CN105080587B - Synthesis gas alkene catalyst and its application method - Google Patents
Synthesis gas alkene catalyst and its application method Download PDFInfo
- Publication number
- CN105080587B CN105080587B CN201410203685.XA CN201410203685A CN105080587B CN 105080587 B CN105080587 B CN 105080587B CN 201410203685 A CN201410203685 A CN 201410203685A CN 105080587 B CN105080587 B CN 105080587B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- parts
- kernel
- silicalite
- synthesis gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of synthesis gas alkene catalyst and its application method, mainly solves the problems, such as low C2 C4 olefine selective differences in F- T synthesis.The catalyst that the present invention uses is in terms of parts by weight, including following components:1 20 parts of shells of SILICALITE 1 and 80 99 parts of kernel, wherein kernel in terms of parts by weight including：A) 80 100 parts are selected from SiO2Or Al2O3Carrier；Be loaded in b thereon) at least one of 3 20 parts of Fe or Co metal or oxide；And c) 1 10 parts selected from least one of Mn, Zn, Mg or Cu metal or oxide；And d) 0.1 5 parts of a kind of oxides or hydroxide in K, Na, Rb or Cs；And e) 0.1 2 parts be selected from least one of Se and Te oxide technical scheme, preferably solve the problem, the commercial Application available for synthesis gas alkene.
Description
Technical field
The present invention relates to a kind of synthesis gas alkene catalyst and its application method.
Technical background
Low-carbon alkene (alkene of carbon atom≤4) using ethene, propylene as representative is the base stock of chemical industry, mesh
Before, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, also alkane, hydrogenated diesel oil, portion
Divide mink cell focus etc..It is more using natural gas or light petroleum fraction as raw material both at home and abroad, using steam cracking work in Ethylene Complex unit
Skill produces low-carbon alkene.Steam cracking is the big power consumption device in petrochemical industry, and is completely dependent on non-renewable oil money
Source.With the increasingly shortage of petroleum resources, it is badly in need of finding alternate resources.So research with substitute gas oil producing olefinic hydrocarbons
Work is then taken seriously, and some famous oil companies and scientific research institutions have all carried out the research and development work of this respect in the world
Make, and achieve achievement attracting people's attention.Currently adjustment using energy source structure to gradually reduce the national economic development pair
Under the background of the dependence of petroleum-based energy, using the natural gas resource of China's rich reserves, pass through (the oxidation of gas making producing synthesis gas
Carbon and hydrogen mixed gas), C2~C4 alkene is then converted to, in the long term, there is very high strategic importance.
The method that synthesis gas changes into alkene includes indirect method and direct method, methanol decomposition preparing low-carbon olefins MTO techniques
With synthesis gas via dimethyl ether preparing low-carbon olefins SDTO techniques, first by synthesis gas synthesizing methanol or dimethyl ether, then by methanol or
Dimethyl ether conversion is into alkene.
Synthesis gas is converted into the Fischer-Tropsch synthesis mistake that low-carbon alkene is actually CO hydrogenation.Nineteen twenty-three section of Germany
Scholar Franz Fisher and Hans Tropsch are found that the reaction of syngas catalytic conversion hydro carbons, therefore, by synthesis gas
The method that reaction prepares hydro carbons is referred to as Fiscber-Tropscb synthesis (Fischer-Tropsch is synthesized, abbreviation F-T synthesis) method, i.e., with CO and H2
Reaction hydro carbons processed, byproduct water and CO2.Nineteen fifty-five South Africa SASOL (South Africa Coal and Gas
Corporation the large-scale fixed bed F-T synthesizers using coal as raw material) have been built up, have then developed recirculating fluidized bed skill
Art, develop fixed fluidized bed and slurry bed technique again recently.Nowadays, SASOL coal year disposal ability has reached 50,000,000,
The annual capacity of oil product and chemicals has reached 7,600,000 tons.The purpose is to by synthesis gas synthetic fuel for past F-T synthesis reaction
With liquefied hydrocarbon, although the use of fluidization, ferrum-based catalyst and the addition of auxiliary agent, improve low-carbon alkene to a certain extent
The yield of hydrocarbon (C2-C4 alkene), but yield of light olefins is not still high, only 20-25%.
