CN109701630A - Coupled catalyst system for the direct producing light olefins of synthesis gas - Google Patents
Coupled catalyst system for the direct producing light olefins of synthesis gas Download PDFInfo
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Abstract
The invention belongs to technical field of chemistry and chemical engineering, specially a kind of coupled catalyst system for the direct producing light olefins of synthesis gas mainly solves the problems, such as that the catalyst selectivity of light olefin for being currently used for synthesis gas alkene is not high.Catalyst couples synthesis gas catalyst for preparing alcohol and alcohol alkene catalyst, realizes one-step method from syngas alkene directly processed.Synthesis gas catalyst for preparing alcohol is improved catalyst with base of molybdenum, general molecular formula MoTt‑XaYbZc, wherein T is selected from least one of S, O or C, and one of X Fe, Co, Ni, Ru, Rh, Pd metal or a variety of, one of Y Cr, Mn, Zn, La, Ce metal or a variety of, Z is one of alkali metal or a variety of；Alcohol alkene catalyst is with CHA skeleton structure molecular sieve.The catalyst preferably solves the problems, such as above, efficiently, continuously and stably produces C2‑4Olefin product can be used in the industrial production of preparation of low carbon olefines by synthetic gas.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to a kind of coupling for the direct producing light olefins of synthesis gas
Catalyst system is especially specifically related to a kind of coupled catalyst system for the efficiently direct preparing ethylene and propylene of synthesis gas.
Background technique
Low-carbon alkene (such as ethylene, propylene) is important industrial chemicals, with the growth of national economy, consumption demand
It is increasing.Although the production of China's ethylene and propylene has had considerable scale, the consumption degree of self-sufficiency is lower, and disparities between supply and demand are still very
It is prominent.With the increasingly reduction of petroleum resources, coal and natural gas will gradually replace petroleum and come as new fuel and industrial chemicals
The synthesis gas olefin process research of clean type fuel is competitively carried out in source, in recent years, each major oil companies, the world, low to capture
Carbon olefin market.
Since China's richness coal oil starvation lacks the endowment of resources of gas, coal and biomass are greatly developed through synthesis gas/methanol-to-olefins
Route substitutes with petrochemical materials alkene route, has important strategic importance；Technically, clean gas
Change technology is vigorously developed, and biomass gasification technology is constantly mature, and either catalyst or technical process all improves to some extent, phase
For letter with the continuous development of gasification technology, the economy of synthesis gas alkene route can be more significant.
Using synthesis gas preparing low-carbon olefins, there are mainly two types of process routes: one is synthesis gas directly to produce low-carbon alkene
Hydrocarbon；One is synthesis gas via methanol or the indirect preparing low-carbon olefins of dimethyl ether (MTO/MTP).But it takes a long view, by synthesizing
The technique of the direct preparing low-carbon olefins of gas is more more economical than indirect method.
Currently, the direct preparing low-carbon olefins of synthesis gas, mainly based on F-T catalyst, prior art discloses
The catalyst systems such as FeMnK, Fe/C, FeAl-ZSM-5 can be used as the catalyst of the direct preparing low-carbon olefins of synthesis gas.
Patent document [CN103157489A] is related to catalyst and its preparation side for the direct producing light olefins of synthesis gas
Method and application.Fe and auxiliary agent are highly dispersed at self-control basic supports surface, catalyst loadings using parallel flow precipitation by invention
Low, manufacture craft is simple, and cost is lower than similar-type products.Catalyst is used for the direct preparing low-carbon olefins of synthesis gas, is being synthesized
CO conversion ratio is up to 75-85% under gas one way catalytic condition, and ethylenic alkoxy rate reaches 4.5-6.0, olefin feed weight in gas organic product
50-60% is reached, 98% or more product liquid is water.Catalyst has good wear resistence and resistance to pressure, can be used for slurry
The use of bed and fixed bed.Catalyst reaction process conditions involved in the present invention are as follows: 200-500 DEG C of temperature, pressure 0-5MPa, close
At gas air speed 600-2400h-1。
Patent document [CN103331171A] refers to that one kind is steamed for the direct preparing low-carbon olefin by conversion parallel connection of synthesis gas
The preparation method and application of the catalyst of oil.The method passes through carbon source pretreatment, dispersion mixing, modification using molysite as presoma
Vapor deposition and etc. simple and easy preparation method, synthesize using iron containing compounds as the direct transformation of synthetic gas of the energy in activated centre
To the catalyst of low-carbon alkene co-production gasoline, catalyst activity and economic cost all have industrialization possibility.
