal (X) form example, combination of the combination of Pt and Pd, the combination of Pd and Ru, Pt and Ru etc. can be enumerated, but be not limited to This.

Content to accounting for catalyst entirety as the metal (X) of the above-mentioned inscape containing metal zeolite catalyst, does not have Especially limitation, is preferably 0.01~30 mass % as element, more preferably 0.01~3 mass %, more preferably 0.01 ~1 mass %, is most preferably 0.05~1 mass %.

In addition, as the inscape containing metal zeolite catalyst, the chemical form of metal (X) is not particularly limited. Specifically, can enumerate elemental metals, alloy, oxide, sulfide, nitride, carbide, boride, halide, hydride, Proton hydrate acids (ア Network ア acid Class), proton hydrate Barbiturates (ア Network ア Suan salt Class), proton hydrate acid ion (ア Network ア acid イ オ Application), hydroxyl acids, carboxylic acid salt, hydroxyl acid ion, oxygen-containing acids, oxyacid salt, oxygen-containing acid ion, metal from Son etc., to any compound, as long as containing at least one in the 8th~10 race's metal of periodic table, can also just contain it at the same time His element.At this time, other elements are not particularly limited containing mode.As the 8th~10 race's metal of periodic table and other yuan The combination of element, can enumerate the combination of platinum and tin, the as be described hereinafter combination of platinum-indium, platinum-zinc disclosed in catalyst modulation example 11 Combination, the combination of platinum-germanium, the combination of platinum and tin-indium, the combination of platinum-palladium-tin, the combination of palladium-tin, the combination of palladium-zinc, palladium-indium Combination, the combination of palladium-germanium, the combination of palladium-ruthenium etc..So containing other yuan in addition to the 8th~10 race's metal of periodic table In the case of element, relative to the 8th~10 race's metal of periodic table, the contents of other metals with atomic ratio measuring is usually 0.1~2.0, Preferably 0.3~1.5 scope.In addition, it is believed that these usual various metals form alloy state on carrier.In addition, to gold Belong to the scientific form of (X), when metal ion can enumerate platinum (II) ion exchanged zeolite, palladium (II) ion exchanged zeolite etc..

As the above-mentioned mesopore zeolite (Z1) containing metal zeolite catalyst is formed, preferably its crystalline texture be MFI type, The mesopore zeolite of MWW types or FER types (Z1 ').In addition, this contains metal zeolite catalyst, it can contain in addition to metal (X) and be selected from The element of one or more of the 3rd race's element (Y1) of periodic table and the 15th race's element (Y2) of periodic table is as inscape, preferably Contain the element selected from one or more of the 3rd race's element (Y1) of periodic table and the 15th race's element (Y2) of periodic table as form will Element, more than one element further preferably selected from the 3rd race's element (Y1) of periodic table and selected from the 15th race's element of periodic table One or more of (Y2) element both sides are as inscape.In addition, in the following description, periodic table the 3rd will be selected from sometimes The element of one or more of the 15th race's element (Y2) of race's element (Y1) and periodic table is collectively referred to as element (Y).Here, as above-mentioned The 3rd race's element (Y1) of periodic table, is preferably Sc, Y, La, Ce, Pr, Sm, is most preferably Ce.As above-mentioned the 15th race of periodic table member Plain (Y2), is preferably P, As, Sb and Bi, is most preferably P.

When it is above-mentioned contain element (Y) containing metal zeolite catalyst and be used as inscape when, to the content of element (Y) without spy Do not limit, but as preferable composition, consisting of can be enumerated.To the 3rd race's element (Y1) of periodic table, contained whole 3 Total concentration for accounting for catalyst of race's element is preferably 0.01~50 mass %, more elects 0.01~10 mass % as, further Preferably 0.01~3 mass %, is most preferably 0.05~1 mass %.In addition, to the 15th race's element (Y2) of periodic table, it is contained Total concentration for accounting for catalyst of 15 whole race's elements be preferably 0.01~30 mass %, more elect 0.01~10 matter as %, more preferably 0.01~5 mass % are measured, is most preferably 0.05~5 mass %.

When containing element (Y) containing metal zeolite catalyst and being used as inscape, to the chemical form of element (Y) without spy Do not limit.Specifically, monomer, oxide, sulfide, nitride, carbide, boride, halide, hydride, water can be enumerated Close proton acids, proton hydrate Barbiturates, proton hydrate acid ion, hydroxyl acids, carboxylic acid salt, hydroxyl acid ion, oxygen-containing Acids, oxyacid salt, oxygen-containing acid ion, metal ion etc..In addition, contain the situation of two or more elements in element (Y) Under, the chemical form of respective element can different or the Composite such as composite oxides forms.

When it is above-mentioned contain element (Y) containing metal zeolite catalyst and be used as inscape when, to metal (X) and element (Y) Combine [(X), (Y)], be not particularly limited, as preferable combination, [(X), (Y1)] and [(X), (Y1), (Y2)] can be enumerated. More specifically, as [(X), (Y1)], [(Pt can be enumerated；Pd)、(Ce)]、[(Pd)、(Ce)]、[(Pd；Ru), (Ce)] etc., this Outside, as [(X), (Y1), (Y2)], [(Pt), (Ce), (P)], [(Pt can be enumerated；Pd)、(Ce)、(P)]、[(Pd)、(Ce)、 (P)]、[(Pd；Ru), (Ce), (P)] etc..Wherein, as particularly preferred combination, can enumerate [(Pt), (Ce), (P)], [(Pd)、(Ce)]、[(Pd)、(Ce)、(P)]、[(Pd；Ru)、(Ce)、(P)].In addition, in described above, such as (Pt；Pd) it is Represent Pt is independent, Pd individually or Pt and Pd any of mixing.

In addition, being combined on above-mentioned preferable [(X), (Y)], to the content of metal (X) and element (Y), do not limit especially System, as preferable content, can enumerate following content.It is excellent in the case that [(X), (Y1), (Y2)] is [(Pt), (Ce), (P)] Select Pt contents be 0.01~3 mass %, Ce content be 0.01~3 mass %, P content be 0.1~3 mass %, more preferably Pt contains To measure as 0.05~1 mass %, Ce content be 0.05~1 mass %, P content is 0.1~3 mass %.[(X), (Y1), (Y2)] is [(Pt；Pd), (Ce), (P)] in the case of, preferably Pt contents are that 0.01~3 mass %, Pd content is 0.01~3 mass %, Ce Content is 0.01~10 mass %, P content is 0.1~3 mass %, and more preferably Pt contents are that 0.05~1 mass %, Pd content is 0.05~1 mass %, Ce content is 0.05~1 mass %, P content is 0.1~3 mass %.[(X), (Y)] for [(Pd), (Ce)] in the case of, preferably Pd contents are that 0.01~1 mass %, Ce content is 0.01~10 mass %.[(X)、(Y1)、 (Y2)] in the case of being [(Pd), (Ce), (P)], preferably Pd contents are that 0.01~1 mass %, Ce content is 0.01~10 matter Measure %, P content is 0.1~10 mass %.[(X), (Y1), (Y2)] is [(Pd；Ru), (Ce), (P)] in the case of, preferably Pd Content be 0.01~1 mass %, Ru content be 0.01~1 mass %, Ce content be 0.01~10 mass %, P content be 0.1~ 10 mass %.

It is preferred containing metal zeolite catalyst in the case of containing the 15th race's element (Y2) of periodic table containing metal zeolite catalyst Contain Al at the same time.At this time, the Al components contained by the catalyst is total, by the worthwhile gauge of the Al atom intrinsic with zeolite, Preferably 1~10 mass %, is preferably 1~5 mass %.In addition, to forming contained by the mesopore zeolite (Z1) of the catalyst The composition of Si and Al, to be converted into the molar ratio (SiO of silica and aluminium oxide₂/Al₂O₃) count, it is preferably 30~100 model Enclose.In addition, in the case where the catalyst contains P as the 15th race's element (Y2) of periodic table, to the P contained by the catalyst and The composition of Al, in terms of atomic molar ratio (P/Al) preferably 0.1~1.0 scope.

It is above-mentioned to contain metal zeolite catalyst, in addition to metal (X) and element (Y), alkali metal (W) can also be contained.Make For alkali metal (W), Li, Na, K, Rb, Cs can be illustrated.In the case of containing alkali metal (W), the amount of (W) is not limited especially System, but be preferably 0.001~0.5 scope based on the molar ratio (W/Al) of the Al in mesopore zeolite (Z1).If should Molar ratio (W/Al) is less than 0.001, then is unable to control the acid amount of mesopore zeolite (Z1), can do nothing to help and suppresses the secondary anti-of gradualness Should.In addition, if the molar ratio (W/Al) more than 0.5, then the sour quantitative change of mesopore zeolite (Z1) is few sometimes, excessive activity reduces.

To the amount of the above-mentioned strong acid center held containing metal zeolite catalyst, it is not particularly limited, but preferably with respect to The scope for being 10~1500 μm of ol per 1g containing metal zeolite.In addition, to the amount of strong acid center, pass through ammonia desorption by heating method (NH₃- TPD) evaluated.On NH₃The measurement result of-TPD, is set to desorption temperature, the longitudinal axis is set to ammonia desorption rate by transverse axis, Point is painted desorption by heating curve and is distributed as acid strength, will only meet and 250 DEG C~800 DEG C scopes are appeared on desorption by heating curve The acid site group at interior peak is used as strong acid center, is quantified.

The above-mentioned form containing metal zeolite catalyst is not particularly limited, powder can be directly used as catalyst, Adhesive etc. can be added as needed on preformed catalyst is made.As preformed catalyst, can enumerate：Powder catalyst is carried out The aggegation block that pressurization, compression form；Or the aggegation block is ground into the compression forming body of appropriate particle diameter；By tablet press machine to powder Body catalyst is compressed solidification to form the compression molding body of specific shape；In powder catalyst add adhesive, Stabilizing agent, water etc. modulate mixture and by mould by extrusion molding body etc. obtained by mixture extrusion, but not It is limited to these.

(modulator approach containing metal zeolite catalyst)

It is according to the present invention to contain metal zeolite catalyst, as long as meeting the character, to the modulator approach of the catalyst It is not particularly limited.The modulator approach of catalyst according to the present invention is roughly divided into following methods (1), (2) and (3).

(1) metal (X) and selected as needed from element (Y1) and element (Y2) one are held on mesopore zeolite (Z1 ') The method of the kind above.

(2) by the oxide (Z2) for the element (Y1) for being carried with metal (X) or being carried with metal (X) with the boiling Stone (Z1 ') and all different inorganic solid compounds (Z3) of the oxide (Z2), with mesopore zeolite (Z1 ') carry out physical mixed Method.

(3) by the oxide (Z2) for the element (Y1) for being carried with metal (X) or being carried with metal (X) with the zeolite The all different inorganic solid compounds (Z3) of (Z1 ') and the oxide (Z2), the mesopore zeolite with being carried with element (Y2) The method that (Z1 ') carries out physical mixed.

In addition, in method (2) and method (3), a part of of metal (X) can be held on mesopore zeolite (Z1 ').Below In explanation, (Z1 '), (Z2) or (Z3) is known as " carrier " sometimes.In addition, the catalyst obtained by method (1) is claimed sometimes It is known as overloading build catalyst for single supported catalyst, by the catalyst obtained by method (2) or method (3).

The present inventor confirms, in present embodiment, using the when containing metal zeolite catalyst of the modulation in the method (1), Although being only carried with the catalyst of metal (X) on mesopore zeolite (Z1 '), as long as using carbon dioxide as oxidizing gas, Just show the effect of present embodiment.In method (1) in the catalyst of modulation, it is preferred that on mesopore zeolite (Z1 ') Hold metal (X) and contain metal zeolite catalyst selected from more than one of element (Y1) and element (Y2), more preferably in Be carried with metal (X), element (Y1) and element (Y2) on hole zeolite (Z1 ') at the same time contains metal zeolite catalyst.

As oxide (Z2) used in method (2) or method (3), element (Y1), cerium oxide (IV), oxygen can be enumerated Change lanthanum, aluminium-cerium composite oxides etc..In addition, as the inorganic solid compounds (Z3) used in method (2) or method (3), can Enumerate strontium titanates, lanthanum manganate, LaFe_0.57Co_0.38Pd_0.05O₃Deng perovskite compound class；Aluminum phosphate class, cerous phosphate class, lanthanum orthophosphate The phosphoric acid salts such as class；And silica, aluminium oxide, boehmite, plan boehmite, zirconium oxide, titanium oxide, magnesia, noncrystalline Silica-alumina, carbon, carborundum etc..In addition, the oxide (Z2) of element (Y1) in method (2) and method (3) and The function of adhesive when inorganic solid compounds (Z3) can also have both as shaping.Element (Y1) oxide (Z2) or When metal (X) is held in inorganic solid compounds (Z3), preferably using the high carrier of Lattice Oxygen supply capacity, it can such as promote The carrier for the catalytic effect that metal (X) produces the reforming reaction caused by oxidizing gas.As such lattice oxygen supply The high solid of ability, can specifically enumerate the perovskite compound such as strontium titanates, lanthanum manganate class, cerium oxide (IV), aluminium-cerium composite oxygen Compound etc., in them, preferably as element (Y1) oxide (Z2) cerium oxide (IV) and be used as inoganic solids chemical combination The perovskite compound of thing (Z3).