The purpose of present carbon-chemical synthesis hydro carbons is to be translated into the low-carbon alkene as basic chemical raw materials, its
Middle ethene and propylene are the materials of current most worthy.Moreover, generated by the direct preparing low-carbon olefins of synthesis gas for single step reaction
Purpose product, its technological process is simpler than indirect method, and economic evaluation is also more worthwhile.Last decade, directly synthesized by synthesis gas
Low-carbon alkene starts to cause concern.
Mainly had by preparing low-carbon olefin catalyst system and catalyzing at present following several.(1) F-T catalyst Dent is improved
Et al. find cobalt-base catalyst can be used for high selectivity synthesizing low-carbon alkene, such as：Co-Cu/Al2O3、 Co-Fe/SiO2、Fe-
Co/C、Co-Ni/MnO2, the system such as Fe-Co alloy/C.The improvement FT catalyst results wherein developed with Rule chemical company are preferable,
In Fe-ZnO-K2The components such as Mn or Ti are added on O catalyst, using high gas circulation, reach CO conversion ratios 80%, low-carbon alkene
Hydrocarbon-selective 70%；(2) Ultra-fine Particle Catalysts Venter etc. has obtained the height of Activated Carbon Supported by carbonyl complex decomposition method
Scattered K-Fe-Mn catalyst, catalyst have a very high activity, C in product2-C4Alkene accounts for 85-90%, and methane detects
Other unique products.Cupta et al. prepares the Fe with catalytic activity using laser pyrolysis processesxSiyCzDeng powder CO conversion ratios
For 40%, C2 =-C4 =Selectivity reaches 87%, only a small amount of methane.Shanxi coalification institute clock is bright et al. using organic salt complex
Edman degradation Edman is successfully developed and develops ultrafine particle Fe/Mn catalyst that is new, having practical background, and CO conversion ratios are more than 95%,
C2 =-C4 =/C2-C4More than 80%.Beijing University of Chemical Technology Zhang Jingchang prepares high degree of dispersion amorphous superfine iron using laser pyrolysis processes
Powder and carbon dust, F-T synthesizing activity new species Fe is successfully made through solid phase reaction3C.Prepare with Fe3C is the Fe-C of main body,
The nanocatalysts such as Fe-C-Mn, Fe-C-Mn-K, CO conversion ratios are up to 90%, and olefine selective is up to more than 80%；(3) amorphous state
Synthetic catalyst Yokoyama et al. uses amorphous state Fe40Ni40P16B4Compound, CO conversion ratios 50%, C2-C5Hydrocarbon-selective
For 65%, and crystalline-state catalyst mainly generates methane；(4) zeolite catalyst, which represents system, the catalysis such as Co-A, Co-Y, Fe-Y
The iron catalyst for the high dispersive that zeolite supports is made in agent, Ballivet-Tketchenko et al., and low-carbon hydrocarbon-selective is at a relatively high,
88-98% is in C2-C4In the range of, other iron catalysts as SILICALITE-1 molecular sieves, mercerising, 13X zeolites support also show
Similar behavior is shown.But these catalyst run into different degrees of difficulty in the programs such as Repeatability, amplification preparation are prepared.
The content of the invention
One of technical problems to be solved by the invention are that C2-C4 olefine selectives are poor in F- T synthesis in conventional art
Problem, there is provided a kind of synthesis gas alkene catalyst, the catalyst are used for F- T synthesis, have C2-C4 olefine selectives high
Advantage, the two of the technical problems to be solved by the invention be to provide it is a kind of with solving the corresponding catalyst system of one of technical problem
Preparation Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of synthesis gas olefin catalytic
Agent, catalyst is in terms of parts by weight including following components:1-20 parts SILICALITE-1 molecules screen shell and the kernel of 80-99 parts,
Wherein kernel in terms of parts by weight including：
A) 80-100 parts are selected from SiO2Or Al2O3Carrier；Be loaded in thereon
B) at least one of 3-20 parts Fe or Co metal or oxide；With
C) 1-10 parts are selected from least one of Mn, Zn, Mg or Cu metal or oxide；With
D) 0.1-5 parts are selected from least one of K, Na, Rb or Cs oxide or hydroxide；With
E) 0.1-2 parts are selected from least one of Se and Te oxide.