Patent document [CN1083415A] is reported by synthesis gas (CO+H2) highly selective produce the low-carbons alkene such as second, propylene
The catalyst of hydrocarbon is the iron-manganese supported with the II A race alkaline earth oxide such as MgO or silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite)
Catalyst system has good synthesizing low-carbon Olefins, benefit under the effect of highly basic (IA race metal) K or Cs assistant
It in pressure is 1.0-5.0MPa with this catalyst, it, can high activity (CO conversion ratio under the reaction condition that temperature is 300-400 DEG C
Up to 90% or more), highly selective (olefine selective up to 66% or more) by synthesis gas preparing low-carbon olefins.Technique of the invention
Process, can be directly by reaction end gas through water absorption and separation CO2And warp in pressure oil absorption and separation C3, C4 component, then, with benzene with
Alkene concentration ethylene reaction in tail gas produces ethylbenzene.Its operational sequence is simple, is suitable for popularization and application.
Patent document [CN1279131A] is related to a kind of ZSM-5 zeolite and porous metal composite material contains porous metals load
The ZSM-5 zeolite of body and direct crystallization on this carrier, the Lacunaris metal carrier at least contain a kind of porous nickel-aluminum, iron-aluminium
Or copper-aluminium alloy, on the basis of porous nickel-aluminum, iron-aluminium or copper-aluminium alloy, the pore volume of Lacunaris metal carrier is 0.02-
0.5mL/g.The combination of zeolite and Lacunaris metal carrier is stronger in the composite material, and zeolite has higher heat, hydro-thermal steady
It is qualitative, there is unique catalytic performance with the Cu-contained catalyst that the composite material is prepared.
Based on the above-mentioned FT in the prior art mainly by Fe for main catalytic active component reacts, sintetics distribution
Limit by the Anderson-Schulz-Flory rule molar distribution of exponential decrease (chain growth according to) and the strong of reaction is put
Heat easily leads to the generation of methane and low-carbon alkanes, and promotes the low-carbon alkene of synthesis that secondary response occurs, and leads to low-carbon alkene
Selectivity decline.
Document Science.2016,351,1065-8, which reports new OX-ZEO process, can significantly improve low-carbon alkene selection
Property, core is a kind of difunctional composite catalyst ZnCrOx/SAPO: the ZnCrOx of spinel structure and mesoporous SAPO boiling
Stone.CO can be activated there are two types of active site and C-C is coupled and separates by catalyst tool.On the one hand, the ZnCrOx of partial oxidation
(zinc chrome oxide) activates CO and H2；On the other hand, C-C is coupled in the acid confinement duct of zeolite and carries out.The catalyst pair
Synthesis gas is directly translated into the very high selectivity (alkene 80%, alkane 14%) that (C2-C4) has up to 94%, and methane is only
2%, wherein CO conversion ratio is 17%.
Document Angew.Chem.Int.Ed.2016,55,1-5 report a kind of bifunctional catalyst, and methanol-fueled CLC is anti-
It should be coupled (methanol-to-olefins) with C-C and react coupling, successful design goes out Zr-Zn/SAPO-34 bifunctional catalyst, in low-carbon alkene
It makes a breakthrough in terms of hydrocarbon-selective.Compared with (1MPa/400 DEG C/H under temperate condition2: CO=2:1), selectivity of light olefin reaches
74%, CO conversion ratio are 11%.
Although selectivity of product is limited to ASF distribution in conclusion FT catalyst activity is higher in the prior art
(58%), this also hinders the direct producing light olefins of synthesis gas to move towards application.Novel coupled catalyst system can break through ASF points
Cloth realizes that synthesis gas is highly selective and prepares low-carbon alkene.Catalyst of the present invention has adaptability to raw material strong, CO conversion ratio
Height, ethylene, propylene selectivity is high, the advantage that ethylene, propylene ratio is adjustable.
Summary of the invention
Poor it is an object of the invention to solve catalyst Sulfur tolerance existing in the prior art, low-carbon alkene selects in product
Property the low and nonadjustable problem of ethylene/propene ratio, provide a kind of new coupling and catalyzing for preparation of low carbon olefines by synthetic gas
System, the coupling and catalyzing system for preparation of low carbon olefines by synthetic gas react when, have Sulfur tolerance it is strong, selectivity of light olefin height and
The advantage that ethylene, propylene ratio is adjustable.
In order to solve the above technical problems, technical scheme is as follows: one kind being used for the direct producing light olefins of synthesis gas
Coupled catalyst system, it is characterised in that coupled catalyst system include catalyst with base of molybdenum and have CHA skeleton structure molecule
Sieve.
In above-mentioned technical proposal, it is preferred that catalyst with base of molybdenum include in molybdenum sulfide, molybdenum oxide and molybdenum carbide at least
A kind of component.
In above-mentioned technical proposal, it is furthermore preferred that catalyst with base of molybdenum includes one in molybdenum sulfide, molybdenum oxide and molybdenum carbide
Kind component；Most preferably, catalyst with base of molybdenum contains molybdenum sulfide.
In above-mentioned technical proposal, it is preferred that catalyst with base of molybdenum general molecular formula is MoTt-XaYbZc, wherein T is selected from S, O or C
At least one of, one of X Fe, Co, Ni, Ru, Rh, Pd metal or a variety of, in Y Cr, Mn, Zn, La, Ce metal
One or more, Z is one of alkali metal or a variety of；
The value range that the value range that the value range of a is 0~4, b is 0~2, c is that 0.1~2.5, t is to meet each member
Atom number needed for plain chemical valence.