In addition, the usage amount of the oxide (Z2) of element (Y1) is not particularly limited, but in order to reduce rudimentary saturated hydrocarbons Class is preferably the scope of 0.1~20 Quality Mgmt Dept relative to 100 Quality Mgmt Dept of mesopore zeolite (Z1) to contacting the influence of decomposition reaction, More elect 1~10 Quality Mgmt Dept as.

It is low to give in high yield for a long time if being added with aluminum contained compound (A) in mesopore zeolite (Z1) in method (3) Level olefines, therefore preferably.As the preferred addition manner of aluminum contained compound (A), can enumerate on mesopore zeolite (Z1) except The mode of aluminum contained compound (A) is further held beyond element (Y2) or as oxide (Z2) or inorganic solid compounds (Z3) using mode of aluminum contained compound (A) etc..On the additive amount of aluminum contained compound (A), will contain in metal zeolite catalyst Total scope for being used as Al atoms, being preferably 1~10 mass % of contained aluminium component, more there is the model for electing 1~5 mass % as Enclose.As aluminum contained compound (A), as long as being not belonging to the material of mesopore zeolite (Z1), be then not particularly limited, preferably using for choosing From boehmite, intend at least one of boehmite, aluminium oxide, aluminium salt and amorphous silica-aluminium oxide aluminum contained compound, more It is preferably selected from boehmite and intends at least one of boehmite compound.Such compound (A) is supported at mesopore zeolite (Z1) when, a part of aluminum contained compound (A) is only held sometimes, and does not hold other compositions, so that in as mesopore zeolite (Z1) with situation as the physical mixed body of aluminum contained compound.However, present inventor confirms, although aluminum contained compound (A) amount is few, as long as being supported on mesopore zeolite (Z1), will play the effect of present embodiment.In addition, in method (3), when When adding aluminum contained compound (A), element (Y2) is preferably phosphorus (P)." the physical mixed body " refers to the method by physical mixed The material of modulation.As " method of physical mixed ", physical mixed method (a)~(e) for example described below can be enumerated.

(holding)

In the case of metal (X), element (Y) and other elements are held on carrier, carrier is：Mesopore zeolite (Z1), member The oxide (Z2) of plain (Y1), the inorganic solid compounds (Z3) all different from the zeolite (Z1) and the oxide (Z2), And their mixture.As the method held, known method can be used, is not particularly limited.For example, as it is known that Following method：Make the metal (X) for containing desirable amount in the form of monomer or compound, element (Y) and other elements Solution, and the impregnation for making it be contacted with mesopore zeolite (Z1), the oxide (Z2) of element (Y1) or inorganic solid compounds (Z3) Method；Make metal (X), element (Y) and other elements gasification in the form of monomer or compound, as gas and mesopore zeolite (Z1), the oxide (Z2) of element (Y1) or the vapour deposition method of inorganic solid compounds (Z3) contact etc..More specifically, as impregnation Method, can enumerate filling perforation method, first wet impregnation (incipient wetness) method, Equilibrium Adsorption Method, evaporation drying method, spray drying Method, sedimentation and ion-exchange etc., as vapour deposition method, can enumerate chemical vapor deposition, physical vapor deposition etc..As preferable side Method, can enumerate easier and without special device the impregnated with method of operation.

As the raw material of the compound containing metal (X), element (Y) and the other elements held, monomeric gold can be used Any compound that category, alloy, oxide, sulfide, nitride, carbide, boride, acid and salt etc. can obtain.

As the raw material of metal (X), specifically, metal (X) can enumerate palladium oxide (II), acid chloride (II), chlorine when being Pd Change palladium (II), palladium nitrate (II), tetramminepalladous chloride (II), four ammonia palladium (II) nitrate etc., metal (X) can enumerate oxidation when being Pt Platinum (IV), chlorine platinum (IV) acid, four ammonia platinum (II) of chlorination, platinum chloride (II), platinum chloride (IV) etc., metal (X) can be enumerated when being Ir Chlordene iridium (IV) acid, oxidation (IV) iridium, iridium chloride (III), iridium chloride (IV) etc., metal (X) can enumerate ruthenic chloride when being Ru (III), the sour potassium of ruthenium-oxide (IV), ruthenium-oxide (VIII), chlordene ruthenium (IV), the sour sodium of chlordene ruthenium (IV), the sour ammonium of chlordene ruthenium (IV), chlorine Change six ammonia rutheniums (III) etc., metal (X) can enumerate rhodium acetate (II), radium chloride (III), rhodium nitrate (III), rhodium oxide when being Rh (III) etc., metal (X) can enumerate nickel oxide (II), nickel nitrate (II), nickel chloride (II), nickel acetate (II) etc. when being Ni.

As containing element (Y1), the raw material of element (Y2) held, elemental metals, alloy, oxide, sulphur can be used Any compound that compound, nitride, carbide, boride, acid and salt etc. can obtain.Specifically, when element (Y1) is Ce Cerium oxide (III), cerium oxide (IV), cerous acetate (III), cerous nitrate (III), cerium chloride (III), cerous carbonate (III) can be enumerated Deng element (Y2) can enumerate orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, pyrophosphoric acid, diammonium hydrogen phosphate etc. when being P.

On holding in process for metal (X), element (Y) and other inscapes, need to make containing metal (X), In the case of the solution of the raw material of groups of elements (Y) and other elements, the form of solution is not particularly limited.Specifically, can lift Go out solution of the dissolution of raw material in solvent, raw material is homogeneously dispersed in colloidal solution in solvent, suspension etc., stock dispersion in In solvent and Shen drops if standing slurry soln etc., and their mixture etc..In addition it is also possible to make containing metal (X), the solution of element (Y) and multiple raw materials in the raw material of other elements.

To making metal (X), the dissolution of raw material of element (Y) and other elements or scattered solvent, it is not particularly limited.Specifically Ground, can enumerate the water-soluble solvent class such as water, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, second The ketone such as the alcohols such as glycol, acetone, methyl ethyl ketone, methylisobutylketone, Anaesthetie Ether, dimethyl ether, tetrahydrofuran, 1,3- bis- Evil The esters such as ethers, ethyl acetate, propyl acetate such as alkane, Isosorbide-5-Nitrae-dioxane, dichloromethane, chloroform, carbon tetrachloride, 1,1-, bis- chloroethenes The halogenated hydrocarbons such as alkane, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, o-dichlorohenzene, benzene,toluene,xylene class, equal front three Benzene, naphthane etc. are aromatic hydrocarbon, acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide etc., and their mixture.

In order to metal (X), element (Y) and other inscapes are used in holding process and in the above-mentioned solution that makes, On the solution of the raw material containing metal (X), it is used directly for holding using what impregnated with method carried out, can also be right in the solution Metal (X) carries out liquid-phase reduction processing, and the colloidal solution containing metal (X) is made to use.To the method for liquid-phase reduction processing It is not particularly limited, following method can be enumerated：In the solution of the raw material containing metal (X) add triethylsilane, etc. it is hydrogeneous The reducing agents such as the carboxylic acids such as silanes, citric acid, sodium citrate, ascorbic acid, sodium borohydride, hydrazine, and added as needed The method of heat；Modulate the solution of the solvent containing reproducibilities such as alcohols, the method heated as needed etc..In addition, carry out During liquid-phase reduction processing, polyvinylpyrrolidone, lauryl mercaptan, Sodium Polyacrylate, methylcellulose, poly- can be added as needed on The protective agents such as ethylene glycol.

Thing directly can be held as urging using be carried with metal (X), element (Y) and other elements as described above Agent, or by carrying out physical mixed with other inscapes come modulation catalyst, can also apply and burn till processing, reduction treatment Or used after applying both processing.On burn till processing, be not particularly limited, preferably enumerate in atmosphere, 250~800 Carry out burning till processing at a temperature of DEG C, more preferably enumerate in atmosphere, carry out at a temperature of 350~600 DEG C burning till processing, especially It is preferred that enumerate in air, carry out burning till processing at a temperature of 450~550 DEG C.On reduction treatment, it is not also specifically limited, tool Body, nitrogen atmosphere processing, reducing agent solution spraying treatment etc. can be enumerated.Nitrogen atmosphere processing is carried out as follows：By with hydrogen or Under the diluted hydrogen atmosphere of inert gas, heated as needed.Reducing agent solution spraying treatment is carried out as follows：As needed By reducing agents such as carboxylic acids, sodium borohydride, the hydrazines such as the Silicon Containing Hydrogen such as triethylsilane alkanes, citric acid, sodium citrate, ascorbic acid It is dissolved in appropriate solvent, solution is made, to holds thing spraying or being added dropwise.

Number to holding operation, is not particularly limited, can be only once hold operation, can also be divided into twice with On repeatedly implement hold operation to be modulated.In the case of multiple inscapes are held more than at twice, at each time In amount, the order that combines and hold of the inscape that hold, be also not particularly limited.

(physical mixed)

When the physical mixed implemented in by the catalyst modulator approach (2) and (3) modulates overloading build catalyst, The method of physical mixed is not particularly limited, as preferable method, specifically, following methods can be enumerated：(a) will be used as mixed Close the method that is all mixed each other using the state of powder of solid constituent of object, (b) make solid as blending objects into It is scattered in same solvent, after forming paste-like, is evaporated dry method, (c) using as the solid of blending objects Formed body is made in component, and method that formed body is mixed with each other, (d) make as each of blending objects respectively as a other layer The mixing that method, (e) and the method for (a)~(c) described in that key element coexists carry out.On (b), can also modulate containing multiple As the formed body of the solid constituent of blending objects, mixed with other formed bodys.As the example of (d), can enumerate solid Each component is accumulated on the reactor of fixed bed successively, the method for forming the catalyst layer being made of multilayer.Wherein, more elect as (a), (b), the method for (c) and (e), is most preferably the method for (a) and (b).

On the solvent used in the physical mixed method of (b), it is not particularly limited, can enumerates for example as by metal (X), the dissolution of raw material or scattered solvent of element (Y) and other elements and the solvent that is illustrated.

On carrying out the catalyst of physical mixed using the above method, can be used directly as catalyst, can also be Application uses after burning till processing, reduction treatment or both processing.To burning till processing, it is not particularly limited, preferably enumerates What is carried out in air, at a temperature of 250~800 DEG C burns till processing, more preferably enumerates in atmosphere, at a temperature of 350~600 DEG C What is carried out burns till processing, particularly preferably enumerate in atmosphere, carry out at a temperature of 450~550 DEG C burn till processing.Pair also original place Reason is it is not also specifically limited, specifically, can enumerate nitrogen atmosphere processing, reducing agent solution spraying treatment etc..Nitrogen atmosphere processing is as follows Carry out：By using under hydrogen or the diluted hydrogen atmosphere of inert gas, heated as needed.Reducing agent solution spraying treatment It is carried out as follows：Make carboxylic acids, the boron such as the Silicon Containing Hydrogen such as triethylsilane alkanes, citric acid, sodium citrate, ascorbic acid as needed The reducing agents such as sodium hydride, hydrazine are dissolved in appropriate solvent, and solution is made, to holding thing spraying or being added dropwise.

As the reactive mode for implementing the manufacturing method of the present invention, there are fixed-bed type, fluidized bed-type and moving bed Formula etc., is not particularly limited, it is appropriate that easily replaces the fixed-bed type of existing naphtha steam cracking.

(contact decomposition reaction)

(catalyst pretreatment)

To containing metal zeolite catalyst for reaction, pretreatment can be applied before the reaction as needed.As pretreatment, Specifically, (1) can be enumerated for the purpose of the adsorbent for removing catalyst surface, while making the non-active gas such as nitrogen and helium Circulation is while carry out high-temperature process, (2) for the purpose of the metal ingredient reduction of catalyst, while making hydrogen or dilution hydrogen circulation While carry out high temperature reduction processing etc..To the species of pretreatment, number, sequentially it is not particularly limited, preferably applies containing above-mentioned (2) pretreatment.

(supply of raw material and oxidizing gas)

To the method for catalyst layer base feed and oxidizing gas, being not particularly limited, in order to make raw material and oxidation Property gas and catalyst layer it is overall uniformly in contact with, to any method all preferably by heat etc. make be under room temperature liquid component Gasification in advance, is all supplied in the form of gas to catalyst layer.In addition, to the admixture of raw material and oxidizing gas, It is not particularly limited, but is supplied after preferably both are mixed to catalyst layer.In addition, oxidizing gas can also be used as catalyst Layer reaction product and generate, and thus with catalyst layer contacts, it may be desirable to the part for making at least oxidizing gas be with Supplied after raw material mixing to catalyst layer.In addition, unstrpped gas and oxidizing gas can be continuously fed respectively, can also Discontinuous supply.For example, it may be suspend the supply of unstrpped gas, only oxidizing gas is supplied to catalyst layer, again Unstrpped gas is supplied to the method for catalyst layer.As the method for discontinuous supply gas, described below can be enumerated One method and second method.First method is, to the both sides of catalyst layer base feed gas and oxidizing gas, in the state Under, suspend the supply of unstrpped gas, and oxidizing gas is supplied to catalyst layer, then unstrpped gas is supplied to catalysis again The method of oxidant layer.Second method is to be only supplied unstrpped gas to catalyst layer, in this condition, suspends the supply of unstrpped gas, And oxidizing gas is supplied, then, unstrpped gas is supplied to the method for catalyst layer again.In second method, again will When unstrpped gas is supplied to catalyst layer, can together with oxidizing gas base feed gas, unstripped gas can also be only supplied Body.

