CN105080597A - Catalyst for preparing olefins from synthetic gas and preparation method thereof - Google Patents

Catalyst for preparing olefins from synthetic gas and preparation method thereof Download PDF

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CN105080597A
CN105080597A CN201410202902.3A CN201410202902A CN105080597A CN 105080597 A CN105080597 A CN 105080597A CN 201410202902 A CN201410202902 A CN 201410202902A CN 105080597 A CN105080597 A CN 105080597A
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catalyst
zsm
kernel
synthesis gas
parts
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CN105080597B (en
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宋卫林
陶跃武
李剑锋
庞颖聪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a catalyst for preparing olefins from synthetic gas and a preparation method thereof, and mainly solves the poor middle and low-C2-C4 olefin selectivity problem of tropsch synthesis. The catalyst for preparing the olefins from the synthetic gas comprises the following components in parts by weight: 1-20 parts of ZSM-5 shell and 80-99 parts of an inner core, the inner core includes the following components in parts by weight: a) 80-100 parts of a carrier selected from SiO2 or Al2O3; b) 3-20 parts of at least one metal or oxide selected from Fe or Co; c) 1-10 parts of at least one metal or oxide selected from Mn, Zn, Mg or Cu; d) 0.1-5 parts of an oxide or a hydroxide selected from K, Na, Rb or Cs; and e) 0.1-2 parts of at least one oxide selected from Se and Te; and by the technical scheme, the problem is well solved, and the catalyst can be used for industrial production of preparing of olefins from synthetic gas.

Description

Synthesis gas alkene catalyst and preparation method thereof
Technical field
The present invention relates to a kind of synthesis gas alkene catalyst and preparation method thereof.
Technical background
The low-carbon alkene being representative with ethene, propylene (alkene of carbon atom≤4) is the base stock of chemical industry, at present, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, also has alkane, hydrogenated diesel oil, part heavy wet goods.Domestic and international is raw material mainly with natural gas or light petroleum fraction, adopts steam cracking process in Ethylene Complex unit to produce low-carbon alkene.Steam cracking is the large power consumption device in petrochemical industry, and relies on non-renewable petroleum resources completely.Along with the day by day shortage of petroleum resources, be badly in need of finding alternate resources.So be then taken seriously with the research work of substitute gas oil producing olefinic hydrocarbons, some famous oil companies and scientific research institutions have all carried out the research and development of this respect in the world, and achieve achievement attracting people's attention.In the structure of current adjustment using energy source progressively to reduce the national economic development under the background of the dependence of petroleum-based energy, utilize the natural gas resource of China's rich reserves, by gas making producing synthesis gas (carbon monoxide and hydrogen mixed gas), be converted into the alkene of C2 ~ C4 again, in the long term, there is very high strategic importance.
Synthetic holography becomes the method for alkene to comprise indirect method and direct method, methanol decomposition preparing low-carbon olefins MTO technique with become gas via dimethyl ether preparing low-carbon olefins SDTO technique, first by synthesis gas synthesizing methanol or dimethyl ether, then become alkene by methyl alcohol or dimethyl ether conversion.
Synthesis gas is converted into the Fischer-Tropsch synthesis mistake that low-carbon alkene is actually CO hydrogenation.Nineteen twenty-three Germany scientist FranzFisher and HansTropsch has found the reaction of syngas catalytic conversion hydro carbons, therefore, the method being prepared hydro carbons by synthesis gas reaction is called Fiscber-Tropscb synthesis (Fischer-Tropsch synthesizes, and is called for short F-T synthesis) method, namely with CO and H 2react hydro carbons processed, byproduct water and CO 2.It take coal as the large-scale fixed bed F-T synthesizer of raw material that nineteen fifty-five South Africa SASOL (SouthAfricaCoalandGasCorporation) has built up, develop circulating fluidized bed technique subsequently, develop again fixed fluidized bed and slurry bed system technology recently.Nowadays, the coal year disposal ability of SASOL has reached 5,000 ten thousand, and the annual capacity of oil product and chemicals reaches 7,600,000 tons.The F-T synthesis reaction in past its objective is by synthesis gas synthetic fuel liquefied hydrocarbon, although the use of fluidization, ferrum-based catalyst and the interpolation of auxiliary agent, improve the yield of low-carbon alkene (C2-C4 alkene) to a certain extent, but yield of light olefins is still not high, only has 20-25%.