In the above-mentioned technical solutions, catalyst kernel preferably comprises 0.5-1.5 parts in Se and Te in terms of parts by weight
At least one oxide；The SILICALITE-1 molecular sieves of shell are preferably prepared using the method for fabricated in situ；The weight of shell
It is preferably 3-12 to measure number；The parts by weight of kernel are preferably 85-95.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Catalyst preparation includes following step
Suddenly：
I), in water, mixing will be made into containing the desired amount of soluble-salt selected from Fe, Co, Mn, Zn, Mg or Cu or alkali soluble
Solution；
II) mixed solution prepared in step I is impregnated and is selected from SiO by the desired amount of2Or Al2O3Carrier on, drying it is standby
With；
III it) will be added to selected from least one of K, Na, Rb or Cs hydroxide solution in step II and be impregnated with activearm
In the carrier divided, dried after reacting 1-30 minutes, fired obtained catalyst kernel；
IV) obtained kernel is added in the solution containing binding agent, binding agent is coated on kernel；
V the crystal seed of SILICALITE-1 molecular sieves) is adsorbed on the kernel for scribble binding agent, then adds Zeolite synthesis
Solution situ synthesizes SILICALITE-1 molecular sieve shells；
VI) finished catalyst will be obtained after the catalyst drying for being assembled with molecular sieve shell, roasting.
In such scheme, binding agent used is organic binder bond；The crystal seed particle diameter of SILICALITE-1 molecular sieves used
Less than 200 nanometers.
Catalyst prepared by the present invention improves the scattered of Components of Catalysts iron by adding various auxiliary agents, promotes going back for iron
Original, and the acidic site that basic component suppresses catalyst is added, improve the activity and selectivity of light olefin of catalyst.Meanwhile with
This catalyst is core, and in one layer of SILICALITE-1 molecular sieve molecular sieve of core outer wrapping, molecular sieve has highly developed hole knot
Structure, reactant carbon monoxide and hydrogen can smoothly reach catalyst core reaction, simultaneously because molecular sieve shape selectivity, limits macromolecular
The generation of product.Moreover, SILICALITE-1 molecular sieves molecular sieve because being free of aluminium, without acidity, is avoided that low-carbon alkene exists
Secondary response occurs when being spread in molecular sieve pore passage, improves the selectivity of low-carbon alkene.
Using the catalyst for preparing of the present invention, at 250-350 DEG C, 0.5-2.5MPa, volume space velocity 1000-4000h-1Bar
Reacted under part, CO conversion ratios>80%, C2-C4Olefin feed weight selectivity>55%, achieve preferable technique effect.
Below by specific embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The water ferric nitrates of 24.9g six, the manganese nitrate that 21.6g mass concentrations are 50% and 5.04g nitrate trihydrate copper are dissolved in water
Wiring solution-forming.
66.3g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
0.15 gram of ammonium selenate is added into the potassium hydroxide solution that 9.5g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 4 hours at 100 DEG C, then 2 hours obtained catalyst kernels are calcined at 600 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 100 DEG C 4 hours, 550 DEG C of roastings, 2 hours obtained catalyst
80Fe6Mn5Cu2K2Se0.1(SiO2)100- 20 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 2】
The water ferric nitrates of 76.2g six, 10.8g zinc nitrate hexahydrates and 10.7g magnesium nitrate hexahydrates are dissolved in water wiring solution-forming.