(reaction temperature)

Contact decomposition reaction is generally the endothermic reaction, therefore reaction temperature is higher, thermodynamically getting over to reaction Favorably, more than 800 DEG C general of high temperature is harsh condition to zeolite catalyst but in naphtha thermal decomposition, its active meeting Reduce in a short time.On the other hand, it is necessary to can be removed in the generation without prejudice to unsaturated hydro carbons and by oxidizing gas The high temperature of degree is reacted as coke and precursors of coke.Due to being restricted by these, catalysis during decomposition reaction is contacted The temperature of oxidant layer, is preferably 500~750 DEG C of scope, more has the scope for electing 600~700 DEG C as.In addition, the stone brain of the present invention Reaction temperature of the oil when the contact decomposition reaction of rudimentary saturated hydrocarbons refers to the temperature of catalyst layer, and the temperature of catalyst layer refers to The mean temperature of catalyst layer entirety.However, due to being heated from outside, near the high reactor wall of local temperature, by The influence of the heat absorption produced by decomposition reaction is big and causes the especially low position of temperature, significantly deviates catalyst layer sometimes Overall mean temperature.Therefore, in order to measure the mean temperature of catalyst layer entirety, it is necessary to select to be not in the portion of particular surroundings Position is measured.It as specific assay method, can enumerate, for example, in the case of with fixed bed type reactor, be cut in reaction tube The both ends of reaction tube axial direction of the immediate vicinity measure catalyst layer in face and the temperature of central part, take the temperature at 3 to be put down Equal method etc..

(reaction pressure)

In the manufacturing method of the present invention, saturated hydrocarbons are converted to decomposition reaction to unsaturated hydro carbons, therefore, it can be stated that former The partial pressure of material is higher, thermodynamically to reaction carry out it is more unfavorable.And if the partial pressure of raw material is too low, from the viewpoint of economy Apparently, it is and not preferred.Therefore, the partial pressure (raw material refers to the total of the partial pressure of total overall reaction product when being mixture) of raw material is preferred In the range of 0.01~0.20MPa.Total head in reactor is not particularly limited, but the preferably model of 0.1~1.0MPa In enclosing.

(quantity delivered of raw material and oxidizing gas)

To the quantity delivered of raw material and oxidizing gas, it is not particularly limited, but in order to obtain one by oxidizing gas Determine coke generation inhibition more than degree, while make the deterioration of the catalyst caused by oxidizing gas, react excessive Influence to minimize caused by carrying out, it is desirable to suppress the quantity delivered of oxidizing gas in specific relative to the ratio of raw material quantity delivered In the range of.As embodiment, the volume (V shared by the gas of the oxidizing gas (S) at the reaction temperatures_S) phase For the volume (V shared by the gas of raw material under reaction temperature (O)_O) ratio (V_S/V_O) be preferably 0.01~2 scope, more have choosing For the scope of 0.01~1 scope, most preferably 0.1~1.In addition, when naphtha is when mixture is raw material, molecular weight is unknown Really, therefore, average molecular weight is assumed to be 86 identical with the molecular weight of n-hexane to calculate V_O, and V_OAnd V_SWith with catalysis Gas volume before oxidant layer contact is calculated.

(time of contact)

To the time of contact of raw material and catalyst, it is not particularly limited, but the time of contact of preferably following degree：Reaction Fully carry out and do not produce the coking for hindering reaction carry out degree.It is and specifically, it is preferable to defined in following formula (1) The weight-space velocity (WHSV) of hole zeolite (Z1) composition quality is 0.1~30h^-1Scope carry out, more preferably in 0.1~15h^-1Scope carry out.

(WHSV[h^-1])=(raw material quantity delivered [g/h])/(quality [g] of mesopore zeolite (Z1) component) ... (1)

Embodiment

Hereinafter, by embodiment, the present invention will be described in further detail, but the present invention appointing from these embodiments What is limited.

[catalyst modulates example 1] (Ru/CeO containing metal zeolite catalyst₂+ P/ZSM5) modulation

Cerium oxide (IV) (StremChemicals company systems) 10g is impregnated in the distilled water of 100ml, under reduced pressure, Room temperature is de-gassed.To the mixed liquor of cerium oxide (the IV)/water, gradually added in room temperature by the hexaammine ruthenium chloride of 1.0g (III) (Sigma-Aldrich's system) is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, Room temperature futher stir 2 it is small when.Using evaporator, while heating is carried out to obtained mixed liquor with 50 DEG C of water-baths while subtracting Pressure is evaporated drying.By after evaporation drying residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, adjust System contains the Ru/CeO of the Ru of 330 μm of ol relative to cerium oxide (IV) per 1.0g₂。

By the way that the SiO of mesopore zeolite will be used as₂/Al₂O₃Molar ratio is 30 NH₄ ⁺Type MFI zeolites (Zeolyst International company systems) burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate SiO₂/Al₂O₃Molar ratio is 30 H⁺The MFI zeolite catalysts (H-ZSM5) of type.By SiO₂/Al₂O₃Molar ratio is that 30 H-ZSM5 (10g) is impregnated in the steaming of 100ml Distilled water, under reduced pressure, is de-gassed in room temperature.To the mixed liquor of the H-ZSM5/ water, gradually added in room temperature by the phosphorus of 0.85g Sour hydrogen diammonium (and the pure medicine company system of light) is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, in room Futher stirred under temperature 2 it is small when.Using evaporator, obtained mixed liquor is heated with 50 DEG C of water-baths, and meanwhile Drying is evaporated under decompression.By after evaporation drying residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, Modulate P/ZSM5.

Using mortar, with the state of powder directly by P/ZSM5 (2.5g) and Ru/CeO₂0.24g fully carries out physics and mixes Close, modulate Ru/CeO₂+P/ZSM5。

[catalyst modulates example 2] (Pd/CeO containing metal zeolite catalyst₂+ P/ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, is de-gassed under reduced pressure, in room temperature.To the cerium oxide (IV) mixed liquor of/water, gradually adds four ammonia palladium (II) chloride monohydrates of 0.87g being dissolved in 100ml at room temperature Distilled water obtained by solution, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, while using Obtained mixed liquor is heated in 50 DEG C of water-baths, is evaporated drying under reduced pressure on one side.By the residue after evaporation drying After drying, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate and contain 330 μ per in 1.0g relative to cerium oxide (IV) The Pd/CeO of the Pd of mol₂。

Using mortar, with the state of powder directly by P/ZSM5 (2.5g) and Pd/CeO₂0.24g is sufficiently carried out physics and mixes Close, modulate Pd/CeO₂+P/ZSM5。

[catalyst modulates example 3] (Ni/CeO containing metal zeolite catalyst₂+ P/ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the cerium oxide (IV) mixed liquor of/water, gradually adds nickel nitrate (II) the chloride hexahydrate of 0.96g (and Wako Pure Chemical Industries in room temperature Company system) be dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when. Using evaporator, while being heated with 50 DEG C of water-baths to obtained mixed liquor, drying is evaporated under reduced pressure on one side.Will After residue drying after evaporation drying, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate every relative to cerium oxide (IV) 1.0g contains the Ni/CeO of the Ni of 330 μm of ol₂。

Using mortar, with the state of powder directly by P/ZSM5 (2.5g) and Ni/CeO₂0.24g is sufficiently carried out physics and mixes Close, modulate Ni/CeO₂+P/ZSM5。

[catalyst modulates example 4] (Pd/CeAlO containing metal zeolite catalyst₃+ P/ZSM5) modulation

By aluminium cerium oxide (Aluminum Cerium Oxide) (CeAlO₃, Sigma-Aldrich's system) 10g leaching Stain under reduced pressure, is de-gassed in the distilled water of 100ml in room temperature.To the CeAlO₃(IV) mixed liquor of/water, room temperature by Gradually add and four ammonia palladium (II) chloride monohydrates of 0.87g are dissolved in solution obtained by the distilled water of 100ml, stirred at 50 DEG C Mix 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, while being carried out with 50 DEG C of water-baths to obtained mixed liquor Heating, is evaporated drying under reduced pressure on one side.After the residue drying after evaporation drying, in atmosphere, at a temperature of 500 DEG C Burn till 4 it is small when, modulate relative to CeAlO₃(IV) Pd/CeAlO of the Pd of 330 μm of ol is contained per 1.0g₃。

Using mortar, P/ZSM5 (2.5g) and Pd/CeAlO30.24g are directly fully carried out by ground physics with the state of powder Mixing, modulates Pd/CeAlO3+P/ZSM5.

[catalyst modulates example 5] (Pd/LaMnO containing metal zeolite catalyst₃+ P/ZSM5) modulation

25 mass % ammonium hydroxide (and Wako Pure Chemical Industries company system) 460ml are mixed with distilled water 140ml, modulate 19 mass % Ammonium hydroxide 600ml.While the modulated ammonium hydroxide of stirring, while being added dropwise the lanthanum nitrate hexahydrate of 8.7g (and the pure medicine of light through 1 when small Industrial group's system) and 5.7g manganese nitrate hexahydrate (Northeast chemical company system) be dissolved in it is molten obtained by the distilled water of 200ml Liquid, in room temperature while futher stirring, while stand 1 it is small when, then stop stirring be stored at room temperature 0.5 it is small when, cured. Filter obtained mixture, after dried screening, crushed with mortar, burn till in atmosphere, at a temperature of 750 DEG C 5 it is small when, adjust LaMnO processed₃。

By LaMnO₃10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the LaMnO₃/ water Mixed liquor, gradually adds in room temperature and four ammonia palladium (II) chloride monohydrates of 0.87g are dissolved in the distilled water of 100ml and obtain Solution, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, while with 50 DEG C of water-baths to institute Obtained mixed liquor is heated, and is evaporated drying under reduced pressure on one side.After the residue drying after evaporation drying, in air In, burn till at a temperature of 500 DEG C 4 it is small when, modulate relative to LaMnO₃Contain the Pd/LaMnO of the Pd of 330 μm of ol per 1.0g₃。

Using mortar, with the state of powder directly by P/ZSM5 (2.5g) and Pd/LaMnO₃0.24g fully carries out ground physics Mixing, modulates Pd/LaMnO₃+P/ZSM5。

[embodiment 1] activity rating：Synthetic naphtha decomposition reaction

Reagent is mixed into 29 mass % of pentane, 14 mass %, 2- methylpentane of n-hexane, 14 mass %, normal octane 29 Quality %, 7 mass % of hexahydrotoluene, 7 mass % of hexamethylene are simultaneously sufficiently stirred, using obtained liquid as compound stone brain Oil.

To modulating the Ru/CeO modulated in example 1 in catalyst₂+ P/ZSM5 catalyst is pressurizeed, compressed, and aggegation is made Block, which is crushed, and whole grain is carried out into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit Synthetic naphtha decomposition reaction, so as to carry out activity rating.The Ru/CeO of 0.86g is filled in reaction tube₂+ P/ZSM5 is used as and urges Agent, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, while being warming up to 600 DEG C.600 At a temperature of DEG C, while making hydrogen be circulated in reactor with the flow of 50Ncc/min, while reduction treatment when progress 1 is small.Also After the reason of original place, at a temperature of 600 DEG C, circulated gases are switched into nitrogen from hydrogen, while making its circulation with the flow of 50Ncc/min To reactor, while pretreatment when progress 1.5 is small, is warming up to 650 DEG C as reaction temperature.At a temperature of 650 DEG C, Stop the circulation of the nitrogen in reaction tube, replace, by the synthetic naphtha of raw material with the flow and vapor of 7.5g/h Supplied to carrying out reaction tube, and pressurizeed so that total head becomes 0.15MPa with the flow of 0.75g/h, make reaction under the following conditions Start, the condition is：WHSV relative to mesopore zeolite quality is 10h^-1, the compound stone brain as raw material at the reaction temperatures The volume ratio V of oil gas body and the vapor as oxidizing gas_S/V_OPartial pressure for 0.48, synthetic naphtha gas is 0.10MPa.After reaction starts, after a predetermined time elapses, reaction product is introduced directly into gas chromatograph (detector： FID), the composition of product is analyzed.The yield of each product calculated based on the quality of carbon component is shown in Table 1.

[embodiment 2]

On modulating the Pd/CeO modulated in example 2 in catalyst₂+ P/ZSM5 catalyst, the Pd/CeO except filling 0.86g₂ + P/ZSM5 is used as beyond catalyst, is operated similarly to Example 1, and activity rating is carried out by synthetic naphtha decomposition reaction. The yield of each product calculated based on the quality of carbon component is shown in Table 1.

[embodiment 3]

On modulating the Pd/CeO modulated in example 2 in catalyst₂+ P/ZSM5 catalyst, except vapor quantity delivered is set It is set to beyond 0.35MPa for 3.8g/h, total head, operates similarly to Example 1, is in the WHSV relative to mesopore zeolite quality 10h^-1、V_S/V_OUnder conditions of 2.4, activity rating is carried out by synthetic naphtha decomposition reaction.Using the quality of carbon component as base The yield for each product that plinth calculates is shown in Table 1.

[embodiment 4]

On modulating the Ni/CeO modulated in example 3 in catalyst₂+ P/ZSM5 catalyst, the Ni/CeO except filling 0.86g₂ + P/ZSM5 is used as beyond catalyst, is operated similarly to Example 1, and activity rating is carried out by synthetic naphtha decomposition reaction. The yield of each product calculated based on the quality of carbon component is shown in Table 1.