In above-mentioned technical proposal, it is preferred that T is selected from one of S, O or C；It is furthermore preferred that T is selected from S.
In above-mentioned technical proposal, it is preferred that the value range of a is 0.1~3.3；It is furthermore preferred that the value range of a is 0.3
~3.
In above-mentioned technical proposal, it is preferred that the value range of b is 0.1~1.8；It is furthermore preferred that the value range of a is 0.2
~1.6.
In above-mentioned technical proposal, it is preferred that the value range of c is 0.15~2.2；It is furthermore preferred that the value range of a is
0.2~2.
In above-mentioned technical proposal, X is preferably at least one of Ni and Co；X is preferably one of Ni and Co；More preferably
For the mixture of Ni and Co.
In above-mentioned technical proposal, the ratio of Ni and Co are preferably (1:2)-(2:1).
In above-mentioned technical proposal, Y is preferably Mn.
In above-mentioned technical proposal, Z is preferably the mixture of Na and K, and the ratio of Na and K are preferably (2:1)-(8:1)；It is more excellent
Choosing, the ratio of Na and K are (1:1)~(6:1).
In above-mentioned technical proposal, it is preferred that oxygenatedchemicals can also be added in raw material；It is furthermore preferred that can also add in raw material
Enter methanol or carbon dioxide.
In above-mentioned technical proposal, (MoTt-XaYbZc+ CHA) catalyst application method it is as follows:
At 320-480 DEG C of reaction temperature, reaction pressure 0.5-8MPa, volume space velocity 800-10,000h-1, in synthesis gas,
CO and H2Volume ratio be 0.3-3.5, synthesis gas and above-mentioned catalyst haptoreaction obtain the product containing low-carbon alkene.
In above-mentioned technical proposal, it is preferable that 360-440 DEG C of reaction temperature；It is highly preferred that reaction temperature is 380-430 DEG C；
Most preferably, reaction temperature is 390-420 DEG C.
In above-mentioned technical proposal, it is preferable that reaction pressure 1-6MPa.
In above-mentioned technical proposal, it is preferable that volume space velocity 1,000-8,000h-1。
Wherein, the calculation of C2-C4 olefine selective are as follows: (2* ethylene product molal quantity+3* propylene product molal quantity+
4* butene product molal quantity) total carbon number molal quantity in/organic product
Compared to existing catalyst, the coupling of catalyst for preparing alcohol and alcohol alkene catalyst is used in the technical program.Its
In, synthesis gas catalyst for preparing alcohol is based on catalyst with base of molybdenum；Chain growth adjuvant component is using gold such as Fe, Co, Ni, Ru, Rh, Pd
Belong to, effectively promotes the chain growth ability of catalyst for preparing alcohol；Structural promoter component is using metals such as Cr, Mn, Zn, La, Ce, effectively
Catalyst specific surface is improved, the dispersion of active sites is promoted；The addition of alkali metal, the effective acid-base property for adjusting catalyst surface
And electronic property, the appropriate hydrogenation capability for weakening activated centre, reduce the content of alkane in the product；Different CHA bones
The selection of frame structure molecular screen helps to realize the adjusting of ethylene/propene ratio, can be according to the price adjustment E/ of ethylene and propylene
P is 0.3~3.6 to obtain good economic benefit.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Mo-Fe0.6Zn0.2Cs0.8Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the zinc nitrate of the ferric nitrate and 0.01mol that weigh 0.03mol is molten
Two kinds of aqueous solution co-precipitations are filtered, washed after precipitating, are dried overnight at 100 DEG C, roast at 500 DEG C by Yu Shui
4h.The Cs of sulfide intermediate load 0.02mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Fe0.6Zn0.2Cs0.8Sulfide catalyst.
SAPO-34 catalyst is prepared as follows: being respectively with phosphoric acid, boehmite, ethyl orthosilicate, morpholine
Phosphorus source, silicon source, silicon source, template, molar ratio Al2O3∶P2O5∶SiO2∶R∶H2O=1: 1: 0.6: 3: 100, be added reaction kettle after it is old
For 24 hours, obtained solid is washed with deionized water to neutrality stirring crystallization at changing 2 hours, 200 DEG C, separates to obtain solid, dries, Muffle
It is roasted 6 hours for 550 DEG C in furnace, obtains SAPO-34 molecular sieve.
The Mo-Fe got ready is restrained by 0.750.6Zn0.2Cs0.8The SAPO-34 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 2]
Mo-Fe0.8Cs0.8Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the ferric nitrate for weighing 0.04mol is dissolved in water, by two kinds of aqueous solutions
Co-precipitation is filtered, washed after precipitating, is dried overnight at 100 DEG C, roasts 4h at 500 DEG C.Sulfide intermediate load
The Cs of 0.02mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-Fe0.8Cs0.8Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Fe got ready is restrained by 0.750.8Cs0.8Sulfide catalyst and 0.75 restrains the SAPO-34 mixing got ready, dress
Enter in the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is anti-into catalytic bed
It answers, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas system
Low-carbon alkene reaction.Reaction result is shown in Table 1.