The object of present carbon-chemical synthesis hydro carbons is translated into the low-carbon alkene as basic chemical raw materials, and wherein ethene and propylene are the materials of current most worthy.And be that single step reaction generates object product by the direct preparing low-carbon olefins of synthesis gas, its technological process is simpler than indirect method, and economic evaluation is also more worthwhile.Last decade, causes concern by the direct synthesizing low-carbon alkene of synthesis gas.
Mainly contained following several at present by preparing low-carbon olefin catalyst system and catalyzing.(1) improve the people such as F-T catalyst Dent and find that cobalt-base catalyst can be used for the synthesizing low-carbon alkene of high selectivity, as: Co-Cu/Al 2o 3, Co-Fe/SiO 2, Fe-Co/C, Co-Ni/MnO 2, the system such as Fe-Co alloy/C.Wherein better with the improvement FT catalyst result of Rule chemical company exploitation, at Fe-ZnO-K 2o catalyst adds the components such as Mn or Ti, adopts high gas circulation, reach CO conversion ratio 80%, selectivity of light olefin 70%; (2) Ultra-fine Particle Catalysts Venter etc. are obtained the high dispersive K-Fe-Mn catalyst of Activated Carbon Supported by carbonyl complex decomposition method, and catalyst has very high activity, C in product 2-C 4alkene accounts for 85-90%, and methane is other the unique products detected.The people such as Cupta utilize laser pyrolysis processes to prepare the Fe with catalytic activity xsi yc zbe 40%, C Deng powder CO conversion ratio 2 =-C 4 =selectively reach 87%, only have a small amount of methane.The people such as Shanxi coalification institute Zhong Ping adopt the edman degradation Edman of organic salt complex successfully to develop and develop novel, to have practical background ultrafine particle Fe/Mn catalyst, and CO conversion ratio is greater than 95%, C 2 =-C 4 =/ C 2-C 4be greater than 80%.Beijing University of Chemical Technology Zhang Jingchang utilizes laser pyrolysis processes to prepare high degree of dispersion amorphous superfine iron powder and carbon dust, through solid phase reaction successfully obtained F-T synthesizing activity new species Fe 3c.Prepare with Fe 3c is the Fe-C of main body, the nanocatalysts such as Fe-C-Mn, Fe-C-Mn-K, and CO conversion ratio reaches 90%, and olefine selective reaches more than 80%; (3) people such as amorphous state synthetic catalyst Yokoyama uses amorphous state Fe 40ni 40p 16b 4compound, CO conversion ratio 50%, C 2-C 5hydrocarbon-selective is 65%, and crystalline-state catalyst mainly generates methane; (4) zeolite catalyst represents system the catalyst such as Co-A, Co-Y, Fe-Y, and the people such as Ballivet-Tketchenko obtain the iron catalyst of the high dispersive that zeolite supports, and lower carbon number hydrocarbons is selective quite high, and 88-98% is at C 2-C 4in scope, other iron catalysts supported as ZSM-5, mercerising, 13X zeolite also demonstrate similar behavior.But these catalyst are being prepared Repeatability, are being amplified and prepare in supervisor the difficulty run in various degree.
Summary of the invention
One of technical problem to be solved by this invention is the problem of C2-C4 olefine selective difference in F-T synthesis in conventional art, a kind of synthesis gas alkene catalyst is provided, this catalyst is used for F-T synthesis, have the advantage that C2-C4 olefine selective is high, two of technical problem to be solved by this invention is to provide a kind of method for preparing catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthesis gas alkene catalyst, and catalyst comprises following component with weight parts: the kernel of 1-20 part ZSM-5 shell and 80-99 part, and wherein kernel comprises with weight parts:
A) 80-100 part is selected from SiO 2or Al 2o 3carrier; With carry thereon
B) at least one metal in 3-20 part Fe or Co or oxide; With
C) 1-10 part is selected from least one metal or oxide in Mn, Zn, Mg or Cu; With
D) 0.1-5 part is selected from least one oxide or hydroxide in K, Na, Rb or Cs; With
E) 0.1-2 part is selected from least one oxide in Se and Te.