[embodiment 5]

On modulating the Pd/CeAlO modulated in example 4 in catalyst₃+ P/ZSM5 catalyst, the Pd/ except filling 0.86g CeAlO₃+ P/ZSM5 is used as beyond catalyst, is operated, is lived by synthetic naphtha decomposition reaction similarly to Example 1 Property evaluation.The yield of each product calculated based on the quality of carbon component is shown in Table 1.

[embodiment 6]

On modulating the Pd/LaMnO modulated in example 5 in catalyst₃+ P/ZSM5 catalyst, the Pd/ except filling 0.86g LaMnO₃+ P/ZSM5 is used as beyond catalyst, is operated, is lived by synthetic naphtha decomposition reaction similarly to Example 1 Property evaluation.The yield of each product calculated based on the quality of carbon component is shown in Table 1.

[comparative example 1]

In atmosphere, at a temperature of 500 DEG C, using as the SiO of mesopore zeolite₂/Al₂O₃Molar ratio is 500 NH₄ ⁺Type MFI Zeolite (Sued-Chemie Catalysts company systems) burn till 4 it is small when, thus modulate SiO₂/Al₂O₃Molar ratio is 500 H⁺Type MFI zeolite catalysts (H-ZSM5).

To SiO₂/Al₂O₃The H-ZSM5 catalyst that molar ratio is 500 is pressurizeed, compressed, and aggegation block is made, by the aggegation Block crushes, and whole grain carries out synthetic naphtha into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit Decomposition reaction, so as to carry out activity rating.The SiO of 0.75g is filled in reaction tube₂/Al₂O₃The H-ZSM5 that molar ratio is 500 makees For catalyst, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, temperature is reacted while being warming up to 650 DEG C of degree.At a temperature of 650 DEG C, stop the circulation of the nitrogen in reaction tube, replace, by the compound stone brain of raw material Oil is supplied to reaction tube with the flow of 7.5g/h, and is pressurizeed so that total head becomes 0.10MPa, makes reaction under the following conditions Start, the condition is：WHSV relative to mesopore zeolite quality is 10h^-1, the compound stone as raw material at the reaction temperatures The volume ratio V of cerebrol gas and the vapor as oxidizing gas_S/V_OPartial pressure for 0, synthetic naphtha gas is 0.11MPa.After reaction starts, after a predetermined time elapses, reaction product is introduced directly into gas chromatograph (detector： FID), the composition of product is analyzed.The yield of each product calculated based on the quality of carbon component is shown in table 1.

[comparative example 2]

On modulating the P/ZSM5 catalyst modulated in example 1 in catalyst, except filling the P/ZSM5 of 0.79g as catalysis Beyond agent, operated in the same manner as comparative example 1, activity rating is carried out by synthetic naphtha decomposition reaction.With the quality of carbon component Based on the yield of each product that calculates be shown in Table 1.

[comparative example 3]

To modulating the Ru/CeO modulated in example 1 in catalyst₂+ P/ZSM5 catalyst is pressurizeed, compressed, and aggegation is made Block, which is crushed, and whole grain is carried out into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit N-hexane decomposition reaction, so as to carry out activity rating.The Ru/CeO of 0.86g is filled in reaction tube₂+ P/ZSM5 is as catalysis Agent, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, while being warming up to 600 DEG C.At 600 DEG C At a temperature of, while making hydrogen be circulated in reactor with the flow of 50Ncc/min, while reduction treatment when progress 1 is small.Reduction After processing, circulated gases are switched into nitrogen from hydrogen at 600 DEG C, while it is circulated in reactor with the flow of 50Ncc/min, While pretreatment when progress 1.5 is small, while being warming up to 650 DEG C of reaction temperature.At a temperature of 650 DEG C, make in reaction tube Nitrogen circulation stop, replacing, the synthetic naphtha of raw material supplied to reaction tube with the flow of 7.5g/h, and is added Press so that total head becomes 0.10MPa, start reaction under the following conditions, the condition is：Relative to mesopore zeolite quality WHSV is 10h^-1, synthetic naphtha gas as raw material and the vapor as oxidizing gas at the reaction temperatures body Product compares V_S/V_OPartial pressure for 0, synthetic naphtha gas is 0.11MPa.After reaction starts, after a predetermined time elapses, it will react Product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.Based on the quality of carbon component The yield of each product calculated is shown in Table 1.

[table 1]

Using containing Pd or Ru as the P/ZSM5 catalyst of inscape and implement synthesis under vapor adding conditional Naphtha decomposition reaction embodiment 1~6 is as a result, with implementing synthetic naphtha decomposition reaction under the conditions of being not added with vapor The result of comparative example 1~3 compare, the ethene when after synthetic naphtha decomposition reaction starts 13 is small and when 21 is small+propylene is received Rate is high.In addition, in V_S/V_OFor implement the embodiment 1,2 and 4~6 of reaction under conditions of less than 2.0 as a result, with V_S/ V_OCompared to implement the result of the embodiment 3 of reaction under conditions of more than 2.0,13 is small after synthetic naphtha decomposition reaction starts When and 21 it is small when ethene+propene yield it is high.And then using the embodiment 1,2,4,5 of the catalyst containing Ce as a result, with Use the Pd/LaMnO containing the La for belonging to the 3rd race's element of periodic table but without Ce₃The knot of the embodiment 6 of+P/ZSM5 catalyst Fruit is compared, and ethene+propene yield when after synthetic naphtha decomposition reaction starts 13 is small and when 21 is small is high.That is, Specify that and contain metal zeolite catalyst containing Pd or Ru, add reaction condition in vapor in use, in catalyst performance and Catalyst life these two aspects is excellent, wherein, in V_S/V_OIt is more excellent during to use under conditions of less than 2.0, particularly contain Ce is further excellent when containing zeolite as the metal of inscape.

[catalyst modulates example 6] (Pd/CeO containing metal zeolite catalyst₂+ Al-P/ZSM5) modulation

Boehmite (and Wako Pure Chemical Industries company system) 0.67g and diammonium hydrogen phosphate (and light are added in the distilled water of 100ml Chun Yao industrial groups system) 1.7g, it is stirred at room temperature, adds in thus obtained mixed liquor and modulated in catalyst modulates example 1 SiO₂/Al₂O₃Molar ratio is 30 H-ZSM5 (10g), is further stirred at room temperature.Using evaporator, while with 50 DEG C of water-baths Obtained mixed liquor is heated, is evaporated drying under reduced pressure on one side.After the residue drying after evaporation drying, Burnt till in air, at a temperature of 600 DEG C 5 it is small when, and then, while make the mixed gas of nitrogen and vapor circulation with as nitrogen The flow of 160Ncc/min and vapor 40Ncc/min, while the steam treatment when 700 DEG C of progress 24 are small, modulates Al- P/ZSM5。

Using mortar, directly modulated with the state of powder by Al-P/ZSM5 (2.7g) and in catalyst modulates example 2 The Pd/CeO of 0.23g₂Physical mixed is sufficiently carried out, modulates Pd/CeO₂+Al-P/ZSM5。

[catalyst modulates example 7] (Ru/CeO containing metal zeolite catalyst₂+ Al-P/ZSM5) modulation

Except modulating the Ru/CeO modulated in example 1 using in catalyst₂0.23g replaces Pd/CeO₂Beyond 0.23g, with urging Agent modulation example 6 similarly operates, and modulates Ru/CeO₂+Al-P/ZSM5。

[catalyst modulates example 8] (Pd-Pt/CeO containing metal zeolite catalyst₂+ Al-P/ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the cerium oxide (IV) mixed liquor of/water, gradually adds four ammonia palladium (II) the chloride monohydrates of 0.44g and the chlorination of 0.85g in room temperature Platinum (IV) acid hexahydrate (and Wako Pure Chemical Industries company system) is dissolved in solution obtained by the distilled water of 100ml, and 2 are stirred at 50 DEG C Hour after, room temperature futher stir 2 it is small when.Using evaporator, while being added with 50 DEG C of water-baths to obtained mixed liquor Heat, is evaporated drying under reduced pressure on one side.After the residue drying after evaporation drying, burn in atmosphere, at a temperature of 500 DEG C Into 4 it is small when, modulate per 1.0g contain 165 μm of ol Pd and 165 μm of ol Pt Pd-Pt/CeO₂。

Using mortar, with the state of powder directly by catalyst modulate the Al-P/ZSM5 (2.7g) that is modulated in example 6 and Pd-Pt/CeO₂0.23g is sufficiently carried out physical mixed, modulates Pd-Pt/CeO₂+Al-P/ZSM5。

[embodiment 7] activity rating：N-hexane decomposition reaction

To modulating the Pd/CeO modulated in example 6 in catalyst₂+ Al-P/ZSM5 catalyst is pressurizeed, compressed, and is made solidifying Glomeration, by the aggegation block crush, whole grain into 0.25mm~0.50mm particle diameter, by using fixed bed flow type reaction unit into Row n-hexane decomposition reaction, so as to carry out activity rating.Pd/CeO is filled in reaction tube₂+ Al-P/ZSM5 (0.94g) conduct Catalyst, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, while being warming up to 400 DEG C. At a temperature of 400 DEG C, hydrogen is set to be circulated in reactor with the flow of 50Ncc/min, while reduction treatment when progress 1 is small.Also After the reason of original place, circulated gases are switched into nitrogen from hydrogen at 400 DEG C, while making it be circulated to reactor with the flow of 50Ncc/min It is interior, while carry out 1.5 it is small when pretreatment, be warming up to 650 DEG C of reaction temperature.At a temperature of 650 DEG C, make in reaction tube The circulation of nitrogen stops, and replaces, and the n-hexane of raw material is supplied with the flow and vapor of 7.5g/h with the flow of 0.75g/h To reaction tube, and total head is become 0.10MPa, start reaction under the following conditions, the condition is：Boiled relative to mesoporous The WHSV of stone quality is 10h^-1, n-hexane gas as raw material at the reaction temperatures and the vapor as oxidizing gas Volume ratio V_S/V_OPartial pressure for 0.48, n-hexane gas is 0.068MPa., after a predetermined time elapses, will after reaction starts Reaction product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.Using the quality of carbon component as The yield for each product that basis calculates is shown in Table 2.

[embodiment 8]

On modulating the Ru/CeO modulated in example 7 in catalyst₂+ Al-P/ZSM5 catalyst, the Ru/ except filling 0.94g CeO₂+ Al-P/ZSM5 is used as beyond catalyst, is operated similarly to Example 7, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 2.

[embodiment 9]

On modulating the Pd-Pt/CeO modulated in example 8 in catalyst₂+ Al-P/ZSM5 catalyst, except filling 0.94g's Pd-Pt/CeO₂+ Al-P/ZSM5 is used as beyond catalyst, is operated, is carried out by n-hexane decomposition reaction similarly to Example 7 Activity rating.The yield of each product calculated based on the quality of carbon component is shown in Table 2.

[comparative example 4]

Pressurizeed, compressed to the Al-P/ZSM5 catalyst modulated in catalyst modulation example 6, aggegation block is made, by this Aggegation block crushes, and whole grain carries out n-hexane point into 0.25mm~0.50mm particle diameters by using fixed bed flow type reaction unit Solution reaction, so as to carry out activity rating.The Al-P/ZSM5 of 0.87g is filled in reaction tube as catalyst, under atmospheric pressure, While nitrogen is set to be circulated in reactor with the flow of 50Ncc/min, while being warming up to 650 DEG C of reaction temperature.In 650 DEG C of temperature Under degree, stop the circulation of nitrogen in reaction tube, take and generation by the n-hexane of raw material with the flow and vapor of 7.5g/h with The flow of 0.75g/h is supplied to reaction tube, and total head is become 0.10MPa, starts reaction under the following conditions, the condition For：WHSV relative to mesopore zeolite quality is 10h^-1, n-hexane gas as raw material at the reaction temperatures and be used as oxygen The volume ratio V of the vapor of the property changed gas_S/V_OPartial pressure for 0.48, n-hexane gas is 0.068MPa.After reaction starts, pass through After the scheduled time, reaction product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.With carbon The yield of each product calculated based on the quality of component is shown in Table 2.

[table 2]

On vapor adding conditional (V_S/V_O=0.48) the n-hexane decomposition reaction under, is mixed using by Pd, Ru or Pd-Pt Compound is supported on cerium oxide (IV) and the embodiment 7~9 containing metal zeolite catalyst of physical mixed is carried out with Al-P/ZSM5 As a result, with use be free of result of the metal (X) as the comparative example 4 of the Al-P/ZSM5 catalyst of inscape compared with, anti- Should start 1 it is small when, 19 it is small when and 29 it is small when ethene+propene yield it is high.That is, it specify that in vapor adding conditional Under, contain Pd, Ru or Pd-Pt mixture and contain metal zeolite catalyst as metal (X), urged with the zeolite without metal (X) Agent is compared, excellent in catalyst performance and catalyst life these two aspects.