60.7g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
2.14 grams of ammonium selenates are added into the sodium hydroxide solution that 5.84g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 8 hours at 80 DEG C, then 8 hours obtained catalyst kernels are calcined at 700 DEG C.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 80 DEG C 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe18Mg1.5Zn3.5Na1Se1.4(SiO2)90-
15 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 3】
The water ferric nitrates of 19.9g six, the manganese nitrate that 31g mass concentrations are 50% and 47.5g cobalt nitrate hexahydrates are dissolved in water and matched somebody with somebody
Into solution.
75.1g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
0.15 gram of ammonium tellurate is added into the potassium hydroxide solution that 0.57g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 7.5 hours at 120 DEG C, then 6 hours obtained catalyst kernels are calcined at 650 DEG C.
Binding agent is used as using APTS (8- amino pyrenes -1,3, the ammonium salt of 6- trisulfonic acids three), SILICALITE-1 molecular sieves
Nanosized seeds are adsorbed in catalyst kernel, are added in Zeolite synthesis liquid and are reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 120 DEG C 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst
98Co10Fe4Mn6K0.1Te0.1(Al2O3)95- 2 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 4】
The water ferric nitrates of 19.9g six, the manganese nitrate that 31g mass concentrations are 50% and 47.5g cobalt nitrate hexahydrates are dissolved in water and matched somebody with somebody
Into solution.
75.1g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
0.15 gram of ammonium tellurate is added into the potassium hydroxide solution that 0.57g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 7.5 hours at 120 DEG C, then 6 hours obtained catalyst kernels are calcined at 650 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 120 DEG C 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst
98Co10Fe4Mn6K0.1Te0.1(Al2O3)95- 2 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 5】
The water ferric nitrates of 19.9g six, the manganese nitrate that 31g mass concentrations are 50% and 47.5g cobalt nitrate hexahydrates are dissolved in water and matched somebody with somebody
Into solution.
75.1g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
0.15 gram of ammonium tellurate is added into the potassium hydroxide solution that 0.57g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 7.5 hours at 120 DEG C, then 6 hours obtained catalyst kernels are calcined at 650 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 120 DEG C 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst
98Co10Fe4Mn6K0.1Te0.1(Al2O3)95- 2 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 6】
The water ferric nitrates of 19.9g six, the manganese nitrate that 31g mass concentrations are 50% and 47.5g cobalt nitrate hexahydrates are dissolved in water and matched somebody with somebody
Into solution.
75.1g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
0.15 gram of ammonium tellurate is added into the potassium hydroxide solution that 0.57g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 7.5 hours at 120 DEG C, then 6 hours obtained catalyst kernels are calcined at 650 DEG C.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 120 DEG C 7.5 hours, 400 DEG C of roastings, 7.5 hours obtained catalyst 98Co10Fe4Mn6K0.1Te0.1
(Al2O3)95- 2 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 7】
By the water ferric nitrates of 24.7g six, the water nickel nitrates of 9.77g six, the manganese nitrate and 3.59g that 25.7g mass concentrations are 50%
Zinc nitrate hexahydrate is dissolved in water wiring solution-forming.
71g alumina supports are weighed, above-mentioned solution is impregnated on carrier, are dried at 60 DEG C outside catalyst granules without more
Remaining moisture.
1.79 grams of ammonium selenates and 0.42 gram of ammonium tellurate are added into the potassium hydroxide solution that 22.6g mass concentrations are 20%, so
Add in catalyst and stir afterwards, place 10 minutes, then dried 10 hours at 90 DEG C, then be made within 9 hours in 400 DEG C of roastings
Catalyst kernel.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 90 DEG C 10 hours, 750 DEG C of roastings, 9 hours obtained catalyst 91Fe5Ni2.5Mn5Zn1K4Se1.0Te0.6
(Al2O3)90- 9 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 8】
56.4g cobalt nitrate hexahydrates, the water nickel nitrates of 15.5g six and 2.86g nitrate trihydrate copper are dissolved in water wiring solution-forming.
