CN104549447A - Catalyst for olefin prepared by synthesis gas and preparation method of catalyst - Google Patents
Catalyst for olefin prepared by synthesis gas and preparation method of catalyst Download PDFInfo
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- CN104549447A CN104549447A CN201310512198.7A CN201310512198A CN104549447A CN 104549447 A CN104549447 A CN 104549447A CN 201310512198 A CN201310512198 A CN 201310512198A CN 104549447 A CN104549447 A CN 104549447A
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Abstract
The invention relates to a catalyst for olefin prepared by synthesis gas and a preparation method of the catalyst, and mainly aims to solve the problem of low selectivity of low C2-C4 olefin in fischer-tropsch synthesis. The problem can be well solved by adopting a technical scheme that the catalyst is prepared from the following components in parts by weight: 1-20 parts of a shell which is one of ZSM-5 and beta zeolite and 80-99 parts of a kernel, wherein the kernel comprises 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 of Fe and Co carried on (a), (c) 1-10 parts of at least one metal or oxide of Mn, Zn, Mg and Cu, and (d) 0.1-5 parts of oxide or hydroxide of K, Na, Rb and Cs. The catalyst can be applied to industrial production of olefin preparation by synthesis gas.
Description
Technical field
The present invention relates to a kind of synthesis gas alkene catalyst and preparation method thereof.
Background technology
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 Franz Fisher and Hans Tropsch 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.Nineteen fifty-five South Africa SASOL(South Africa Coal and Gas Corporation) to have built up take coal as the large-scale fixed bed F-T synthesizer of raw material, 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.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 selectivity of light olefin is 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 low C2-C4 olefine selective difference in F-T synthesis in conventional art, provides a kind of synthesis gas alkene catalyst, and this catalyst is used for F-T synthesis, has C
2-C
4the advantage that 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, catalyst comprises following component with weight parts: 1-20 part is selected from the kernel of shell a kind of in ZSM-5 or β zeolite 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 a kind of oxide or hydroxide in K, Na, Rb or Cs.
In technique scheme, the Si/Al mol ratio of ZSM-5 or the β zeolite of catalyst shell is greater than 10, and preferable range is that Si/Al mol ratio is greater than 30; The parts by weight preferable range of shell is 3-12; The parts by weight preferable range of kernel is 85-95.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: catalyst preparing comprises the steps:
) 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;
) by step
aequum is selected from SiO by the mixed solution dipping of middle preparation
2or Al
2o
3carrier on, and be dried to outside catalyst granules and there is no unnecessary moisture;
) K, Na, Rb or Cs hydroxide solution will be selected from be added to step
in be impregnated with in the carrier of active component, reaction 1-30 minute, dries 4-12 hour at 80-140 DEG C, then at 400-800 DEG C of roasting 2-10 hour, obtained catalyst kernel;
) pulp spraying containing corresponding molecular sieve is coated onto step
on obtained catalyst kernel, dry 4-12 hour at 80-150 DEG C, at 400-800 DEG C of roasting 2-10 hour, obtained catalyst.
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.Simultaneously, with this catalyst for core, at core outer wrapping one deck 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, make large molecular product stay in catalyst, be cracked into low carbon product in the active sites of catalyst surface, improve the selective of low-carbon alkene.
Adopt catalyst prepared by the present invention, at 250-350 DEG C, 0.5-2.5MPa, volume space velocity 1000-4000h
-1condition under react, CO conversion ratio >80%, C
2-C
4olefine selective >55%, 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.
Add the potassium hydroxide solution 9.51g that mass concentration is 20%, stir, place 10 minutes, then dry 4 hours at 100 DEG C, then at 600 DEG C of roastings, 2 hours obtained catalyst kernels.
The pulp spraying being the ZSM-5 molecular sieve of 30 containing 20 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 100 DEG C of dryings 4 hours, 550 DEG C of roastings, 2 hours obtained catalyst 80Fe
6mn
5cu
2k
2(SiO
2)
100-20(ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 2]
By 77.4g six water ferric nitrate, 10.9g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 10.86g magnesium nitrate hexahydrate.
Take 61.7g 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.