[catalyst modulates example 9] (Pd-Ru/CeO containing metal zeolite catalyst₂+ Al-P/ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the cerium oxide (IV) mixed liquor of/water, gradually adds four ammonia palladium (II) the chloride monohydrates of 0.87g and the chlorination six of 1.0g in room temperature Ammino ruthenium (III) is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, futher stir 2 in room temperature Hour.Using evaporator, while being heated with 50 DEG C of water-baths to obtained mixed liquor, it is evaporated under reduced pressure on one side dry It is dry.By after evaporation drying residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to cerium oxide (IV) Pd-Ru/CeO of the Ru of Pd and 330 μm of ol of 330 μm of ol is contained per 1.0g₂。

Except using Pd-Ru/CeO₂0.23g replaces Pd/CeO₂Beyond 0.23g, grasped in the same manner as catalyst modulation example 6 Make, modulate Pd-Ru/CeO₂+Al-P/ZSM5。

[embodiment 10] activity rating：N-hexane decomposition reaction

On modulating the Pd-Ru/CeO modulated in example 9 in catalyst₂+ Al-P/ZSM5 catalyst, except filling 0.94g's Pd-Ru/CeO₂+ Al-P/ZSM5 is used as beyond catalyst, is operated, is carried out by n-hexane decomposition reaction similarly to Example 7 Activity rating.The yield of each product calculated based on the quality of carbon component is shown in Table 3.

[embodiment 11]

Respectively to modulating the Al-P/ZSM5 modulated in example 6 and the Pd-Ru/ modulated in catalyst modulation example 9 in catalyst CeO₂Pressurizeed, compressed, aggegation block is made, which is crushed, particle diameter of the whole grain into 0.25mm~0.50mm.First will Al-P/ZSM5 (0.87g) through whole grain is filled into reaction tube, then starts the Pd-Ru/CeO of wadding warp whole grain₂0.075g, So that Pd-Ru/CeO₂Layer and Al-P/ZSM5 catalyst layers coexisted respectively as a other layer, with raw material successively with Pd-Ru/ CeO₂Layer, the mode of Al-P/ZSM5 layers of contact configure.Using the reactor of such catalyst filling, grasp similarly to Example 7 Make, activity rating is carried out by n-hexane decomposition reaction.The yield of each product calculated based on the quality of carbon component shows In table 3.

[table 3]

On using containing Pd-Ru/CeOs of the Pd and Ru as metal (X) as inscape₂+ Al-P/ZSM5 physics Mixed catalyst and in vapor adding conditional (V_S/V_O=0.48) the n-hexane decomposition reaction carried out under, uses the shape with powder State is by Pd-Ru/CeO₂The embodiment 10 of the catalyst of physical mixed is carried out each other with Al-P/ZSM5 as a result, and making Pd- Ru/CeO₂Layer and Al-P/ZSM5 layers are respectively as coexist embodiment 11 of a other layer as a result, knot with the comparative example 4 of table 2 Fruit is compared, reaction start rear 1 it is small when, 19 it is small when and 29 it is small when ethene+propene yield it is high.That is, it specify that in water Under steam adding conditional, use will contain the component of metal (X) and the component containing mesopore zeolite carries out the catalysis of physical mixed During agent, the physical mixed catalyst that makes each component be coexisted as other layer, with the zeolite catalyst phase without metal (X) Than catalyst performance and catalyst life these two aspects are excellent, the physical mixed that each component is mixed with each other with the state of powder Catalyst, it is more excellent in catalyst performance and catalyst life these two aspects.

[catalyst modulates example 10] contains the modulation of metal zeolite catalyst (Pt-Ce/Al-P/ZSM5)

To modulating the Al-P/ZSM5 (2.0g) modulated in example 6 in catalyst, become by the loading amount of Pt in terms of Pt atoms The loading amount of 0.50 mass %, Ce is in a manner of Ce atoms are counted as 0.30 mass % by the sour hexahydrate of platinum chloride (IV) and nitre Sour cerium (III) hexahydrate (and Wako Pure Chemical Industries company system) is dissolved in suitable distilled water, is contained using the solution by just wet Leaching (incipient wetness) method is held.To powder obtained by drying, it is added dropwise by the way that by hydrazine monohydrate, (and light is pure Medicine industrial group system) the hydrazine aqueous solution of 0.13mol/L that is dissolved in distilled water to modulate, after Pt liquid-phase reductions, use distilled water Filtering cleaning, when 100 DEG C of dryings 24 are small, modulates Pt-Ce/Al-P/ZSM5.

[embodiment 12] activity rating：N-hexane decomposition reaction

Pressurizeed, compressed to the Pt-Ce/Al-P/ZSM5 modulated in catalyst modulation example 10, aggegation block is made, will The aggegation block crush, whole grain into 0.25mm~0.50mm particle diameter, by using fixed bed flow type reaction unit carry out just oneself Alkane decomposition reaction, so as to carry out activity rating.The Pt-Ce/Al-P/ZSM5 of 0.91g is filled in reaction tube as catalyst, Under atmospheric pressure, while making nitrogen be circulated in reactor, while being warming up to 650 DEG C of reaction temperature.In making reaction tube at 650 DEG C The circulation of nitrogen stops, and replaces, and the n-hexane of raw material is supplied with the flow and vapor of 7.5g/h with the flow of 2.3g/h To reaction tube, and total head is become 0.10MPa, start reaction under the following conditions, the condition is：Boiled relative to mesoporous The WHSV of stone quality is 10h^-1, n-hexane gas as raw material at the reaction temperatures and the vapor as oxidizing gas Volume ratio V_S/V_OPartial pressure for 1.4, n-hexane gas is 0.041MPa., after a predetermined time elapses, will be anti-after reaction starts Product is answered to be introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.By using the quality of carbon component as The yield for each product that basis calculates is shown in Table 4.

[comparative example 5]

On the Al-P/ZSM5 catalyst modulated in catalyst modulation example 6, the Al-P/ZSM5 conducts except filling 0.87g Beyond catalyst, operate, evaluated by n-hexane decomposition reaction similarly to Example 12.Using the quality of carbon component as base The yield for each product that plinth calculates is shown in Table 4.

[embodiment 13] activity rating：N-hexane decomposition reaction

To modulating the Pd/CeO modulated in example 6 in catalyst₂+ Al-P/ZSM5 catalyst is pressurizeed, compressed, and is made solidifying Glomeration, by the aggegation block crush, whole grain into 0.25mm~0.50mm particle diameter, by using fixed bed flow type reaction unit into Row n-hexane decomposition reaction, so as to carry out activity rating.Pd/CeO is filled in reaction tube₂+ Al-P/ZSM5 (2.4g) is used as and urges Agent, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, while being warming up to 400 DEG C.400 At DEG C, hydrogen is set to be circulated in reactor with the flow of 50Ncc/min, while reduction treatment when progress 1 is small.After reduction treatment, Circulated gases are switched into nitrogen from hydrogen at 400 DEG C, while it is circulated in reactor with the flow of 50Ncc/min, while into Pretreatment when row 1.5 is small, is warming up to 635 DEG C of reaction temperature.At a temperature of 635 DEG C, make the circulation of the nitrogen in reaction tube Stop, replacing, the n-hexane of raw material with the flow of 7.5g/h and is supplied vapor to anti-with the flow of 3.0g/h Ying Guan, and total head is become 0.10MPa, start reaction under the following conditions, the condition is：Relative to mesopore zeolite quality WHSV be 4.0h^-1, n-hexane gas as raw material and the vapor as oxidizing gas at the reaction temperatures body Product compares V_S/V_OPartial pressure for 1.9, n-hexane gas is 0.034MPa.After reaction starts, after a predetermined time elapses, reaction is given birth to It is introduced directly into thing to gas chromatograph (detector：FID), the composition of product is analyzed.Calculated based on the quality of carbon component The yield of each product gone out is shown in Table 4.

[comparative example 6]

Pressurizeed, compressed to the Al-P/ZSM5 catalyst modulated in modulating example 6 in catalyst, aggegation block is made, should Aggegation block crushes, and whole grain carries out n-hexane into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit Decomposition reaction, so as to carry out activity rating.The Al-P/ZSM5 of 2.2g is filled in reaction tube as catalyst, under atmospheric pressure, While nitrogen is set to be circulated in reactor with the flow of 50Ncc/min, while being warming up to 635 DEG C of reaction temperature.In 635 DEG C of temperature Under degree, stop the circulation of nitrogen in reaction tube, replace, by the n-hexane of raw material with the flow of 7.5g/h and by water Steam is supplied to reaction tube with the flow of 3.0g/h, and total head is become 0.10MPa, starts reaction under the following conditions, institute The condition of stating is：WHSV relative to mesopore zeolite quality is 4.0h^-1, n-hexane gas as raw material at the reaction temperatures with Volume ratio V as the vapor of oxidizing gas_S/V_OPartial pressure for 1.9, n-hexane gas is 0.034MPa.Reaction starts Afterwards, after a predetermined time elapses, reaction product is introduced directly into gas chromatograph (detector：FID), product is analyzed Composition.The yield of each product calculated based on the quality of carbon component is shown in Table 4.

[table 4]

On in addition vapor to V_S/V_OThe n-hexane decomposition reaction carried out under conditions of=1.4, makees using containing Pt For metal (X) Pt-Ce/Al-P/ZSM5 catalyst embodiment 12 as a result, with using the Al-P/ZSM5 without metal (X) The result of the comparative example 5 of catalyst is compared, reaction start rear 9 it is small when and 17 it is small when ethene+propene yield it is high.In addition, close In in addition vapor to V_S/V_OThe n-hexane decomposition reaction carried out under conditions of=1.9, using Pd is contained as metal (X) Pd/CeO₂+ Al-P/ZSM5 catalyst embodiment 13 is as a result, with using the Al-P/ZSM5 catalyst without metal (X) The result of comparative example 6 is compared, reaction start rear 1 it is small when, 11 it is small when and 27 it is small when ethene+propene yield it is also high.

[catalyst modulates example 11] contains the modulation of metal zeolite catalyst (P/Pt-Zn/ZSM5)

By the way that the SiO of mesopore zeolite will be used as₂/Al₂O₃Molar ratio is 61 NH₄ ⁺Type MFI zeolites in atmosphere, 500 DEG C At a temperature of burn till 4 it is small when, modulate SiO₂/Al₂O₃Molar ratio is 50 H⁺Type MFI zeolite catalysts (H-ZSM5).To SiO₂/ Al₂O₃Molar ratio is 50 H-ZSM5 (2.0g), becomes the loading amount of 0.50 mass %, Zn in terms of Pt atoms by the loading amount of Pt By Zn atoms count as in a manner of 0.30 mass % by the sour hexahydrate of platinum chloride (IV) and zinc chloride (and Wako Pure Chemical Industries company System) it is dissolved in suitable distilled water, using the solution, carried by incipient wetness (incipient wetness) method Hold.To powder obtained by drying, it is added dropwise by the way that hydrazine monohydrate (and Wako Pure Chemical Industries company system) is dissolved in distilled water to adjust The hydrazine aqueous solution of the 0.13mol/L of system, after Pt liquid-phase reductions, is cleaned with distillation water filtration, when 100 DEG C of dryings 24 are small, is adjusted Pt-Zn/ZSM5 processed.To being impregnated with 85% phosphate aqueous solution (and Wako Pure Chemical Industries company system) in obtained Pt-Zn/ZSM5 0.087g, after being dried, burn till in atmosphere, at a temperature of 650 DEG C 10 it is small when, modulate P/Pt-Zn/ZSM5.

[embodiment 14] activity rating：N-hexane decomposition reaction

Pressurizeed, compressed to the P/Pt-Zn/ZSM5 catalyst modulated in catalyst modulation example 11, aggegation block is made, The aggegation block is crushed, whole grain is carried out just into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit Hexane decomposition reaction, so as to carry out activity rating.P/Pt-Zn/ZSM5 (1.1g) is filled in reaction tube and is used as catalyst, big Under air pressure, while making nitrogen be circulated in reactor, while being warming up to 650 DEG C of reaction temperature.Nitrogen in making reaction tube at 650 DEG C Circulation stop, replacing, the n-hexane of raw material supplied with the flow and vapor of 7.5g/h with the flow of 0.75g/h To reaction tube, and total head is become 0.10MPa, start reaction under the following conditions, the condition is：Boiled relative to mesoporous The WHSV of stone quality is 6.8h^-1, n-hexane gas as raw material at the reaction temperatures and the water steaming as oxidizing gas The volume ratio V of gas_S/V_OPartial pressure for 0.48, n-hexane gas is 0.068MPa.After reaction starts, after a predetermined time elapses, Reaction product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.With the quality of carbon component Based on the yield of each product that calculates be shown in Table 5.

[comparative example 7]

To modulating the SiO modulated in example 11 in catalyst₂/Al₂O₃Molar ratio is 61 H-ZSM5 (2.0g), is impregnated with 85% Phosphate aqueous solution (and Wako Pure Chemical Industries company system) 0.087g, after dry, burn till in atmosphere, at a temperature of 650 DEG C 10 it is small when, Modulate P/ZSM5.Pressurizeed, compressed to obtained powder, aggegation block is made, which is crushed, whole grain is into 0.25mm After the particle diameter of~0.50mm, use in the reaction.

On the SiO modulated₂/Al₂O₃Molar ratio is 61 P/ZSM5, except filling P/ZSM5 (1.1g) is as catalysis Beyond agent, operate, evaluated by n-hexane decomposition reaction similarly to Example 14.Calculated based on the quality of carbon component The yield of each product gone out is shown in Table 5.