59.6g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
1.42g ammonium tellurates are added into the cesium hydroxide solution that 17.7g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 5 hours at 140 DEG C, then 4 hours obtained catalyst kernels are calcined at 550 DEG C.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 140 DEG C 5 hours, 450 DEG C of roastings, 7 hours obtained catalyst 82Co15Ni5Cu1.2Cs5Se1.0(Al2O3)95-
18 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 9】
By the water ferric nitrates of 94.8g six, manganese nitrate, 8.6g zinc nitrate hexahydrates and the 7.19g that 24.6g mass concentrations are 50%
Nitrate trihydrate copper is dissolved in water wiring solution-forming.
60.5g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
0.85 gram of ammonium selenate is added into the potassium hydroxide solution that 1.1g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 6.5 hours at 110 DEG C, then 5 hours obtained catalyst kernels are calcined at 750 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 110 DEG C 6.5 hours, 700 DEG C of roastings, 4 hours obtained catalyst
93Fe20Mn5Cu2.5Zn2.5K0.2Se0.5(SiO2)80- 7 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 10】
The manganese nitrate, 22.2g cobalt nitrate hexahydrates, 3.373g six for being 50% by the water ferric nitrates of 23.2g six, 29g mass concentrations
Water zinc nitrate, 3.91g magnesium nitrate hexahydrates and 5.63g nitrate trihydrate copper are dissolved in water wiring solution-forming.
63g silica supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
1.98 grams of ammonium tellurates are added into the potassium hydroxide solution that 8g mass concentrations are 20%, then adds in catalyst and stirs
Uniformly, place 10 minutes, then dried 12 hours at 150 DEG C, then 5.5 hours obtained catalyst kernels are calcined at 500 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 150 DEG C 12 hours, 600 DEG C of roastings, 3 hours obtained catalyst
86Co5Fe5Mn6Cu2Zn1Mg0.5K1.5Te1.5(SiO2)85- 14 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight
Number.
【Embodiment 11】
The water ferric nitrates of 40.2g six, the manganese nitrate that 15.7g mass concentrations are 50% and 14.4g magnesium nitrate hexahydrates are dissolved in water
Wiring solution-forming.
68.1g alumina supports are weighed, above-mentioned solution is impregnated on carrier, being dried at 60 DEG C outside catalyst granules does not have
Unnecessary moisture.
2.57 grams of ammonium selenates are added into the potassium hydroxide solution that 13.2g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 12 hours at 150 DEG C, then 7 hours obtained catalyst kernels are calcined at 800 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 95 DEG C 7 hours, 500 DEG C of roastings, 10 hours obtained catalyst
87Fe8Mg1.7Mn3K2.3Se1.8(Al2O3)85- 13 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 12】
The water ferric nitrates of 14.6g six and 13.3g nitrate trihydrate copper are dissolved in water wiring solution-forming.
76.1g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
2.0 grams of ammonium tellurates are added into the potassium hydroxide solution that 25.1g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 9 hours at 105 DEG C, then 3 hours obtained catalyst kernels are calcined at 450 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 105 DEG C 9 hours, 800 DEG C of roastings, 6 hours obtained catalyst
90Fe3Cu4.5K4.5Te0.4(SiO2)98- 10 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 13】
Manganese nitrate, 39.5g cobalt nitrate hexahydrates and 12.5g nitrate trihydrate copper that 10.7g mass concentrations are 50% are dissolved in water
Wiring solution-forming.
66g alumina supports are weighed, above-mentioned solution is impregnated on carrier, are dried at 60 DEG C outside catalyst granules without more
Remaining moisture.
0.59 gram of ammonium selenate is added into the rubidium hydroxide solution that 4.75g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 6 hours at 130 DEG C, then 19 hours obtained catalyst kernels are calcined at 700 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 130 DEG C 6 hours, 650 DEG C of roastings, 8 hours obtained catalyst
83Co10Mn2.5Cu5Rb1.2Se2.0(Al2O3)100- 17 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 14】
The water ferric nitrates of 76.2g six, 10.8g zinc nitrate hexahydrates and 10.7g magnesium nitrate hexahydrates are dissolved in water wiring solution-forming.