Add the sodium hydroxide solution 14g that mass concentration is 20%, stir, place 10 minutes, then dry 8 hours at 80 DEG C, then at 700 DEG C of roastings, 8 hours obtained catalyst kernels.
The pulp spraying being the beta-molecular sieve of 45 containing 15 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 80 DEG C of dryings 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe
18mg
1.5zn
3.5na
1(SiO
2)
90-15 β, 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, 31.01g mass concentration.
Take 75.4g 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.
Add the potassium hydroxide solution 0.55g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 10 containing 2 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98 Co
10fe
4mn
6k
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, 31.01g mass concentration.
Take 75.4g 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.
Add the potassium hydroxide solution 0.55g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 5 containing 2 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98 Co
10fe
4mn
6k
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, 31.01g mass concentration.
Take 75.4g 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.
Add the potassium hydroxide solution 0.55g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 40 containing 2 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98 Co
10fe
4mn
6k
0.1(Al
2o
3)
95-2(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, 31.01g mass concentration.
Take 75.4g 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.
Add the potassium hydroxide solution 0.55g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 150 containing 2 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 120 DEG C of dryings 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98 Co
10fe
4mn
6k
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 3.65g zinc nitrate hexahydrate of 50% by 25.1g six water ferric nitrate, 9.9g six water nickel nitrate, 26.1g mass concentration.
Take 72.1g 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.
Add the potassium hydroxide solution 23g that mass concentration is 20%, stir, place 10 minutes, then dry 10 hours at 90 DEG C, then at 400 DEG C of roastings, 9 hours obtained catalyst kernels.
The pulp spraying being the beta-molecular sieve of 150 containing 9 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 90 DEG C of dryings 10 hours, 750 DEG C of roastings, 9 hours obtained catalyst 91 Fe
5ni
2.5mn
5zn
1k
4(Al
2o
3)
90-9 β, the outer numeral of bracket is parts by weight.
[embodiment 8]
By 63.2g cobalt nitrate hexahydrate, 17.4g six water nickel nitrate and the water-soluble wiring solution-forming of 3.21g nitrate trihydrate copper.
Take 66.9g 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.
Add the cesium hydroxide solution 20g that mass concentration is 20%, stir, place 10 minutes, then dry 5 hours at 140 DEG C, then at 550 DEG C of roastings, 4 hours obtained catalyst kernels.
The pulp spraying being the beta-molecular sieve of 100 containing 18 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 140 DEG C of dryings 5 hours, 450 DEG C of roastings, 7 hours obtained catalyst 82 Co
15ni
5cu
1.2cs
5(Al
2o
3)
95-18 β, the outer numeral of bracket is parts by weight.
[embodiment 9]
Be the manganese nitrate of 50%, 8.65g zinc nitrate hexahydrate and the water-soluble wiring solution-forming of 7.23g nitrate trihydrate copper by 95.4g six water ferric nitrate, 24.8g mass concentration.
Take 60.85g 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.
Add the potassium hydroxide solution 0.9g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 70 containing 7 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 110 DEG C of dryings 6.5 hours, 700 DEG C of roastings, 4 hours obtained catalyst 93Fe
20mn
5cu
2.5zn
2.5k
0.2(SiO
2)
80-7(ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 10]
Be the manganese nitrate of 50%, 22.6g cobalt nitrate hexahydrate, 3.43g zinc nitrate hexahydrate, 3.97g magnesium nitrate hexahydrate and the water-soluble wiring solution-forming of 5.73g nitrate trihydrate copper by 23.6g six water ferric nitrate, 29.4g mass concentration.
Take 64g 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.
Add the potassium hydroxide solution 8.1g that mass concentration is 20%, 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.
The pulp spraying being the ZSM-5 molecular sieve of 90 containing 14 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 150 DEG C of dryings 12 hours, 600 DEG C of roastings, 3 hours obtained catalyst 86 Co
5fe
5mn
6cu
2zn
1mg
0.5k
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 14.7g magnesium nitrate hexahydrate of 50% by 41g six water ferric nitrate, 16g mass concentration.
Take 69.5g 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.
Add the potassium hydroxide solution 13.5g that mass concentration is 20%, stir, place 10 minutes, then dry 12 hours at 150 DEG C, then at 800 DEG C of roastings, 7 hours obtained catalyst kernels.