In technique scheme, catalyst kernel is preferably selected from least one oxide in Se and Te containing 0.5-1.5 part with weight parts; The Si/Al mol ratio preferable range of the ZSM-5 of shell is 10 ~ 80; The Si/Al mol ratio preferable range of the ZSM-5 of shell is 20-60; The parts by weight of shell are preferably 3-12; The parts by weight of kernel are preferably 85-95.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation of catalyst comprises the steps:
I) by the soluble-salt being selected from Fe, Co, Mn, Zn, Mg or Cu containing aequum or alkali water-soluble, be made into mixed solution;
II) aequum is selected from SiO by the mixed solution prepared in step I dipping 2or Al 2o 3carrier on, and dry for standby;
III) at least one hydroxide solution be selected from K, Na, Rb or Cs is added in Step II is impregnated with in the carrier of active component, react 1-30 minute post-drying, obtain catalyst kernel through roasting;
IV) obtained kernel is added in the solution containing binding agent, kernel coats binding agent;
V) on the kernel scribbling binding agent, adsorb the crystal seed of ZSM-5, then add Zeolite synthesis solution situ synthesis ZSM-5 shell;
VI) after being dried by the catalyst being assembled with molecular sieve shell, roasting obtains finished catalyst.
In such scheme, binding agent used is organic binder bond; The crystal seed particle diameter of ZSM-5 used is less than 200 nanometers.
Catalyst prepared by the present invention adds with crossing the dispersion that various auxiliary agent improves Components of Catalysts iron, promotes the reduction of iron, and adds the acidic site of basic component suppression catalyst, improves activity and the selectivity of light olefin of catalyst.Meanwhile, with this catalyst for core, at core outer wrapping one deck ZSM-5 molecular sieve, molecular sieve has highly developed pore structure, and reactant carbon monoxide and hydrogen can arrive catalyst core reaction smoothly, simultaneously due to molecular sieve shape selectivity, limit the generation of large molecular product.And the acidic site that ZSM-5 molecular sieve has, energy catalytic pyrolysis generate longer-chain hydrocarbons, generates low carbon product, improves the selective of low-carbon alkene.
Adopt catalyst prepared by the present invention, at reaction temperature 250-350 DEG C, reaction pressure 0.5-2.5MPa, H 2/ CO volume ratio is 0.5-3, volume space velocity 1000-4000h -1condition under react, CO conversion ratio >80%, C 2-C 4the selective >55% of olefin feed weight, achieves good technique effect.
Below by specific embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Be manganese nitrate and the water-soluble wiring solution-forming of 5.04g nitrate trihydrate copper of 50% by 24.9g six water ferric nitrate, 21.6g mass concentration.
Take 66.3g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium selenate is added the potassium hydroxide solution that 9.5g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 4 hours at 100 DEG C, then at 600 DEG C of roastings, 2 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 14 is generated outward at catalyst kernel, 100 DEG C of dryings 4 hours, 550 DEG C of roastings, 2 hours obtained catalyst 80Fe 6mn 5cu 2k 2se 0.1(SiO 2) 100-20 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 2]
By 76.2g six water ferric nitrate, 10.8g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 10.7g magnesium nitrate hexahydrate.
Take 60.7g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
2.14 grams of ammonium selenates are added the sodium hydroxide solution that 5.84g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 8 hours at 80 DEG C, then at 700 DEG C of roastings, 8 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 22 is generated outward at catalyst kernel, 80 DEG C of dryings 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe 18mg 1.5zn 3.5na 1se 1.4(SiO 2) 90-15 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 3]
Be manganese nitrate and the water-soluble wiring solution-forming of 47.5g cobalt nitrate hexahydrate of 50% by 19.9g six water ferric nitrate, 31g mass concentration.
Take 75.1g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium tellurate is added the potassium hydroxide solution that 0.57g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 7.5 hours at 120 DEG C, then at 650 DEG C of roastings, 6 hours obtained catalyst kernels.
Adopt APTS (the amino pyrene-1 of 8-, 3,6-trisulfonic acid three ammonium salt) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 75 is generated outward at catalyst kernel, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98Co 10fe 4mn 6k 0.1te 0.1(Al 2o 3) 95-2 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 4]
Be manganese nitrate and the water-soluble wiring solution-forming of 47.5g cobalt nitrate hexahydrate of 50% by 19.9g six water ferric nitrate, 31g mass concentration.