60.8g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
0.84 gram of ammonium tellurate and 1.07 grams of ammonium selenates are added into the sodium hydroxide solution that 5.88g mass concentrations are 20%, so
Add in catalyst and stir afterwards, place 10 minutes, then dried 8 hours at 80 DEG C, then be made within 8 hours and urge in 700 DEG C of roastings
Agent kernel.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 80 DEG C 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe18Mg1.5Zn3.5Na1Se0.7Te0.7
(SiO2)90- 15 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Embodiment 15】
The water ferric nitrates of 76.3g six, 10.8g zinc nitrate hexahydrates and 10.7g magnesium nitrate hexahydrates are dissolved in water wiring solution-forming.
60.9g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
1.69 grams of ammonium tellurates are added into the sodium hydroxide solution that 5.88g mass concentrations are 20%, then added in catalyst
Stir, place 10 minutes, then dried 8 hours at 80 DEG C, then 8 hours obtained catalyst kernels are calcined at 700 DEG C.
Binding agent is used as using PSS (sulfonated polystyrene), SILICALITE-1 molecular sieve nanosized seeds are adsorbed in and urged
On agent kernel, it is added in Zeolite synthesis liquid and reacts, one layer of SILICALITE-1 molecular sieve is generated outside catalyst kernel
Molecule screen shell, dried at 80 DEG C 8 hours, 600 DEG C of roastings, 2 hours obtained catalyst 85Fe18Mg1.5Zn3.5Na1Te1.4(SiO2)90-
15 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
【Comparative example 1】
The water ferric nitrates of 24.9g six, the manganese nitrate that 21.6g mass concentrations are 50% and 5.04g nitrate trihydrate copper are dissolved in water
Wiring solution-forming.
66.3g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
0.15 gram of ammonium selenate is added into the potassium hydroxide solution that 9.5g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 4 hours at 100 DEG C, then 2 hours obtained catalyst are calcined at 600 DEG C
Fe6Mn5Cu2K2Se0.1(SiO2)100。
【Comparative example 2】
The water ferric nitrates of 24.9g six, the manganese nitrate that 21.6g mass concentrations are 50% and 5.04g nitrate trihydrate copper are dissolved in water
Wiring solution-forming.
66.3g SILICALITE-1 molecular sieve carriers are weighed, above-mentioned solution is impregnated on carrier, is dried to and urges at 60 DEG C
Without unnecessary moisture outside catalyst particles.
0.15 gram of ammonium selenate is added into the potassium hydroxide solution that 9.5g mass concentrations are 20%, then adds in catalyst and stirs
Mix uniformly, place 10 minutes, then dried 4 hours at 100 DEG C, then 2 hours obtained catalyst are calcined at 600 DEG C
Fe6Mn5Cu2K2Se0.1(SILICALITE-1 molecular sieves)100。
【Comparative example 3】
The water ferric nitrates of 24.9g six, the manganese nitrate that 21.6g mass concentrations are 50% and 5.04g nitrate trihydrate copper are dissolved in water
Wiring solution-forming.
66.3g silica supports are weighed, above-mentioned solution is impregnated on carrier, is dried to outside catalyst granules and does not have at 60 DEG C
There is unnecessary moisture.
The potassium hydroxide solution that 9.5g mass concentrations are 20% is added in catalyst and stirred, placement 10 minutes, so
Dried 4 hours at 100 DEG C afterwards, then 2 hours obtained catalyst kernels are calcined at 600 DEG C.
Binding agent is used as using PDDA (diallyl dimethyl ammoniumchloride), SILICALITE-1 molecular sieves is nanocrystalline
Kind is adsorbed in catalyst kernel, is added in Zeolite synthesis liquid and is reacted, and one layer is generated outside catalyst kernel
SILICALITE-1 molecular sieve molecule screen shells, dried at 100 DEG C 4 hours, 550 DEG C of roastings, 2 hours obtained catalyst
80Fe6Mn5Cu2K2Se0.1(SiO2)100- 20 (SILICALITE-1 molecular sieves), the outer numeral of bracket is parts by weight.