The pulp spraying being the ZSM-5 molecular sieve of 20 containing 13 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 95 DEG C of dryings 7 hours, 500 DEG C of roastings, 10 hours obtained catalyst 87 Fe
8mg
1.7mn
3k
2.3(Al
2o
3)
85-13(ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 12]
By 14.9g six water ferric nitrate and the water-soluble wiring solution-forming of 13.6g nitrate trihydrate copper.
Take 77.8g 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.
Add the potassium hydroxide solution 25.6g that mass concentration is 20%, stir, place 10 minutes, then dry 9 hours at 105 DEG C, then at 450 DEG C of roastings, 3 hours obtained catalyst kernels.
The pulp spraying being the ZSM-5 molecular sieve of 200 containing 10 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 105 DEG C of dryings 9 hours, 800 DEG C of roastings, 6 hours obtained catalyst 90Fe
3cu
4.5k
4.5(SiO
2)
98-10(ZSM-5), the outer numeral of bracket is parts by weight.
[embodiment 13]
Be the manganese nitrate of 50%, 39.7g cobalt nitrate hexahydrate and the water-soluble wiring solution-forming of 12.6g nitrate trihydrate copper by 10.8g mass concentration.
Take 66.3g 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.
Add the rubidium hydroxide solution 4.75g that mass concentration is 20%, stir, place 10 minutes, then dry 6 hours at 130 DEG C, then at 700 DEG C of roastings, 19 hours obtained catalyst kernels.
The pulp spraying being the beta-molecular sieve of 200 containing 17 grams of Si/Al mol ratios is coated onto in obtained catalyst core, 130 DEG C of dryings 6 hours, 650 DEG C of roastings, 8 hours obtained catalyst 83Co
10mn
2.5cu
5rb
1.2(Al
2o
3)
100-17 β, 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.
Add the potassium hydroxide solution 9.51g that mass concentration is 20%, 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
2(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.
Add the potassium hydroxide solution 9.51g that mass concentration is 20%, 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
2(ZSM-5)
100.
Adopt the catalyst prepared of embodiment 1-10 and comparative example 1-2 at reaction temperature 250-350 DEG C, reaction pressure 0.5-2.5MPa, volume space velocity 1000-4000h
-1condition under react, catalyst composition in table 1, actual conditions and reaction result are in table 2.
Table 1
Table 2
| Catalyst | Reaction temperature/DEG C | Reaction pressure/MPa | Volume space velocity/h -1 | CO conversion ratio/% | C 2-C 4Olefine selective/% |
| Embodiment 1 | 280 | 1.0 | 3000 | 87.6 | 70 |
| Embodiment 2 | 275 | 1.5 | 1800 | 84.5 | 68 |
| Embodiment 3 | 330 | 0.8 | 1000 | 86.7 | 63 |
| Embodiment 4 | 330 | 0.8 | 1000 | 87.4 | 56 |
| Embodiment 5 | 330 | 0.8 | 1000 | 87.1 | 69 |
| Embodiment 6 | 330 | 0.8 | 1000 | 86.8 | 69.5 |
| Embodiment 7 | 350 | 0.5 | 4000 | 80.5 | 57 |
| Embodiment 8 | 250 | 2.0 | 2200 | 89.4 | 62 |
| Embodiment 9 | 260 | 1.8 | 1500 | 88.4 | 58 |
| Embodiment 10 | 270 | 2.5 | 3500 | 92.1 | 72 |
| Embodiment 11 | 310 | 1.4 | 1300 | 87.3 | 65 |
| Embodiment 12 | 265 | 0.9 | 2500 | 82.5 | 60 |
| Embodiment 13 | 300 | 0.7 | 2000 | 91.2 | 55 |
| Comparative example 1 | 280 | 1.0 | 3000 | 87.9 | 34 |
| Comparative example 2 | 280 | 1.0 | 3000 | 70.3 | 46 |
Claims (10)
1. a synthesis gas alkene catalyst, catalyst, with weight parts, comprises following component: 1 ~ 20 part of kernel being selected from shell a kind of in ZSM-5 or β zeolite and 80 ~ 99 parts, and wherein kernel comprises with weight parts:
A) 80 ~ 100 parts are selected from SiO
2or Al
2o
3carrier; With carry thereon
B) at least one metal in 3 ~ 20 parts of 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 a kind of oxide or hydroxide in K, Na, Rb or Cs.