[embodiment 3]
Mo-Zn0.8Cs0.8Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the zinc nitrate for weighing 0.04mol is dissolved in water, by two kinds of aqueous solutions
Co-precipitation is filtered, washed after precipitating, is dried overnight at 100 DEG C, roasts 4h at 500 DEG C.Sulfide intermediate load
The Cs of 0.02mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-Zn0.8Cs0.8Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Zn got ready is restrained by 0.750.8Cs0.8Sulfide catalyst and 0.75 restrains the SAPO-34 mixing got ready, dress
Enter in the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is anti-into catalytic bed
It answers, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas system
Low-carbon alkene reaction.Reaction result is shown in Table 1.
[embodiment 4]
Mo-Na sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the acetic acid for weighing 0.10mol is dissolved in water, simultaneously by two kinds of aqueous solutions
Stream is co-precipitated, and is filtered, washed after precipitating, is dried overnight at 100 DEG C, roasts 4h at 500 DEG C.Sulfide intermediate load
The Na of 0.025mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-Na sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Na sulfide catalyst got ready and 0.75 is restrained by 0.75 and restrains the SAPO-34 mixing got ready, is packed into one
In the crystal reaction tube that internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is reacted into catalytic bed, instead
Answering temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis of gas produced low-carbon
Olefine reaction.Reaction result is shown in Table 1.
[embodiment 5]
Mo-Na0.6K0.4Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the acetic acid for weighing 0.10mol is dissolved in water, simultaneously by two kinds of aqueous solutions
Stream is co-precipitated, and is filtered, washed after precipitating, is dried overnight at 100 DEG C, roasts 4h at 500 DEG C.Sulfide intermediate load
The Na of 0.015mol2CO3With the K of 0.01mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Na0.6K0.4Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Na got ready is restrained by 0.750.6K0.4Sulfide catalyst and 0.75 restrains the SAPO-34 mixing got ready, dress
Enter in the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is anti-into catalytic bed
It answers, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas system
Low-carbon alkene reaction.Reaction result is shown in Table 1.
[embodiment 6]
Mo-K sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the acetic acid for weighing 0.10mol is dissolved in water, simultaneously by two kinds of aqueous solutions
Stream is co-precipitated, and is filtered, washed after precipitating, is dried overnight at 100 DEG C, roasts 4h at 500 DEG C.Sulfide intermediate load
The K of 0.025mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-K sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-K sulfide catalyst got ready and 0.75 is restrained by 0.75 and restrains the SAPO-34 mixing got ready, is packed into one
In the crystal reaction tube that internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is reacted into catalytic bed, instead
Answering temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis of gas produced low-carbon
Olefine reaction.Reaction result is shown in Table 1.
[embodiment 7]
Mo-Ni0.5Mn0.1K0.6Oxide catalyst is prepared as follows:
The manganese nitrate for weighing the ammonium molybdate of 0.05mol, the nickel nitrate of 0.025mol, 0.01mol, is stirred, at 100 DEG C
Under be dried overnight, roast 6h at 500 DEG C.After the completion of roasting, catalyst intermediate loads the K of 0.015mol2CO3, at 80 DEG C
Drying overnight, roasts 1h at 400 DEG C, obtains Mo-Ni0.5Mn0.1K0.6Oxide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.5Mn0.1K0.6The SAPO-34 that oxide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 8]
Mo-Ni0.5Mn0.1K0.6Carbide catalyst is prepared as follows:
The manganese nitrate for weighing the ammonium molybdate of 0.05mol, the nickel nitrate of 0.025mol, 0.01mol, is stirred, at 100 DEG C
Under be dried overnight, roast 6h at 500 DEG C.After the completion of roasting, after the completion of roasting, in CH4Atmosphere, be carbonized at 500 DEG C 4h, obtains
Carbide, carbide intermediate load the K of 0.015mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain
Mo-Ni0.5Mn0.1K0.6Carbide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.5Mn0.1K0.6The SAPO-34 that carbide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 9]
Mo-Ni0.5Mn0.1K0.6Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, weighs the nickel acetate of 0.025mol and the manganese nitrate of 0.005mol
It is dissolved in water, by two kinds of aqueous solution co-precipitations, is filtered, washed after precipitating, is dried overnight at 100 DEG C, is roasted at 500 DEG C
4h.The K of sulfide intermediate load 0.015mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Ni0.5Mn0.1K0.6Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.5Mn0.1K0.6The SAPO-34 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 10]
Mo-Ni0.2Co0.3Mn0.1K0.6Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, weigh the nickel acetate of 0.01mol, the cobalt acetate of 0.015mol and
The manganese nitrate of 0.005mol is dissolved in water, and two kinds of aqueous solution co-precipitations are filtered, washed after precipitating, dried at 100 DEG C
Night roasts 4h at 500 DEG C.The K of sulfide intermediate load 0.015mol2CO3, dried overnight, at 400 DEG C at 80 DEG C
1h is roasted, Mo-Ni is obtained0.2Co0.3Mn0.1K0.6Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.2Co0.3Mn0.1K0.6Sulfide catalyst and 0.75 restrains the SAPO-34 got ready
Mixing is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, enter
Catalytic bed reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out
Preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 1.
[embodiment 11]
Mo-Ni0.1Co0.4Mn0.1K0.6Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, weigh the nickel acetate of 0.005mol, the cobalt acetate of 0.02mol and
The manganese nitrate of 0.005mol is dissolved in water, and two kinds of aqueous solution co-precipitations are filtered, washed after precipitating, dried at 100 DEG C
Night roasts 4h at 500 DEG C.The K of sulfide intermediate load 0.015mol2CO3, dried overnight, at 400 DEG C at 80 DEG C
1h is roasted, Mo-Ni is obtained0.1Co0.4Mn0.1K0.6Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.1Co0.4Mn0.1K0.6Sulfide catalyst and 0.75 restrains the SAPO-34 got ready
Mixing is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, enter
Catalytic bed reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out
Preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 1.
[embodiment 12]
Mo-Co0.5Mn0.1K0.6Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, weighs the cobalt acetate of 0.025mol and the manganese nitrate of 0.005mol
It is dissolved in water, by two kinds of aqueous solution co-precipitations, is filtered, washed after precipitating, is dried overnight at 100 DEG C, is roasted at 500 DEG C
4h.The K of sulfide intermediate load 0.015mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Co0.5Mn0.1K0.6Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Co got ready is restrained by 0.750.5Mn0.1K0.6The SAPO-34 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 13]
Mo-Ru0.08Ce0.1Na0.4Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, weighs the ruthenic chloride of 0.004mol and the cerous nitrate of 0.005mol
It is dissolved in water, by two kinds of aqueous solution co-precipitations, is filtered, washed after precipitating, is dried overnight at 100 DEG C, is roasted at 500 DEG C
4h.The Na of sulfide intermediate load 0.01mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Ru0.08Ce0.1Na0.4Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ru got ready is restrained by 0.750.08Ce0.1Na0.4The SAPO-34 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 14]
Mo-Rh0.04La0.6Cs0.2Sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the lanthanum nitrate of the rhodium nitrate and 0.03mol that weigh 0.002mol is molten
Two kinds of aqueous solution co-precipitations are filtered, washed after precipitating, are dried overnight at 100 DEG C, roast at 500 DEG C by Yu Shui
4h.The Cs of sulfide intermediate load 0.005mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Rh0.04La0.6Cs0.2Sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Rh got ready is restrained by 0.750.04La0.6Cs0.2The SAPO-34 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 15]
Mo-Pd0.1Cr0.2K sulfide catalyst is prepared as follows:
The ammonium thiomolybdate for weighing 0.05mol is dissolved in water, and the chromic nitrate of the palladium chloride and 0.01mol that weigh 0.005mol is molten
Two kinds of aqueous solution co-precipitations are filtered, washed after precipitating, are dried overnight at 100 DEG C, roast at 500 DEG C by Yu Shui
4h.The K of sulfide intermediate load 0.025mol2CO3, dried overnight at 80 DEG C, roast 1h at 400 DEG C, obtain Mo-
Pd0.1Cr0.2K sulfide catalyst.
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Pd got ready is restrained by 1.360.1Cr0.2K sulfide catalyst and 0.17 restrains the SAPO-34 mixing got ready,
It is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into catalytic bed
Reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas
Reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 16]
Mo-Pd0.1Cr0.2K sulfide catalyst is prepared by [embodiment 13].
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Pd got ready is restrained by 1.140.1Cr0.2K sulfide catalyst and 0.38 restrains the SAPO-34 mixing got ready,
It is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into catalytic bed
Reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas
Reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 17]
Mo-Pd0.1Cr0.2K sulfide catalyst is prepared by [embodiment 13].
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Pd got ready is restrained by 0.750.1Cr0.2K sulfide catalyst and 0.75 restrains the SAPO-34 mixing got ready,
It is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into catalytic bed
Reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas
Reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 18]
Mo-Pd0.1Cr0.2K sulfide catalyst is prepared by [embodiment 13].
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Pd got ready is restrained by 0.380.1Cr0.2K sulfide catalyst and 1.14 restrains the SAPO-34 mixing got ready,
It is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into catalytic bed
Reaction, reaction temperature are 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis gas
Reaction for preparing light olefins.Reaction result is shown in Table 1.
[embodiment 19]
Mo-Fe0.6Zn0.2Cs0.8Sulfide catalyst is prepared by [embodiment 1].