[table 5]

On vapor adding conditional (V_S/V_O=0.48) the n-hexane decomposition reaction under, using Pt is contained as metal (X) P/Pt-Zn/ZSM5 catalyst embodiment 14 as a result, with the comparison using the P/ZSM5 catalyst without metal (X) The result of example 7 is compared, reaction start rear 41 it is small when ethene+propene yield it is high.

[catalyst modulates example 12] contains the modulation of metal zeolite catalyst (Ru/ZSM5)

The SiO that will be modulated in comparative example 1₂/Al₂O₃The H-ZSM5 (5.0g) that molar ratio is 500 is impregnated in 20ml distillations Water, under reduced pressure, is de-gassed in room temperature.To the mixed liquor of the zeolite/water, it is added dropwise the monobutyltin trichloride of 0.051g at room temperature Six ammino rutheniums (III) are dissolved in solution obtained by the distilled water of 80ml, 50 DEG C stirring 2 it is small when after, futher stir 2 in room temperature Hour.Using evaporator, while being heated with 50 DEG C of water-baths to obtained mixed liquor, it is evaporated under reduced pressure on one side dry It is dry.After the residue drying after evaporation drying, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate and contain 330 per 1.0g The Ru/ZSM5 of the Ru of μm ol.

[catalyst modulates example 13] (Pd/Al containing metal zeolite catalyst₂O₃+ H-ZSM5) modulation

Gama-alumina (sumitomo chemical company system) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is carried out in room temperature Degassing.To the mixed liquor of the gama-alumina/water, gradually add be hydrated four ammonia palladium (II) chlorides one of 0.87g at room temperature Thing is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Use Evaporator, while being heated with to 50 DEG C of water-baths to obtained mixed liquor, is evaporated drying under reduced pressure on one side.It will steam After drying of sending out residue dried, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to every Al₂O₃1.0g contain The Pd/Al of the Pd of 330 μm of ol₂O₃。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and Pd/Al₂O₃0.25g is sufficiently carried out physical mixed, modulates Pd/Al₂O₃+H-ZSM5。

[catalyst modulates example 14] (Pd/SiO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Aerosil (Sigma-Aldrich's system) 10g is impregnated in the distilled water of 100ml, is being depressurized Under, it is de-gassed in room temperature.To the mixed liquor of the aerosil/water, gradually add the four ammonia palladiums of 0.87g at room temperature (II) chloride monohydrate is dissolved in solution obtained by the distilled water of 100ml, when 50 DEG C of stirrings 2 are small after, in room temperature into one When step stirring 2 is small.Using evaporator, while heated with 50 DEG C of water-baths to obtained mixed liquor, on one side under reduced pressure into Row evaporation drying.After the residue drying after evaporation drying, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulation is opposite In SiO₂Contain the Pd/SiO of the Pd of 330 μm of ol per 1.0g₂。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and Pd/SiO₂0.25g is sufficiently carried out physical mixed, modulates Pd/SiO₂+H-ZSM5。

[catalyst modulates example 15] (Pd/La containing metal zeolite catalyst₂O₃+ H-ZSM5) modulation

Lanthana (III) (and Wako Pure Chemical Industries company system) 10g is impregnated in the distilled water of 100ml, under reduced pressure, Room temperature is de-gassed.To the mixed liquor of lanthana (the III)/water, gradually added in room temperature by four ammonia palladium (II) chlorinations of 0.87g Thing monohydrate is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, it is small to futher stir 2 in room temperature When.Using evaporator, while being heated with 50 DEG C of water-baths to obtained mixed liquor, it is evaporated under reduced pressure on one side dry It is dry.By after evaporation drying residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to La₂O₃Often 1.0g contains the Pd/La of the Pd of 330 μm of ol₂O₃。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and Pd/La₂O₃0.25g is sufficiently carried out physical mixed, modulates Pd/La₂O₃+H-ZSM5。

[catalyst modulates example 16] (Pd/ZrO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Zirconium oxide (IV) (and Wako Pure Chemical Industries company system) 10g is impregnated in the distilled water of 100ml, under reduced pressure, Room temperature is de-gassed.To the mixed liquor of zirconium oxide (the IV)/water, gradually added in room temperature by four ammonia palladium (II) chlorinations of 0.87g Thing monohydrate is dissolved in solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, it is small to futher stir 2 in room temperature When.Using evaporator, while being heated with 50 DEG C of water-baths to obtained mixed liquor, it is evaporated under reduced pressure on one side dry It is dry.By after evaporation drying residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to ZrO₂Often 1.0g contains the Pd/ZrO of the Pd of 330 μm of ol₂。

Using mortar, the SiO that will be modulated with the state of powder in comparative example 1₂/Al₂O₃The H-ZSM5 of molar ratio 500 (2.5g) and Pd/ZrO₂0.25g is sufficiently carried out physical mixed, modulates Pd/ZrO₂+H-ZSM5。

[catalyst modulates example 17] (Pd/SrTiO containing metal zeolite catalyst₃+ H-ZSM5) modulation

Using mortar, with the state of powder directly by strontium carbonate (and Wako Pure Chemical Industries company system) 10g and titanium oxide (IV) (adding river Physicochemical company system) 5.4g fully trifle physical mixeds, burn till in atmosphere, at a temperature of 1150 DEG C 10 it is small when, adjust SrTiO processed₃。

The SrTiO that will be modulated₃10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To this SrTiO₃The mixed liquor of/water, gradually adds be dissolved in four ammonia palladium (II) chloride monohydrates of 0.87g at room temperature Solution obtained by the distilled water of 100ml, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, one Obtained mixed liquor is heated with 50 DEG C of water-baths in side, is evaporated drying under reduced pressure on one side.After evaporation drying Residue drying after, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to SrTiO₃Contain 330 μm of ol per 1.0g Pd Pd/SrTiO₃。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and Pd/SrTiO₃0.25g is sufficiently carried out physical mixed, modulates Pd/SrTiO₃+H-ZSM5。

[embodiment 15] activity rating：N-hexane decomposition reaction

Pressurizeed, compressed to the Ru/ZSM5 catalyst modulated in catalyst modulation example 12, aggegation block is made, by this Aggegation block crushes, and whole grain carries out n-hexane into the particle diameter of 0.25mm~0.50mm by using fixed bed flow type reaction unit Decomposition reaction, so as to carry out activity rating.The Ru/ZSM5 of 0.75g is filled in reaction tube as catalyst, under atmospheric pressure, While nitrogen is set to be circulated in reactor, while being warming up to 650 DEG C.Stop the circulation of the nitrogen in reaction tube at 650 DEG C, take and generation It, the n-hexane of raw material is supplied to reaction tube with the flow and carbonic acid gas of 7.5g/h with the flow of 1.9g/h, and make total head As 0.17MPa, start reaction under the following conditions, the condition is：WHSV relative to mesopore zeolite quality is 10h^-1、 The volume ratio V of the n-hexane gas and the carbonic acid gas as oxidizing gas as raw material at the reaction temperatures_S/V_OFor 0.50, The partial pressure of n-hexane gas is 0.11MPa.Reaction start after, after a predetermined time elapses, by reaction product be introduced directly into Gas chromatograph (detector：FID), the composition of product is analyzed.Each product calculated based on the quality of carbon component Yield is shown in Table 6.

[embodiment 16]

On modulating the Pd/Al modulated in example 13 in catalyst₂O₃+ H-ZSM5 catalyst, the Pd/ except filling 0.83g Al₂O₃+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 6.

[embodiment 17]

On modulating the Pd/SiO modulated in example 14 in catalyst₂+ H-ZSM5 catalyst, the Pd/ except filling 0.83g SiO₂+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 6.

[embodiment 18]

On the Pd/La modulated in catalyst modulation example 15₂O₃+ H-ZSM5 catalyst, the Pd/ except filling 0.83g La₂O₃+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component.

[embodiment 19]

On modulating the Pd/ZrO modulated in example 16 in catalyst₂+ H-ZSM5 catalyst, the Pd/ except filling 0.83g ZrO₂+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 6.

[embodiment 20]

On modulating the Pd/SrTiO modulated in example 17 in catalyst₃+ H-ZSM5 catalyst, the Pd/ except filling 0.83g SrTiO₃+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 6.

[comparative example 8]

To the SiO modulated in comparative example 1₂/Al₂O₃The H-ZSM5 catalyst that molar ratio is 500 is pressurizeed, compressed, and is made Into aggegation block, which is crushed, whole grain is reacted by using fixed bed flow type and filled into the particle diameter of 0.25mm~0.50mm Put and carry out n-hexane decomposition reaction, so as to carry out activity rating.The H-ZSM5 of 0.75g is filled in reaction tube as catalyst, Under atmospheric pressure, while making nitrogen be circulated in reactor, while being warming up to 650 DEG C of reaction temperature.In making reaction tube at 650 DEG C Nitrogen circulation stop, replacing, the n-hexane of raw material supplied to reaction tube with the flow of 7.5g/h and becomes total head 0.11MPa, starts reaction under the following conditions, and the condition is：WHSV relative to mesopore zeolite quality is 10h^-1, anti- The volume ratio V of the n-hexane gas and the carbonic acid gas as oxidizing gas as raw material at a temperature of answering_S/V_OFor 0, n-hexane The partial pressure of gas is 0.11MPa.After reaction starts, after a predetermined time elapses, reaction product is introduced directly into gas phase color Spectrometer (detector：FID), the composition of product is analyzed.The yield of each product calculated based on the quality of carbon component shows In table 6.

[comparative example 9]

On modulating the Ru/ZSM5 catalyst modulated in example 12 in catalyst, the Ru/ZSM5 conducts except filling 0.75g Catalyst, do not supply carbonic acid gas, total head be set to beyond 0.11MPa, operates, is boiled relative to mesoporous similarly to Example 15 The WHSV of stone quality is 10h^-1、V_S/V_OUnder conditions of 0, activity rating is carried out by n-hexane decomposition reaction.With carbon component The yield of each product calculated based on quality is shown in Table 6.

[comparative example 10]

To the SiO modulated in comparative example 1₂/Al₂O₃The H-ZSM5 catalyst that molar ratio is 500 is pressurizeed, compressed, and is made Into aggegation block, which is crushed, whole grain is reacted by using fixed bed flow type and filled into the particle diameter of 0.25mm~0.50mm Put and carry out n-hexane decomposition reaction, so as to carry out activity rating.The H-ZSM5 of 0.75g is filled in reaction tube as catalyst, Under atmospheric pressure, while making nitrogen be circulated in reactor, while being warming up to 650 DEG C of reaction temperature.In making reaction tube at 650 DEG C Nitrogen circulation stop, replacing, by the n-hexane of raw material with the flow and carbonic acid gas of 7.5g/h with the flow of 1.9g/h Supply is to reaction tube and pressurizes, and total head is become 0.17MPa, starts reaction under the following conditions, the condition is：Relatively In the WHSV of mesopore zeolite quality be 10h^-1, n-hexane gas as raw material under early reaction temperature and be used as oxidizing gas Carbonic acid gas volume ratio V_S/V_OPartial pressure for 0.50, n-hexane gas is 0.11MPa.After reaction starts, by pre- timing Between after, reaction product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.With the matter of carbon component The yield of each product calculated based on amount is shown in Table 6.

[comparative example 11]

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and cerium oxide (IV) 0.25g is sufficiently carried out physical mixed, modulates CeO₂+H-ZSM5。

On the CeO modulated₂+ H-ZSM5 catalyst, the CeO except filling 0.83g₂+ H-ZSM5 as catalyst with Outside, operated in the same manner as comparative example 10, activity rating is carried out by n-hexane decomposition reaction.Calculated based on the quality of carbon component The yield of each product gone out is shown in Table 6.

[table 6]

Implemented using Pd or Ru is contained as inscape containing metal zeolite catalyst and under carbonic acid gas adding conditional N-hexane decomposition reaction embodiment 15~20 is as a result, with implementing n-hexane decomposition reaction under the conditions of being not added with carbonic acid gas Comparative example 8 is compared with 9 result, n-hexane decomposition reaction start rear 1 it is small when, 22 it is small when and 37 it is small when ethene+propene yield It is high.In addition, embodiment 15~20 as a result, with use be free of metal (X) as inscape catalyst and in carbonic acid gas Implement the result of the comparative example 10 of n-hexane decomposition reaction under adding conditional and use containing Ce but be free of metal (X) conduct The catalyst of inscape and the appointing in the result of the comparative example 11 of implementation n-hexane decomposition reaction under carbonic acid gas adding conditional One result is compared, when 1 is small, 22 it is small when and 37 it is small when ethene+propene yield it is high.That is, specify that containing Pd or Ru contains metal zeolite catalyst as metal (X), and reaction condition is added in use, catalyst performance and catalyst in carbonic acid gas Service life these two aspects is excellent.