Take 75.1g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium tellurate is added the potassium hydroxide solution that 0.57g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 7.5 hours at 120 DEG C, then at 650 DEG C of roastings, 6 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 80 is generated outward at catalyst kernel, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98Co 10fe 4mn 6k 0.1te 0.1(Al 2o 3) 95-2 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 5]
Be manganese nitrate and the water-soluble wiring solution-forming of 47.5g cobalt nitrate hexahydrate of 50% by 19.9g six water ferric nitrate, 31g mass concentration.
Take 75.1g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium tellurate is added the potassium hydroxide solution that 0.57g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 7.5 hours at 120 DEG C, then at 650 DEG C of roastings, 6 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 10 is generated outward at catalyst kernel, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98Co 10fe 4mn 6k 0.1te 0.1(Al 2o 3) 9595-2 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 6]
Be manganese nitrate and the water-soluble wiring solution-forming of 47.5g cobalt nitrate hexahydrate of 50% by 19.9g six water ferric nitrate, 31g mass concentration.
Take 75.1g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium tellurate is added the potassium hydroxide solution that 0.57g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 7.5 hours at 120 DEG C, then at 650 DEG C of roastings, 6 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 47 is generated outward at catalyst kernel, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98Co 10fe 4mn 6k 0.1te 0.1(Al 2o 3) 95-2 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 7]
Be manganese nitrate and the water-soluble wiring solution-forming of 3.59g zinc nitrate hexahydrate of 50% by 24.7g six water ferric nitrate, 9.77g six water nickel nitrate, 25.7g mass concentration.
Take 71g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
1.79 grams of ammonium selenates and 0.42 gram of ammonium tellurate are added the potassium hydroxide solution that 22.6g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 10 hours at 90 DEG C, then at 400 DEG C of roastings, 9 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 58 is generated outward at catalyst kernel, 90 DEG C of dryings 10 hours, 750 DEG C of roastings, 9 hours obtained catalyst 91Fe 5ni 2.5mn 5zn 1k 4se 1.0te 0.6(Al 2o 3) 90-9 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 8]
By 56.4g cobalt nitrate hexahydrate, 15.5g six water nickel nitrate and the water-soluble wiring solution-forming of 2.86g nitrate trihydrate copper.
Take 59.6g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
1.42g ammonium tellurate is added the cesium hydroxide solution that 17.7g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 5 hours at 140 DEG C, then at 550 DEG C of roastings, 4 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 29 is generated outward at catalyst kernel, 140 DEG C of dryings 5 hours, 450 DEG C of roastings, 7 hours obtained catalyst 82Co 15ni 5cu 1.2cs 5se 1.0(Al 2o 3) 95-18 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 9]
Be the manganese nitrate of 50%, 8.6g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 7.19g nitrate trihydrate copper by 94.8g six water ferric nitrate, 24.6g mass concentration.
Take 60.5g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.85 gram of ammonium selenate is added the potassium hydroxide solution that 1.1g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 6.5 hours at 110 DEG C, then at 750 DEG C of roastings, 5 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 34 is generated outward at catalyst kernel, 110 DEG C of dryings 6.5 hours, 700 DEG C of roastings, 4 hours obtained catalyst 93Fe 20mn 5cu 2.5zn 2.5k 0.2se 0.5(SiO 2) 80-7 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 10]
Be the manganese nitrate of 50%, 22.2g cobalt nitrate hexahydrate, 3.373g zinc nitrate hexahydrate, 3.91g magnesium nitrate hexahydrate and the water-soluble wiring solution-forming of 5.63g nitrate trihydrate copper by 23.2g six water ferric nitrate, 29g mass concentration.
Take 63g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
1.98 grams of ammonium tellurates are added the potassium hydroxide solution that 8g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 12 hours at 150 DEG C, then at 500 DEG C of roastings, 5.5 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 51 is generated outward at catalyst kernel, 150 DEG C of dryings 12 hours, 600 DEG C of roastings, 3 hours obtained catalyst 86Co 5fe 5mn 6cu 2zn 1mg 0.5k 1.5te 1.5(SiO 2) 85-14 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 11]
Be manganese nitrate and the water-soluble wiring solution-forming of 14.4g magnesium nitrate hexahydrate of 50% by 40.2g six water ferric nitrate, 15.7g mass concentration.