SAPO-34 catalyst is prepared by [embodiment 1].
SSZ-13 catalyst is prepared as follows: with boehmite, ethyl orthosilicate, N, N, N- trimethyl adamantane
Ammonium hydroxide is respectively silicon source, silicon source, template, molar ratio Al2O3∶SiO2∶R∶H2O=1: 40: 5: 900, after reaction kettle is added
Crystallization 48h is stirred at ageing 2 hours, 150 DEG C, obtained solid is washed with deionized water to neutrality, separates to obtain solid, dries, horse
Not 550 DEG C roasting 6 hours in furnace, obtain SSZ-13 molecular sieve.
The Mo-Fe got ready is restrained by 0.750.6Zn0.2Cs0.8Sulfide catalyst, 0.5 restrain the SAPO-34 that gets ready and
0.25 restrains the SSZ-13 mixing got ready, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:
50) it is passed through in reaction tube, is reacted into catalytic bed, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume is empty
Speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 2.
[embodiment 20]
Mo-Fe0.6Zn0.2Cs0.8Sulfide catalyst is prepared by [embodiment 1].
SAPO-34 catalyst is prepared by [embodiment 1].SSZ-13 catalyst is prepared by [embodiment 19].
The Mo-Fe got ready is restrained by 0.750.6Zn0.2Cs0.8Sulfide catalyst, 0.25 restrain the SAPO-34 that gets ready and
0.5 restrains the SSZ-13 mixing got ready, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:
50) it is passed through in reaction tube, is reacted into catalytic bed, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume is empty
Speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 2.
[embodiment 21]
Mo-Fe0.6Zn0.2Cs0.8Sulfide catalyst is prepared by [embodiment 1].
SSZ-13 catalyst is prepared by [embodiment 19].
The Mo-Fe got ready is restrained by 0.750.6Zn0.2Cs0.8The SSZ-13 that sulfide catalyst and 0.75 restraint are got ready is mixed
It closes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, into urging
Change bed reaction, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of closed
At gas reaction for preparing light olefins.Reaction result is shown in Table 2.
[embodiment 22~26]
The catalyst that Example 1 is prepared is reacted for preparation of low carbon olefines by synthetic gas, reaction condition and evaluation result
It is shown in Table 3.
[embodiment 27]
Mo-Ni0.1Co0.4Mn0.1K0.6Sulfide catalyst is prepared by [embodiment 11].
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.710.1Co0.4Mn0.1K0.6Sulfide catalyst and 0.79 restrains the SAPO-34 got ready
Mixing is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=70:30) it is passed through in reaction tube, enter
Catalytic bed reaction, reaction temperature are 400 DEG C, and reaction system pressure is 3MPa, and gas volume air speed is 7,000h-1Under the conditions of carry out
Preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 5.
[embodiment 28]
Mo-Ni0.1Co0.4Mn0.1K0.6Sulfide catalyst is prepared by [embodiment 11].
SAPO-34 catalyst is prepared by [embodiment 1].
The Mo-Ni got ready is restrained by 0.750.1Co0.4Mn0.1K0.6Sulfide catalyst and 0.75 restrains the SAPO-34 got ready
Mixing is fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide:nHydrogen sulfide=49.99:50:0.01) it is passed through
In reaction tube, to be reacted into catalytic bed, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,
000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas life experiment, reaction result is shown in Table 6 within the 200th hour.
[comparative example 1]
According to the preparation method of document [Science, 2016,351,1065-1068], Zn is synthesized3.5CrAl and SAPO-34.
By 0.75 gram of Zn3.5CrAl and 0.75 gram of SAPO-34 mixing, is packed into the crystal reaction tube that an internal diameter is 6 millimeters
In, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, reaction system pressure
Power is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 4.
[comparative example 2]
According to the preparation method of document [Angewandte Chemie, 2016,128,4803-4806], ZnZr is synthesized2With
SAPO-34。
By 0.75 gram of ZnZr2It mixes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters with 0.75 gram of SAPO-34, it will
(nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, and reaction system pressure is
4MPa, gas volume air speed are 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 4.
[comparative example 3]
According to the preparation method of patent document [CN103157489A], FeMnCuK catalyst is synthesized.
1.50 grams of FeMnCuK catalyst are fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide=
It 50:50) is passed through in reaction tube, is reacted into catalytic bed, reaction temperature is 400 DEG C, and reaction system pressure is 4MPa, gas volume
Air speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 4.
[comparative example 4]
According to the preparation method of patent document [CN1279131A], ZSM-5 boiling of the direct crystallization in Fe-Al alloy is synthesized
Stone.
ZSM-5 zeolite catalyst of 1.50 grams of direct crystallizations in Fe-Al alloy is packed into the stone that an internal diameter is 6 millimeters
In English reaction tube, by (nHydrogen:nCarbon monoxide=50:50) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, instead
Answering system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result
It is shown in Table 4.