[catalyst modulates example 18] (Pd/CeO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the cerium oxide (IV) mixed liquor of/water, gradually adds in room temperature four ammonia palladium (II) chloride monohydrates of 0.17g being dissolved in 100ml's Solution obtained by distilled water, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.While evaporator is used, with 50 Obtained mixed liquor is heated in DEG C water-bath, is evaporated drying under reduced pressure on one side.Residue after evaporation drying is done After dry, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to CeO₂Contain the Pd/ of the Pd of 66 μm of ol per 1.0g CeO₂。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and the Pd/CeO modulated₂0.25g is sufficiently carried out physical mixed, modulates and contains relative to zeolite per 1.0g The Pd/CeO of the Pd of 6.6 μm of ol₂+H-ZSM5。

[catalyst modulates example 19] (Pd/CeO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and the Pd/CeO modulated in catalyst modulation example 2₂0.25g is sufficiently carried out physical mixed, modulate relative to Zeolite contains the Pd/CeO of the Pd of 33 μm of ol per 1.0g₂+H-ZSM5。

[catalyst modulates example 20] (Pd/CeO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the oxidation The mixed liquor of cerium (IV)/water, gradually adds in room temperature four ammonia palladium (II) chloride monohydrates of 1.7g being dissolved in 100ml's Solution obtained by distilled water, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, while with 50 Obtained mixed liquor is heated in DEG C water-bath, is evaporated drying under reduced pressure on one side.Residue after evaporation drying is done After dry, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to CeO₂Contain the Pd/ of the Pd of 660 μm of ol per 1.0g CeO₂。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and the Pd/CeO modulated₂0.25g is sufficiently carried out physical mixed, modulates and contains 66 per 1.0g relative to zeolite The Pd/CeO of the Pd of μm ol₂+H-ZSM5。

[catalyst modulates example 21] (Ru/CeO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and the Ru/CeO modulated in catalyst modulation example 1₂0.25g is sufficiently carried out physical mixed, modulate relative to Zeolite contains the Ru/CeO of the Ru of 33 μm of ol per 1.0g₂+H-ZSM5。

[catalyst modulates example 22] (Rh/CeO containing metal zeolite catalyst₂+ H-ZSM5) modulation

Cerium oxide (IV) 10g is impregnated in the distilled water of 100ml, under reduced pressure, is de-gassed in room temperature.To the cerium oxide (IV) mixed liquor of/water, the rhodium nitrate (III) (Northeast chemical company system) that 0.96g is gradually added in room temperature are dissolved in 100ml's Solution obtained by distilled water, 50 DEG C stirring 2 it is small when after, room temperature futher stir 2 it is small when.Using evaporator, while with 50 Obtained solution is heated in DEG C water-bath, is evaporated drying under reduced pressure on one side.Residue after evaporation drying is dried Afterwards, burn till in atmosphere, at a temperature of 500 DEG C 4 it is small when, modulate relative to CeO₂Contain the Rh/ of the Rh of 330 μm of ol per 1.0g CeO₂。

Using mortar, the SiO that will directly be modulated with the state of powder in comparative example 1₂/Al₂O₃Molar ratio is 500 H- ZSM5 (2.5g) and the Rh/CeO modulated₂0.25g is sufficiently carried out physical mixed, modulates and contains 33 per 1.0g relative to zeolite The Rh/CeO of the Rh of μm ol₂+H-ZSM5。

[catalyst modulates example 23] (Pd/CeO containing metal zeolite catalyst₂+ Ru/ZSM5) modulation

Using mortar, with the state of powder directly by catalyst modulate the Ru/ZSM5 (2.5g) that is modulated in example 12 and The Pd/CeO modulated in catalyst modulation example 2₂0.25g is sufficiently carried out physical mixed, modulates and contains relative to zeolite per 1.0g The Pd/CeO of the Ru of Pd and 33 μm of ol of 33 μm of ol₂+Ru/ZSM5。

[embodiment 21]

Pd/CeO on the Pd for containing 6.6 μm of ol per 1.0g relative to zeolite modulated in modulating example 18 in catalyst₂+ H-ZSM5 catalyst, the Pd/CeO except filling 0.83g₂+ H-ZSM5 is used as beyond catalyst, is grasped similarly to Example 15 Make, activity rating is carried out by n-hexane decomposition reaction.The yield of each product calculated based on the quality of carbon component shows In table 7.

[embodiment 22]

Pd/CeO on the Pd for containing 33 μm of ol per 1.0g relative to zeolite modulated in modulating example 19 in catalyst₂+ H-ZSM5 catalyst, the Pd/CeO except filling 0.83g₂+ H-ZSM is used as beyond catalyst, is operated similarly to Example 15, Activity rating is carried out by n-hexane decomposition reaction.The yield of each product calculated based on the quality of carbon component is shown in table In 7.

[embodiment 23]

Pd/CeO on the Pd for containing 66 μm of ol per 1.0g relative to zeolite modulated in modulating example 20 in catalyst₂+ H-ZSM5 catalyst, the Pd/CeO except filling 0.83g₂+ H-ZSM5 is used as beyond catalyst, is grasped similarly to Example 15 Make, activity rating is carried out by n-hexane decomposition reaction.The yield of each product calculated based on the quality of carbon component shows In table 7.

[embodiment 24]

On modulating the Ru/CeO modulated in example 21 in catalyst₂+ H-ZSM5 catalyst, the Ru/ except filling 0.83g CeO₂+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 7.

[embodiment 25]

On modulating the Rh/CeO modulated in example 22 in catalyst₂+ H-ZSM5 catalyst, the Rh/ except filling 0.83g CeO₂+ H-ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 7.

[embodiment 26]

On modulating the Pd/CeO modulated in example 23 in catalyst₂+ Ru/ZSM5 catalyst, the Pd/ except filling 0.83g CeO₂+ Ru/ZSM5 is used as beyond catalyst, is operated similarly to Example 15, and carrying out activity by n-hexane decomposition reaction comments Valency.The yield of each product calculated based on the quality of carbon component is shown in Table 7.

[comparative example 12]

Pd/CeO on the Pd for containing 33 μm of ol per 1.0g relative to zeolite modulated in modulating example 19 in catalyst₂+H- ZSM5 catalyst, the Pd/CeO except filling 0.83g₂+ H-ZSM5 is used as beyond catalyst, is operated, is passed through in the same manner as comparative example 9 N-hexane decomposition reaction carries out activity rating.The yield of each product calculated based on the quality of carbon component is shown in Table 7.

[table 7]

Contain metal zeolite catalyst and the reality under carbonic acid gas adding conditional as inscape using Pd, Ru or Rh is contained The embodiment 21~26 of n-hexane decomposition reaction is applied as a result, containing Pd as inscape containing metal zeolite catalysis with using Agent is simultaneously implemented the result of comparative example 12 of n-hexane decomposition reaction under the conditions of carbonic acid gas is not added with and is compared, and synthetic naphtha decomposes Reaction start rear 1 it is small when, 22 it is small when and 37 it is small when ethene+propene yield it is high.In addition, under carbonic acid gas adding conditional into Capable n-hexane decomposition reaction, using containing the knot of metal (X) and Ce as the embodiment 21~26 of the catalyst of inscape Fruit, though with use contain Ce as inscape but without metal (X) catalyst table 6 comparative example 11 result, with And use containing metal (X) as inscape but the result of embodiment 15~20 of the table 6 of the catalyst without Ce is compared, 1 it is small when, 22 it is small when and 37 it is small when ethene+propene yield it is also high.Contain Pd, Ru or Rh as gold that is, specify that Belong to (X) contains metal zeolite catalyst, in the case where carbonic acid gas adds reaction condition in use, in catalyst performance and catalyst life These two aspects is excellent, more excellent when further containing Ce as groups of elements (Y).

[catalyst modulates example 24] (Pd/CeO containing metal zeolite catalyst₂+ P/Pt-Ce/ZSM5) modulation

To modulating the SiO modulated in example 11 in catalyst₂/Al₂O₃Molar ratio is 50 H-ZSM5 (2.0g), with the load of Pt The amount of holding counts the loading amount as 0.50 mass %, Ce in a manner of Ce atoms are counted as 0.30 mass % by Pt atoms, makes chlorination Platinum (IV) acid hexahydrate and cerous nitrate (III) hexahydrate (and Wako Pure Chemical Industries company system) are dissolved in suitable distilled water, Using the solution, held by incipient wetness (incipient wetness) method.To powder obtained by drying, it is added dropwise By the way that hydrazine monohydrate (and Wako Pure Chemical Industries company system) is dissolved in distilled water come the hydrazine aqueous solution of 0.13mol/L modulated, After Pt liquid-phase reductions, cleaned with distillation water filtration, when 100 DEG C of dryings 24 are small, modulate Pt-Ce/ZSM5.To obtained 85% phosphate aqueous solution (and Wako Pure Chemical Industries company system) 0.087g is impregnated with Pt-Ce/ZSM5, after being dried, in atmosphere, Burnt till at a temperature of 650 DEG C 10 it is small when, modulate P/Pt-Ce/ZSM5.

Using mortar, directly modulated with the state of powder by P/Pt-Ce/ZSM5 (2.0g) and in catalyst modulates example 2 Pd/CeO20.19g be sufficiently carried out physical mixed, modulate Pd/CeO₂+P/Pt-Ce/ZSM5。

[embodiment 27] activity rating：N-hexane decomposition reaction

To modulating the Pd/CeO modulated in example 24 in catalyst₂+ P/Pt-Ce/ZSM5 catalyst is pressurizeed, compressed, system Into aggegation block, which is crushed, whole grain is reacted by using fixed bed flow type and filled into the particle diameter of 0.25mm~0.50mm Put and carry out n-hexane decomposition reaction, so as to carry out activity rating.The Pd/CeO of 1.8g is filled in reaction tube₂+P/Pt-Ce/ ZSM5 is as catalyst, under atmospheric pressure, while making nitrogen be circulated in reactor with the flow of 50Ncc/min, while being warming up to 600℃.At a temperature of 600 DEG C, while hydrogen is circulated in reactor with the flow of 50Ncc/min, while when progress 1 is small Reduction treatment.After reduction treatment, circulated gases are switched into nitrogen from hydrogen at 600 DEG C, while making its stream with the flow of 50Ncc/min Pass in reactor, while carry out 1.5 it is small when pretreatment, be warming up to 630 DEG C of reaction temperature.In making reaction tube at 630 DEG C Nitrogen circulation stop, replacing, by the n-hexane of raw material with the flow of 7.5g/h and by carbonic acid gas with the stream of 7.7g/h Amount supply makes total head become 0.11MPa to reaction tube, starts reaction under the following conditions, the condition is：In The WHSV of hole zeolite quality is 5.0h^-1, n-hexane gas as raw material at the reaction temperatures with as oxidizing gas The volume ratio V of carbonic acid gas_S/V_OPartial pressure for 2.0, n-hexane gas is 0.037MPa.After reaction starts, by the scheduled time Afterwards, reaction product is introduced directly into gas chromatograph (detector：FID), the composition of product is analyzed.With the matter of carbon component The yield of each product calculated based on amount is shown in Table 8.

[embodiment 28]

On modulating the Pd/CeO modulated in example 24 in catalyst₂+ P/Pt-Ce/ZSM5 catalyst, except carbonic acid gas is supplied Be set to 11g/h to amount, total head is set to beyond 0.11MPa, operate similarly to Example 27, relative to mesopore zeolite quality WHSV is 10h^-1、V_S/V_OUnder conditions of partial pressure for 3.0, n-hexane gas is 0.028MPa, by n-hexane decomposition reaction into Row activity rating.The yield of each product calculated based on the quality of carbon component is shown in Table 8.

[comparative example 13]

To the SiO modulated in comparative example 1₂/Al₂O₃The H-ZSM5 catalyst that molar ratio is 500 is pressurizeed, compressed, and is made Into aggegation block, which is crushed, whole grain is reacted by using fixed bed flow type and filled into the particle diameter of 0.25mm~0.50mm Put and carry out n-hexane decomposition reaction, so as to carry out activity rating.The H-ZSM5 of 1.5g is filled in reaction tube as catalyst, Under atmospheric pressure, while being made with the flow of 50Ncc/min in nitrogen flow-through reactor, while being warming up to 630 DEG C of reaction temperature. 630 DEG C of circulations for making the nitrogen in reaction tube stop, and replace, by the n-hexane of raw material with the flow of 7.5g/h and by carbonic acid Gas is supplied to reaction tube with the flow of 7.7g/h, and total head is become 0.11MPa, starts reaction under the following conditions, described Condition is：WHSV relative to mesopore zeolite quality is 5.0h^-1The n-hexane gas as raw material at the reaction temperatures is with making For the volume ratio V of the carbonic acid gas of oxidizing gas_S/V_OPartial pressure for 2.0, n-hexane gas is 0.037MPa.After reaction starts, After a predetermined time elapses, reaction product is introduced directly into gas chromatograph (detector：FID), the group of product is analyzed Into.The yield of each product calculated based on the quality of carbon component is shown in Table 8.

[comparative example 14]

On the SiO modulated in comparative example 1₂/Al₂O₃Molar ratio is 500 H-ZSM5 catalyst, except by carbonic acid gas Quantity delivered is set to 11g/h, total head is set to beyond 0.11MPa, is operated in the same manner as comparative example 13, relative to mesopore zeolite quality WHSV be 5h^-1、V_S/V_OUnder conditions of 3.0, activity rating is carried out by n-hexane decomposition reaction.With the quality of carbon component Based on the yield of each product that calculates be shown in Table 8.

[table 8]

In the n-hexane decomposition reaction carried out under carbonic acid gas adding conditional, inscape is used as using Pd and Pt is contained 27 (V of embodiment containing metal zeolite catalyst_S/V_O=2.0) and 28 (V of embodiment_S/V_O=3.0) as a result, with without gold Belong to the 13 (V of comparative example of (X) as inscape_S/V_O=2.0) and 14 (V of comparative example_S/V_O=3.0) result is compared, small 1 When, 22 it is small when お I び 37 it is small when ethene+propene yield it is high.Contain Pd and Pt as metal (X) that is, specify that Contain metal zeolite catalyst, carbonic acid gas add reaction condition under in use, even in by carbonic acid gas relative to raw material just oneself The volume ratio of alkane gas is improved to V_S/V_OIt is also excellent in catalyst performance and catalyst life these two aspects when=3.0.