Take 68.1g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
2.57 grams of ammonium selenates are added the potassium hydroxide solution that 13.2g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 12 hours at 150 DEG C, then at 800 DEG C of roastings, 7 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 63 is generated outward at catalyst kernel, 95 DEG C of dryings 7 hours, 500 DEG C of roastings, 10 hours obtained catalyst 87Fe 8mg 1.7mn 3k 2.3se 1.8(Al 2o 3) 85-13 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 12]
By 14.6g six water ferric nitrate and the water-soluble wiring solution-forming of 13.3g nitrate trihydrate copper.
Take 76.1g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
2.0 grams of ammonium tellurates are added the potassium hydroxide solution that 25.1g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 9 hours at 105 DEG C, then at 450 DEG C of roastings, 3 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 31 is generated outward at catalyst kernel, 105 DEG C of dryings 9 hours, 800 DEG C of roastings, 6 hours obtained catalyst 90Fe 3cu 4.5k 4.5te 2.0(SiO 2) 98-10 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 13]
Be the manganese nitrate of 50%, 39.5g cobalt nitrate hexahydrate and the water-soluble wiring solution-forming of 12.5g nitrate trihydrate copper by 10.7g mass concentration.
Take 66g alumina support, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.59 gram of ammonium selenate is added the rubidium hydroxide solution that 4.75g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 6 hours at 130 DEG C, then at 700 DEG C of roastings, 19 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 18 is generated outward at catalyst kernel, 130 DEG C of dryings 6 hours, 650 DEG C of roastings, 8 hours obtained catalyst 83Co 10mn 2.5cu 5rb 1.2se 0.4(Al 2o 3) 100-17ZSM-5, the outer numeral of bracket is parts by weight.
[embodiment 14]
By 76.2g six water ferric nitrate, 10.8g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 10.7g magnesium nitrate hexahydrate.
Take 60.8g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.84 gram of ammonium tellurate and 1.07 grams of ammonium selenates are added the sodium hydroxide solution that 5.88g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 8 hours at 80 DEG C, then at 700 DEG C of roastings, 8 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 22 is generated outward at catalyst kernel, 80 DEG C of dryings 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe 18mg 1.5zn 3.5na 1se 0.7te 0.7(SiO 2) 90-15 (ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 15]
By 76.3g six water ferric nitrate, 10.8g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 10.7g magnesium nitrate hexahydrate.
Take 60.9g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
1.69 grams of ammonium tellurates are added the sodium hydroxide solution that 5.88g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 8 hours at 80 DEG C, then at 700 DEG C of roastings, 8 hours obtained catalyst kernels.
Adopt PSS (sulfonated polystyrene) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 22 is generated outward at catalyst kernel, 80 DEG C of dryings 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe 18mg 1.5zn 3.5na 1te 1.4(SiO 2) 90-15 (ZSM-5), the outer numeral of bracket is parts by weight.
[comparative example 1]
Be manganese nitrate and the water-soluble wiring solution-forming of 5.04g nitrate trihydrate copper of 50% by 24.9g six water ferric nitrate, 21.6g mass concentration.
Take 66.3g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium selenate is added the potassium hydroxide solution that 9.5g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 4 hours at 100 DEG C, then at 600 DEG C of roastings, 2 hours obtained catalyst Fes 6mn 5cu 2k 2se 0.1(SiO 2) 100.
[comparative example 2]
Be manganese nitrate and the water-soluble wiring solution-forming of 5.04g nitrate trihydrate copper of 50% by 24.9g six water ferric nitrate, 21.6g mass concentration.
Take 66.3g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
0.15 gram of ammonium selenate is added the potassium hydroxide solution that 9.5g mass concentration is 20%, then adds in catalyst and stir, place 10 minutes, then dry 4 hours at 100 DEG C, then at 600 DEG C of roastings, 2 hours obtained catalyst Fes 6mn 5cu 2k 2se 0.1(ZSM-5) 100.
[comparative example 3]
Be manganese nitrate and the water-soluble wiring solution-forming of 5.04g nitrate trihydrate copper of 50% by 24.9g six water ferric nitrate, 21.6g mass concentration.
Take 66.3g silica supports, by above-mentioned solution impregnation on carrier, be dried to outside catalyst granules at 60 DEG C and there is no unnecessary moisture.
By 9.5g mass concentration be 20% potassium hydroxide solution add in catalyst and stir, place 10 minutes, then dry 4 hours at 100 DEG C, then at 600 DEG C of roastings, 2 hours obtained catalyst kernels.
Adopt PDDA (diallyl dimethyl ammoniumchloride) as binding agent, ZSM-5 nanosized seeds is adsorbed on catalyst kernel, join in Zeolite synthesis liquid and react, the ZSM-5 molecular sieve shell that one deck silica alumina ratio is 14 is generated outward at catalyst kernel, 100 DEG C of dryings 4 hours, 550 DEG C of roastings, 2 hours obtained catalyst 80Fe 6mn 5cu 2k 2se 0.1(SiO 2) 100-20 (ZSM-5), the outer numeral of bracket is parts by weight.
Adopt the catalyst prepared of embodiment 1-13 and comparative example 1-3 at reaction temperature 250-350 DEG C, reaction pressure 0.5-2.5MPa, H 2/ CO volume ratio is 0.5-3, volume space velocity 1000-4000h -1condition under react, actual conditions and the results are shown in Table for 3 (120 hours reaction time).
Table 1
Table 2

Claims (10)

1. a synthesis gas alkene catalyst, catalyst comprises following component with weight parts:
The kernel of 1-20 part ZSM-5 shell and 80-99 part, wherein kernel comprises with weight parts:
A) 80-100 part is selected from SiO 2or Al 2o 3carrier; With carry thereon
B) at least one metal in 3-20 part Fe or Co or oxide; With
C) 1-10 part is selected from least one metal or oxide in Mn, Zn, Mg or Cu; With
D) 0.1-5 part is selected from least one oxide or hydroxide in K, Na, Rb or Cs; With
E) 0.1-2 part is selected from least one oxide in Se and Te.
2. synthesis gas alkene catalyst according to claim 1, is characterized in that catalyst kernel contains 0.5-1.5 part with weight parts and is selected from least one oxide in Se and Te.
3. synthesis gas alkene catalyst according to claim 1, is characterized in that the Si/Al mol ratio of the ZSM-5 of shell is 10-80.
4. synthesis gas alkene catalyst according to claim 1, is characterized in that the Si/Al mol ratio of the ZSM-5 of shell is 20-60.
5. synthesis gas alkene catalyst according to claim 1, is characterized in that the parts by weight of shell are 3-12.
6. synthesis gas alkene catalyst according to claim 1, is characterized in that the parts by weight of kernel are 85-95.
7. the preparation method of synthesis gas alkene catalyst described in claim 1, comprises the steps:
I) by the soluble-salt being selected from Fe, Co, Mn, Zn, Mg or Cu containing aequum or alkali water-soluble, be made into mixed solution;
II) aequum is selected from SiO by the mixed solution prepared in step I dipping 2or Al 2o 3carrier on, and dry for standby;
III) at least one hydroxide solution be selected from K, Na, Rb or Cs is added in Step II is impregnated with in the carrier of active component, react 1-30 minute post-drying, obtain catalyst kernel through roasting;
IV) obtained kernel is added in the solution containing binding agent, kernel coats binding agent;
V) on the kernel scribbling binding agent, adsorb the crystal seed of ZSM-5, then add Zeolite synthesis solution situ synthesis ZSM-5 shell;
VI) after being dried by the catalyst being assembled with molecular sieve shell, roasting obtains finished catalyst.
8. synthesis gas alkene catalyst preparation method according to claim 7, is characterized in that binding agent used is organic binder bond.
9. synthesis gas alkene catalyst preparation method according to claim 7, is characterized in that the crystal seed particle diameter of ZSM-5 used is less than 200 nanometers.
10. a method for synthesis gas alkene, synthesis gas at reaction temperature 250-350 DEG C, reaction pressure 0.5-2.5MPa, H 2/ CO volume ratio is 0.5-3, volume space velocity 1000-4000h -1condition under react Formed hydrogen compound with catalyst exposure described in any one of claim 1-6.
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