[comparative example 5]
According to the preparation method of document [Science, 2016,351,1065-1068], Zn is synthesized3.5CrAl and SAPO-34.
By 0.71 gram of Zn3.5CrAl and 0.79 gram of SAPO-34 mixing, is packed into the crystal reaction tube that an internal diameter is 6 millimeters
In, by (nHydrogen:nCarbon monoxide=70:30) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, reaction system pressure
Power is 3MPa, and gas volume air speed is 7,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas reaction.Reaction result is shown in Table 5.
[comparative example 6]
According to the preparation method of document [Science, 2016,351,1065-1068], Zn is synthesized3.5CrAl and SAPO-34.
By 0.75 gram of Zn3.5CrAl and 0.75 gram of SAPO-34 mixing, is packed into the crystal reaction tube that an internal diameter is 6 millimeters
In, by (nHydrogen:nCarbon monoxide:nHydrogen sulfide=49.99:50:0.01) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature 400
DEG C, reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of to carry out the preparation of low carbon olefines by synthetic gas service life real
It tests, reaction result is shown in Table 6 within the 200th hour.
[comparative example 7]
According to the preparation method of document [Angewandte Chemie, 2016,128,4803-4806], ZnZr is synthesized2With
SAPO-34。
By 0.75 gram of ZnZr2It mixes, is fitted into the crystal reaction tube that an internal diameter is 6 millimeters with 0.75 gram of SAPO-34, it will
(nHydrogen:nCarbon monoxide:nHydrogen sulfide=49.99:50:0.01) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, instead
Answering system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas life experiment, the
Reaction result is shown in Table 6 within 200 hours.
[comparative example 8]
According to the preparation method of patent document [CN103157489A], FeMnCuK catalyst is synthesized.
1.50 grams of FeMnCuK catalyst are fitted into the crystal reaction tube that an internal diameter is 6 millimeters, by (nHydrogen:nCarbon monoxide:
nHydrogen sulfide=49.99:50:0.01) it is passed through in reaction tube, it is reacted into catalytic bed, reaction temperature is 400 DEG C, reaction system pressure
For 4MPa, gas volume air speed is 2,000h-1Under the conditions of carry out preparation of low carbon olefines by synthetic gas life experiment, the 200th hour react
It the results are shown in Table 6.
[comparative example 9]
According to the preparation method of patent document [CN1279131A], ZSM-5 boiling of the direct crystallization in Fe-Al alloy is synthesized
Stone.
ZSM-5 zeolite catalyst of 1.50 grams of direct crystallizations in Fe-Al alloy is packed into the stone that an internal diameter is 6 millimeters
In English reaction tube, by (nHydrogen:nCarbon monoxide:nHydrogen sulfide=49.99:50:0.01) it is passed through in reaction tube, it is reacted into catalytic bed, reaction
Temperature is 400 DEG C, and reaction system pressure is 4MPa, and gas volume air speed is 2,000h-1Under the conditions of carry out synthesis of gas produced low-carbon alkene
Hydrocarbon life experiment, reaction result is shown in Table 6 within the 200th hour.
Table 1
Table 2
| CO hydrogenation catalyst | CHA molecular sieve and weight ratio | Ethylene selectivity/% | Propylene Selectivity/% | |
| Embodiment 1 | Mo-Fe0.6Zn0.2Cs0.8 | SAPO-34 | 13.9 | 45.8 |
| Embodiment 19 | Mo-Fe0.6Zn0.2Cs0.8 | SAPO-34:SSZ-13=2:1 | 22.5 | 34.6 |
| Embodiment 20 | Mo-Fe0.6Zn0.2Cs0.8 | SAPO-34:SSZ-13=1:2 | 36.1 | 20.3 |
| Embodiment 21 | Mo-Fe0.6Zn0.2Cs0.8 | SSZ-13 | 45.0 | 12.4 |
Table 3
| Temperature/DEG C | Pressure/MPa | Air speed/h-1 | Conversion ratio/% | C2-4 olefine selective/% | |
| Embodiment 1 | 400 | 4 | 2000 | 28.3 | 74.8 |
| Embodiment 22 | 380 | 7 | 4000 | 21.1 | 72.2 |
| Embodiment 23 | 390 | 6 | 3000 | 25.8 | 73.5 |
| Embodiment 24 | 410 | 3 | 6000 | 28.5 | 73.2 |
| Embodiment 25 | 420 | 2 | 5000 | 30.4 | 71.0 |
| Embodiment 26 | 430 | 0.5 | 7000 | 34.5 | 69.1 |
Table 4
| Catalyst | Conversion ratio/% | C2-4 olefine selective/% | |
| Embodiment 11 | Mo-Ni0.1Co0.4Mn0.1K0.6+ SAPO-34 (weight ratio 1: 1) | 31.5 | 80.3 |
| Comparative example 1 | Zn3.5CrAl+SAPO-34 (weight ratio 1: 1) | 38.2 | 65.8 |
| Comparative example 2 | ZnZr2+ SAPO-34 (weight ratio 1: 1) | 35.7 | 62.1 |
| Comparative example 3 | FeMnCuK | 55.0 | 49.5 |
| Comparative example 4 | ZSM-5/FeAl | 45.4 | 50.7 |
Table 5
| Catalyst | Conversion ratio/% | C2-4 olefine selective/% | |
| Embodiment 27 | Mo-Ni0.1Co0.4Mn0.1K0.6+ SAPO-34 (weight ratio 1: 1) | 16.6 | 84.3 |