The catalyst prepared using embodiment 1-13 and comparative example 1-3 is in 250-350 DEG C of reaction temperature, reaction pressure 0.5-
2.5MPa, H2/ CO volume ratios are 0.5-3, volume space velocity 1000-4000h-1Under conditions of react, actual conditions and the results are shown in Table 2
(120 hours reaction time).
Table 1
Table 2
Claims (8)
1. a kind of synthesis gas alkene catalyst, catalyst is in terms of parts by weight including following components:
1-20 parts SILICALITE-1 molecules screen shell and the kernel of 80-99 parts, wherein kernel in terms of parts by weight including：
A) 80-100 parts are selected from SiO2Or Al2O3Carrier；Be loaded in thereon
B) at least one of 3-20 parts Fe or Co metal or oxide；With
C) 1-10 parts are selected from least one of Mn, Zn, Mg or Cu metal or oxide；With
D) 0.1-5 parts are selected from least one of K, Na, Rb or Cs oxide or hydroxide；With
E) 0.1-2 parts are selected from least one of Se and Te oxide.
2. synthesis gas alkene catalyst according to claim 1, it is characterised in that catalyst kernel is in terms of parts by weight
At least one of Se and Te oxide are selected from containing 0.5-1.5 parts.
3. synthesis gas alkene catalyst according to claim 1, it is characterised in that the parts by weight of shell are 3-12.
4. synthesis gas alkene catalyst according to claim 1, it is characterised in that the parts by weight of kernel are 85-95.
5. the preparation method of synthesis gas alkene catalyst, comprises the following steps described in claim 1：
I), in water, mixed solution will be made into containing the desired amount of soluble-salt selected from Fe, Co, Mn, Zn, Mg or Cu or alkali soluble；
II) mixed solution prepared in step I is impregnated and is selected from SiO by the desired amount of2Or Al2O3Carrier on, be dried for standby；
III it) will be added to selected from least one of K, Na, Rb or Cs hydroxide solution in step II and be impregnated with active component
In carrier, dried after reacting 1-30 minutes, fired obtained catalyst kernel；
IV) obtained kernel is added in the solution containing binding agent, binding agent is coated on kernel；
V the crystal seed of SILICALITE-1 molecular sieves) is adsorbed on the kernel for scribble binding agent, then adds Zeolite synthesis solution
Situ synthesizes SILICALITE-1 molecular sieve shells；
VI) finished catalyst will be obtained after the catalyst drying for being assembled with molecular sieve shell, roasting.
6. synthesis gas alkene catalyst preparation method according to claim 5, it is characterised in that binding agent used is to have
Machine binding agent.
7. synthesis gas alkene catalyst preparation method according to claim 5, it is characterised in that SILICALITE- used
The crystal seed particle diameter of 1 molecular sieve is less than 200 nanometers.