2. synthesis gas alkene catalyst according to claim 1, is characterized in that the Si/Al mol ratio of ZSM-5 or the β zeolite of shell is more than or equal to 10.
3. synthesis gas alkene catalyst according to claim 1, is characterized in that the Si/Al mol ratio of ZSM-5 or the β zeolite of shell is more than or equal to 30.
4. synthesis gas alkene catalyst according to claim 1, is characterized in that the parts by weight of shell are 3 ~ 12 parts.
5. synthesis gas alkene catalyst according to claim 1, is characterized in that the parts by weight of kernel are 85 ~ 95 parts.
6. the preparation method of synthesis gas alkene catalyst described in claim 1, comprises the steps:
) 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;
) by step
aequum is selected from SiO by the mixed solution dipping of middle preparation
2or Al
2o
3carrier on, and be dried to outside catalyst granules and there is no unnecessary moisture;
) K, Na, Rb or Cs hydroxide solution will be selected from be added to step
in be impregnated with in the carrier of active component, reaction 1-30 minute, dries 4-12 hour at 80-140 DEG C, then 400 ~ 800 DEG C of roastings 2 ~ 10 hours, obtained catalyst kernel;
) pulp spraying containing corresponding molecular sieve is coated onto step
on obtained catalyst kernel, dry 4 ~ 12 hours at 80 ~ 150 DEG C, 400 ~ 800 DEG C of roastings 2 ~ 10 hours, obtained catalyst.
7. a method for synthesis gas alkene, synthesis gas reaction temperature 250 ~ 350 DEG C, reaction pressure 0.5 ~ 2.5MPa, volume space velocity 1000 ~ 4000h
-1condition under react Formed hydrogen compound with catalyst exposure described in claim 1.
8. the method for synthesis gas alkene according to claim 7, is characterized in that reaction temperature is 280 ~ 300 DEG C.
9. the method for synthesis gas alkene according to claim 7, is characterized in that reaction pressure 1 ~ 2MPa.
10. the method for synthesis gas alkene according to claim 7, is characterized in that volume space velocity is 2000 ~ 3000h
-1.
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| CN105728020A (en) * | 2016-03-03 | 2016-07-06 | 华侨大学 | Preparation method for core-shell type iron carbide catalyst |
| CN106861750A (en) * | 2017-02-16 | 2017-06-20 | 浙江科技学院 | The preparation method of the nucleocapsid catalyst of modified H beta-molecular sieves cladding and product and application |
| CN107774298A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Porous metals/molecular sieve composite catalyst, its preparation method and the purposes in preparing low-carbon olefin |
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| CN108144643B (en) * | 2016-12-05 | 2020-03-10 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas |
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| CN109651031B (en) * | 2017-10-10 | 2021-08-03 | 中国石油化工股份有限公司 | Method for directly producing low-carbon olefin by using synthesis gas |
| CN109651031A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method that synthesis gas directly produces low-carbon alkene |
| CN107824214A (en) * | 2017-11-10 | 2018-03-23 | 中石化炼化工程（集团）股份有限公司 | A kind of method of synthesis gas preparing low-carbon olefins |
| CN107824214B (en) * | 2017-11-10 | 2020-09-01 | 中石化炼化工程（集团）股份有限公司 | Method for preparing low-carbon olefin from synthesis gas |
| CN109939667B (en) * | 2018-01-26 | 2021-01-05 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas |
| CN109939667A (en) * | 2018-01-26 | 2019-06-28 | 中国科学院大连化学物理研究所 | A kind of method that catalyst and synthesis gas directly convert producing light olefins |
| CN112619691A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for directly producing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN112619691B (en) * | 2019-10-09 | 2022-08-12 | 中国石油化工股份有限公司 | Catalyst for directly producing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN112705257A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and forming method and application thereof |
| CN112705257B (en) * | 2019-10-25 | 2023-03-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and forming method and application thereof |
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