| Comparative example 5 | Zn3.5CrAl+SAPO-34 (weight ratio 1: 1) | 17.2 | 78.8 |
Table 6
| Catalyst | Conversion ratio/% | C2-4 olefine selective/% | |
| Embodiment 28 | Mo-Ni0.1Co0.4Mn0.1K0.6+ SAPO-34 (weight ratio 1:1) | 29.2 | 77.6 |
| Comparative example 6 | Zn3.5CrAl+SAPO-34 (weight ratio 1:1) | 24.6 | 61.0 |
| Comparative example 7 | ZnZr2+ SAPO-34 (weight ratio 1:1) | 21.5 | 58.8 |
| Comparative example 8 | FeMnCuK | 47.5 | 46.7 |
| Comparative example 9 | ZSM-5/FeAl | 38.2 | 47.1 |
Claims (13)
1. a kind of coupled catalyst system for the direct producing light olefins of synthesis gas, it is characterised in that coupled catalyst system packet
It includes catalyst with base of molybdenum and there is CHA skeleton structure molecular sieve.
2. being used for the coupled catalyst system of the direct producing light olefins of synthesis gas according to claim l, it is characterised in that
Catalyst with base of molybdenum includes selected from least one of molybdenum sulfide, molybdenum oxide and molybdenum carbide component.
3. being used for the coupled catalyst system of the direct producing light olefins of synthesis gas according to claim l, it is characterised in that:
Catalyst with base of molybdenum general molecular formula is MoTt-XaYbZc, wherein T is selected from least one of S, O or C, X Fe, Co, Ni, Ru, Rh,
One of Pd metal is a variety of, one of Y Cr, Mn, Zn, La, Ce metal or a variety of, Z be one of alkali metal or
It is a variety of；
The value range that the value range that the value range of a is 0~4, b is 0~2, c is that 0.1~2.5, t is to meet each element
Atom number needed for conjunction valence.
4. the coupled catalyst system according to claim 1 for the direct producing light olefins of synthesis gas, it is characterised in that:
It is SAPO-34 and/or SSZ-13 with CHA skeleton structure molecular sieve.
5. the coupled catalyst system according to claim 3 for the direct producing light olefins of synthesis gas, it is characterised in that a
Value range be 0.1~3.3.
6. the coupled catalyst system according to claim 3 for the direct producing light olefins of synthesis gas, it is characterised in that b
Value range be 0.1~1.8.
7. the coupled catalyst system according to claim 3 for the direct producing light olefins of synthesis gas, it is characterised in that c
Value range be 0.1~2.2.
8. the coupled catalyst system according to claim 3 for the direct producing light olefins of synthesis gas, it is characterised in that X
Selected from Co and/or Ni.
9. the coupled catalyst system according to claim 3 for the direct producing light olefins of synthesis gas, it is characterised in that
Alkali metal is selected from least one of Na, K and Cs.
10. the coupled catalyst system according to claim 1 for the direct producing light olefins of synthesis gas, it is characterised in that
Catalyst with base of molybdenum and weight ratio with CHA skeleton structure molecular sieve are (1:10)~(10:1).
11. the coupled catalyst system according to claim 10 for the direct producing light olefins of synthesis gas, feature exist
In catalyst with base of molybdenum and weight ratio with CHA skeleton structure molecular sieve be (1:6)~(6:1).
12. the coupled catalyst system according to claim 11 for the direct producing light olefins of synthesis gas, feature exist
In catalyst with base of molybdenum and weight ratio with CHA skeleton structure molecular sieve be (1:4)~(4:1).
13. a kind of method for preparation of low carbon olefines by synthetic gas, at 320-480 DEG C of reaction temperature, reaction pressure 0.5-8MPa, body
Product air speed is 800-10000h-1, in synthesis gas, CO and H2Volume ratio be 0.3-3.5, synthesis gas and claim 1-12 are any
The item coupled catalyst system haptoreaction obtains the product containing low-carbon alkene.
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| CN112705218A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof |
| CN114950508A (en) * | 2022-06-30 | 2022-08-30 | 陕西师范大学 | Catalyst and method for preparing low-carbon olefin by directly converting sulfur-containing synthesis gas |
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| CN112705218A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof |
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| CN114950508B (en) * | 2022-06-30 | 2023-08-22 | 陕西师范大学 | Catalyst and method for preparing low-carbon olefin by direct conversion of sulfur-containing synthesis gas |
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