On following item, can also contain within the scope of the invention.

A kind of (2-1) manufacture method of light alkene class, is that the carbon number using ethene, propylene as principal component is 2~4 The manufacture method of light alkene class, it is characterised in that make the saturated hydrocarbons using the boiling point under 1 air pressure as 35~180 DEG C of scopes be The raw material (O) and oxidizing gas (S) of principal component are contacted with containing metal zeolite catalyst, described to contain containing metal zeolite catalyst The 8th~10 race's metal (X) of periodic table and with by ten tetrahedral TO₄(T represents Si atoms or Al atoms, and O represents oxygen Atom) mesopore zeolite (Z1) of ten-ring structure that forms of unit is used as inscape.

The manufacture method of the light alkene class of (2-2) as described in (2-1), the oxidizing gas (S) are selected from vapor With more than a kind in carbonic acid gas.

The manufacture method of the light alkene class of (2-3) as described in (2-1) or (2-2), makes the raw material (O) and the oxygen Change property gas (S) with it is described contacted containing metal zeolite catalyst when catalyst temperature under, i.e., the raw material (O) contact divide Under reaction temperature in solution reaction, in other words, at a temperature of the catalyst layer in contacting decomposition reaction, the oxidizing gas (S) volume (V shared by gas_S) volume (V shared by relative to the raw material (O) gas_O) ratio (V_S/V_O) it is 0.01~2 Scope.

The manufacture method of the light alkene class of (2-4) as any one of (2-1)~(2-3), raw material (O's) connects Touch the scope that the reaction temperature in decomposition reaction is 500~750 DEG C.

The manufacture method of the light alkene class of (2-5) as any one of (2-1)~(2-4), mesopore zeolite (Z1) are The mesopore zeolite (Z1 ') of MFI type, MWW types or FER types.

The manufacture method of the light alkene class of (2-6) as any one of (2-1)~(2-5), it is described to contain metal zeolite Catalyst further contains one in the group for being selected from and being made of the 3rd race's element (Y1) of periodic table and the 15th race's element (Y2) of periodic table For the element of the kind above as inscape, the element (Y2) is the element selected from one or more of P, As, Sb and Bi.

The manufacture method of the light alkene class of (2-7) as described in (2-6), it is described to contain the member containing metal zeolite catalyst Plain (Y2), the 15th race's element (Y2) of periodic table is P.

The manufacture method of the light alkene class of (2-8) as described in (2-6) or (2-7), it is described to contain containing metal zeolite catalyst There is the element (Y1), the 3rd race's element (Y1) of periodic table is Ce.

The manufacture method of the light alkene class of (2-9) as any one of (2-5)~(2-8), the mesopore zeolite (Z1) it is the mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, the metal (X) is held on the mesopore zeolite (Z1 ').

The manufacture method of the light alkene class of (2-10) as described in (2-9), further carries on the mesopore zeolite (Z1 ') The element selected from one or more of the group being made of the 3rd race's element (Y1) of periodic table and the 15th race's element (Y2) of periodic table is held, The element (Y2) is more than one the element selected from P, As, Sb and Bi.

The manufacture method of the light alkene class of (2-11) as described in (2-6), contains the element containing metal zeolite catalyst (Y1), the mesopore zeolite (Z1) be MFI type, MWW types or FER types mesopore zeolite (Z1 '), containing metal zeolite catalyst be The physical mixed body of the metal (X) held on the oxide (Z2) of the element (Y1) and the mesopore zeolite (Z1 ').

The manufacture method of the light alkene class of (2-11 ') as described in (2-11), the element (Y1) are Ce.

The manufacture method of the light alkene class of (2-12) as described in (2-6), contains the element containing metal zeolite catalyst (Y1) and the element (Y2), the mesopore zeolite (Z1) is the mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, containing metal Zeolite catalyst is the metal (X) held on the oxide (Z2) of the element (Y1) and is carried with the element (Y2) The mesopore zeolite (Z1 ') physical mixed body.

The manufacture method of the light alkene class of (2-12 ') as described in (2-12), the element (Y1) are Ce.

The manufacture method of the light alkene class of (2-12 ") as described in (2-12), the element (Y2) are P.

The manufacture method of the light alkene class of (2-13) as described in (2-12), on the mesopore zeolite (Z1 ') further Hold Al.

The manufacture method of the light alkene class of (2-14) as described in (2-13), contains as described containing metal zeolite catalyst As necessary element, the Al being supported on the mesopore zeolite (Z1 ') is derived from selected from boehmite, is intended vigorous nurse the P of element (Y2) At least one of stone, aluminium oxide, aluminium salt and amorphous silica-aluminium oxide aluminum contained compound (A).

The manufacture method of the light alkene class of (2-15) as described in (2-14), the aluminum contained compound (A) for boehmite or Intend any of boehmite.

The manufacture method of the light alkene class of (2-16) as any one of (2-13)~(2-15), the mesopore zeolite The composition of Si and Al contained by (Z1 '), by the molar ratio (SiO for being converted into silica and aluminium oxide₂/Al₂O₃) it is calculated as 30~ 100 scope, also, the total of the Al components containing contained by metal zeolite catalyst is calculated as 1~10 matter with Al atoms Measure the scope of %.

The manufacture method of the light alkene class of (2-17) as any one of (2-14)~(2-16), it is described to be boiled containing metal The composition of P and Al contained by stone catalyst, 0.1~1.0 scope is calculated as with atomic molar ratio (P/Al).

The manufacture method of the light alkene class of (2-18) as any one of (2-11)~(2-17), the oxide (Z2) it is cerium oxide.

The manufacture method of the light alkene class of (2-19) as any one of (2-11)~(2-18), the inoganic solids Compound (Z3) is perovskite compound.

The manufacture method of the light alkene class of (2-20) as described in (2-6), contains the element containing metal zeolite catalyst (Y1), the mesopore zeolite (Z1) is the mesopore zeolite (Z1 ') of MFI type, MWW types or FER types, is institute containing metal zeolite catalyst State the metal that the metal (X) that the oxide (Z2) of element (Y1) is held is held with the mesopore zeolite (Z1 ') (X) physical mixed body.

The manufacture method of the light alkene class of (2-20 ') as described in (2-20), the element (Y1) are Ce.

The manufacture method of the light alkene class of (2-21) as described in (2-20), further carries on the mesopore zeolite (Z1 ') Hold the element selected from one or more of the element (Y1) and the element (Y2).

The manufacture method of the light alkene class of (2-22) as described in (2-10), further carries on the mesopore zeolite (Z1 ') Hold Al.

The manufacture method of the light alkene class of (2-23) as any one of (2-1)~(2-22), the metal (X) are Metal in Ru, Rh, Ir, Ni, Pd and Pt.

The manufacture method of the light alkene class of (2-24) as described in (2-5), is the metal (X) containing metal zeolite catalyst Physical mixed body with the metal (X) held on the mesopore zeolite (Z1 '), the metal (X) be supported at it is described In all different inorganic solid compounds (Z3) of the oxide (Z2) of the 3rd race's element (Y1) of mesopore zeolite (Z1 ') and periodic table.

The manufacture method of the light alkene class of (2-25) as described in (2-5), is the metal (X) containing metal zeolite catalyst Physical mixed body with the mesopore zeolite (Z1 ') for being carried with the 15th race's element (Y2) of periodic table, the metal (X) are supported at The inorganic solid compounds all different from the oxide (Z2) of the 3rd race's element (Y1) of the mesopore zeolite (Z1 ') and periodic table (Z3) on.

The manufacture method of the light alkene class of (2-26) as described in (2-5), is the metal (X) containing metal zeolite catalyst With the physical mixed body of the mesopore zeolite (Z1 '), the metal (X) is supported at and the mesopore zeolite (Z1 ') and periodic table In all different inorganic solid compounds (Z3) of the oxide (Z2) of 3rd race's element (Y1).

[industrial applicability]

The present invention can be used in the manufacture method using the unsaturated hydro carbons containing metal zeolite catalyst.

Claims (20)

1. a kind of carbon number using ethene, propylene as principal component is the manufacture method of 2~4 light alkene class, its feature exists In making the raw material (O) and oxidizing gas (S) using saturated hydrocarbons that the boiling point under 1 air pressure is 35~180 DEG C of scopes as principal component Contacted with containing metal zeolite catalyst, it is described to contain the 8th~10 race's metal (X) of periodic table and tool containing metal zeolite catalyst Have by ten tetrahedral TO₄The mesopore zeolite (Z1) for the ten-ring structure that unit is formed is used as inscape, and wherein T represents Si Atom or Al atoms, O represent oxygen atom,

It is described further to contain selected from by the 3rd race's element (Y1) of periodic table and the 15th race's element of periodic table containing metal zeolite catalyst (Y2) element of one or more of group of composition is as inscape,

The element (Y2) is the element selected from one or more of P, As, Sb and Bi,

The mesopore zeolite (Z1) is the mesopore zeolite (Z1 ') of MFI type, MWW types or FER types,

It is described to contain the metal (X) or carried that metal zeolite catalyst is the oxide (Z2) for being supported at the element (Y1) It is held in the metal of the inorganic solid compounds (Z3) all different from the mesopore zeolite (Z1 ') and the oxide (Z2) (X), with the physical mixed body of the mesopore zeolite (Z1 '),

The inorganic solid compounds (Z3) are perovskite compound or zirconium oxide.

2. the manufacture method of light alkene class as claimed in claim 1, the oxidizing gas (S) is selected from vapor and carbon More than a kind in acid gas.

3. the manufacture method of light alkene class as claimed in claim 1 or 2, in the contact decomposition reaction of the raw material (O) Reaction temperature under, the volume (V shared by the gas of the oxidizing gas (S)_S) relative to shared by the raw material (O) gas Volume (V_O) ratio (V_S/V_O) be 0.01~2 scope.

4. the manufacture method of light alkene class as claimed in claim 1, the reaction in the contact decomposition reaction of the raw material (O) Temperature is 500~750 DEG C of scope.

5. the manufacture method of light alkene class as claimed in claim 1,

It is described to contain the element (Y2) containing metal zeolite catalyst,

The element (Y2) is P.

6. the manufacture method of the light alkene class as described in claim 1 or 5,

It is described to contain the element (Y1) containing metal zeolite catalyst,

The element (Y1) is Ce.

7. the manufacture method of light alkene class as claimed in claim 1,

The metal (X) is carried with the mesopore zeolite (Z1 ').

8. the manufacture method of light alkene class as claimed in claim 7,

Also held selected from by the 3rd race's element (Y1) of periodic table and the 15th race's element of periodic table in the mesopore zeolite (Z1 ') (Y2) element of one or more of group of composition,

The element (Y2) is the element selected from one or more of P, As, Sb and Bi.

9. the manufacture method of light alkene class as claimed in claim 1,

It is described to contain the metal (X) or carried that metal zeolite catalyst is the oxide (Z2) for being supported at the element (Y1) It is held in the metal of the inorganic solid compounds (Z3) all different from the mesopore zeolite (Z1 ') and the oxide (Z2) (X), be carried with the element (Y2) the mesopore zeolite (Z1 ') physical mixed body.

10. the manufacture method of light alkene class as claimed in claim 9, Al is also carried with the mesopore zeolite (Z1 ').

11. the manufacture method of light alkene class as claimed in claim 10, contains as the member containing metal zeolite catalyst The P of plain (Y2) as must element, be supported at the mesopore zeolite (Z1 ') Al derive from selected from boehmite, intend boehmite, At least one of aluminium oxide, aluminium salt and amorphous silica-aluminium oxide aluminum contained compound (A).

12. the manufacture method of light alkene class as claimed in claim 11, the aluminum contained compound (A) is boehmite or intends vigorous Nurse stone it is any.

13. the manufacture method of the light alkene class as any one of claim 10~12,

The composition of Si and Al contained by the mesopore zeolite (Z1 '), by the molar ratio for being converted into silica and aluminium oxide (SiO₂/Al₂O₃) be calculated as 30~100 scope, also, the Al components containing contained by metal zeolite catalyst it is total with Al atoms are calculated as the scope of 1~10 mass %.

14. the manufacture method of the light alkene class as described in claim 11 or 12,

The composition of the P and Al containing contained by metal zeolite catalyst, 0.1~1.0 is calculated as with atomic molar ratio (P/Al) Scope.

15. the manufacture method of light alkene class as claimed in claim 1, the oxide (Z2) is cerium oxide.

16. the manufacture method of light alkene class as claimed in claim 1, the inorganic solid compounds (Z3) are perovskite Compound.

17. the manufacture method of light alkene class as claimed in claim 1,

The metal (X) is also held on the mesopore zeolite (Z1 ').

18. the manufacture method of light alkene class as claimed in claim 17, choosing is also carried with the mesopore zeolite (Z1 ') From the element of one or more of the element (Y1) and the element (Y2).

19. the manufacture method of light alkene class as claimed in claim 8, Al is also carried with the mesopore zeolite (Z1 ').

20. the manufacture method of light alkene class as claimed in claim 1, the metal (X) is selected from Ru, Rh, Ir, Ni, Pd And the metal in Pt.