8. a kind of method of synthesis gas alkene, synthesis gas is in 250-350 DEG C of reaction temperature, reaction pressure 0.5-2.5MPa, H2/
CO volume ratios are 0.5-3, volume space velocity 1000-4000h-1Under conditions of contacted with any one of the claim 1-4 catalyst
Reaction generation hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410203685.XA CN105080587B (en) | 2014-05-14 | 2014-05-14 | Synthesis gas alkene catalyst and its application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410203685.XA CN105080587B (en) | 2014-05-14 | 2014-05-14 | Synthesis gas alkene catalyst and its application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080587A CN105080587A (en) | 2015-11-25 |
| CN105080587B true CN105080587B (en) | 2017-12-15 |
Family
ID=54562452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410203685.XA Active CN105080587B (en) | 2014-05-14 | 2014-05-14 | Synthesis gas alkene catalyst and its application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080587B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261199B (en) * | 2018-09-27 | 2021-03-19 | 太原理工大学 | Catalyst for directly preparing low-carbon olefin from high-stability synthesis gas, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340503A (en) * | 1980-08-15 | 1982-07-20 | The United States Of America As Represented By The United States Department Of Energy | Catalyst for converting synthesis gas to light olefins |
| CN101767040A (en) * | 2009-12-25 | 2010-07-07 | 中国科学院过程工程研究所 | Capsule type catalyst for preparing low-carbon olefin by catalyzing synthesis gas and preparation method thereof |
| CN102292154A (en) * | 2008-12-08 | 2011-12-21 | Sasol技术股份有限公司 | Olefin selective FT catalyst composition and preparation thereof |
| CN103521253A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparation of low-carbon olefine from synthesis gas through one-step method and preparation method thereof |
-
2014
- 2014-05-14 CN CN201410203685.XA patent/CN105080587B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340503A (en) * | 1980-08-15 | 1982-07-20 | The United States Of America As Represented By The United States Department Of Energy | Catalyst for converting synthesis gas to light olefins |
| CN102292154A (en) * | 2008-12-08 | 2011-12-21 | Sasol技术股份有限公司 | Olefin selective FT catalyst composition and preparation thereof |
| CN101767040A (en) * | 2009-12-25 | 2010-07-07 | 中国科学院过程工程研究所 | Capsule type catalyst for preparing low-carbon olefin by catalyzing synthesis gas and preparation method thereof |
| CN103521253A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparation of low-carbon olefine from synthesis gas through one-step method and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080587A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549447B (en) | Synthesis gas alkene catalyst and preparation method thereof | |
| CN105080597B (en) | Synthesis gas alkene catalyst and preparation method thereof | |
| CN104549343B (en) | Preparation of low carbon olefines by synthetic gas catalyst, preparation method and its usage | |
| CN103521240B (en) | Catalyst for preparing olefin employing synthesis gas and preparation method thereof | |
| CN104226327B (en) | For synthesis gas alkene catalyst and preparation method thereof | |
| CN104549359B (en) | Production light olefins catalyst, the preparation method and its application method of catalyst | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN104107698B (en) | Synthesis gas is prepared the Catalysts and its preparation method of alkene | |
| CN111036278A (en) | Method for preparing low-carbon olefin from synthesis gas | |
| CN103664436A (en) | Method for directly transforming synthesis gas into low-carbon olefin | |
| CN108014816A (en) | A kind of preparation method and application of CO hydrogenation synthesis mixing primary alconol coproduction alkene catalyst | |
| CN105080587B (en) | Synthesis gas alkene catalyst and its application method | |
| CN109647426A (en) | The ferrum-based catalyst of the direct producing light olefins of synthesis gas | |
| CN106807421B (en) | A kind of catalyst and its preparation method and application for synthesis gas mixed alcohol | |
| CN104549358B (en) | The catalyst of synthesizing low-carbon alkene, preparation method and its using method | |
| CN109092291B (en) | Catalyst for preparing low-carbon olefin from synthesis gas | |
| CN109647492B (en) | Catalyst for directly producing low-carbon olefin by synthesis gas | |
| CN102039133A (en) | Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof | |
| CN104549315B (en) | Preparation of low carbon olefines by synthetic gas catalyst, preparation method and its application method | |
| CN110639495B (en) | Catalyst for synthesizing low-carbon olefin by synthesis gas and application of catalyst in synthesizing low-carbon olefin | |
| CN109092293B (en) | Catalyst for directly preparing low-carbon olefin from synthesis gas | |
| CN109092292B (en) | Catalyst for preparing low-carbon olefin by CO hydrogenation | |
| CN109097091B (en) | Reaction method for directly preparing low-carbon olefin from synthesis gas | |
| CN109096024B (en) | Reaction method for preparing low-carbon olefin by CO hydrogenation | |
| CN109092290B (en) | CO and H2Reaction method for directly preparing low-carbon olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |