CN104907080B - A kind of ferrum-based catalyst and its preparation method and application - Google Patents
A kind of ferrum-based catalyst and its preparation method and application Download PDFInfo
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- CN104907080B CN104907080B CN201510253235.6A CN201510253235A CN104907080B CN 104907080 B CN104907080 B CN 104907080B CN 201510253235 A CN201510253235 A CN 201510253235A CN 104907080 B CN104907080 B CN 104907080B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 150000002739 metals Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003245 coal Substances 0.000 claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 10
- 239000011029 spinel Substances 0.000 claims abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 72
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229940047670 sodium acrylate Drugs 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 22
- 238000001816 cooling Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 description 3
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of ferrum-based catalysts and its preparation method and application.The ferrum-based catalyst is the mono-dispersion microballoon of metal-doped spinel structure ferriferrous oxide nano primary grains cluster, and wherein the molar ratio of doping metals total atom and iron atom is (1-50): (99-50)；It can be prepared using hot solvent method, obtained ferrum-based catalyst can be applied to coal based synthetic gas and prepare low-carbon alkene.
Description
Technical field
It is applied to F- T synthesis the present invention relates to one kind and prepares low-carbon alkene, is applied to coal base more particularly, to one kind and synthesizes
Gas prepares ferrum-based catalyst of low-carbon alkene and preparation method thereof.
Background technique
Low-carbon alkene (ethylene, propylene) is important Organic Chemicals.By the indirect reformer of coal, natural gas and biomass
Route production of chemicals is one of the optimal path for realizing clear energy sources.The process first converts natural gas, coal and biomass
For synthesis gas (CO and H2), then chemical products with high added-value is produced by raw material of synthesis gas.Carbon monoxide (CO) catalytic hydrogenation
It is one of more complicated reaction system, under the conditions of differential responses, can produce from methane to paraffin, alkene and various oxidations
Object.Synthesis gas directly prepare low-carbon alkene (F- T synthesis prepares low-carbon alkene FTO) product composition it is sufficiently complex, by-product is such as
The generation of CH4, CO2 are inevitable, and the generation of a large amount of C5+ also seriously affects total yield of light olefins.Furthermore Primary product alkene
Secondary response such as plus hydrogen, disproportionation, polymerization reaction also limit the raising of olefine selective.The core solved is needed to ask at present
Topic is while improving olefine selective, and the effective product that controls is distributed.
Summary of the invention
The present invention is intended to provide a kind of catalyst that coal based synthetic gas can be improved and prepare the low olefine selective of low-carbon alkene
And preparation method thereof.
In the first aspect of the present invention, a kind of iron-based catalysis that low-carbon alkene is prepared applied to coal based synthetic gas is provided
Agent, the ferrum-based catalyst are the mono-dispersion microballoon of metal-doped spinel structure ferriferrous oxide nano primary grains cluster,
Wherein the molar ratio of doping metals total atom and iron atom is (1-50): (99-50).
In another preferred example, there is the lattice position of ferrous ion to be doped metallic atom in the spinel structure to account for
According to.
In another preferred example, the partial size of the nanometer primary grains is adjustable within the scope of 5-20nm, and the monodisperse is micro-
The partial size of ball is adjustable within the scope of 100-800nm.
In another preferred example, the molar ratio of doping metals total atom and iron atom is (5-33.3): (95-66.7).
In another preferred example, the doping metals atom is one or both of Mn, Mg, Cu, Zn；More preferable manganese
Atom and/or magnesium atom.
In the second aspect of the present invention, a kind of preparation side of ferrum-based catalyst provided present invention as described above is provided
Method, the method includes the steps:
Iron chloride, doped metal salt presoma are dissolved into alcoholic solvent, the organic modifier containing carboxyl, mixing is added
It is placed 8-72 hours in 200 DEG C after uniformly, the ferrum-based catalyst provided present invention as described above.
In another preferred example, the doped metal salt presoma is selected from the hydrochloride or nitrate of doping metals；Institute
It states alcoholic solvent and is selected from one or both of ethylene glycol, diethylene glycol, glycerine, butanediol；Described contains the organic of carboxyl
Dressing agent is selected from one or both of sodium acetate, sodium acrylate, sodium citrate.
In another preferred example, concentration of total metal salt in alcoholic solvent is 0.05-0.50M, more preferable 0.10-0.25M；
In another preferred example, the molar ratio of organic modifier and total metallic atom is 2-8, more preferable 4-6.
In the third aspect of the present invention, provides the ferrum-based catalyst that one kind provides present invention as described above and closed in coal base
The application in low-carbon alkene is prepared at gas.
In the fourth aspect of the present invention, a kind of method that coal based synthetic gas prepares low-carbon alkene is provided, in reaction temperature
250-350 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1000-16000h of degree-1Under conditions of, synthesis gas and as described above
Ferrum-based catalyst haptoreaction provided by the invention generate hydrocarbon.
Accordingly, the present invention provides a kind of catalysis that coal based synthetic gas can be improved and prepare the low olefine selective of low-carbon alkene
Agent and preparation method thereof.
Detailed description of the invention
Fig. 1 shows the XRD spectrum of Mn doped iron base catalyst in embodiment 8 provided by the invention, from gold known to XRD diagram
The ferrum-based catalyst for belonging to doping is in spinel structure, and calculating average grain diameter is about 12.2nm.
Fig. 2 shows the SEM of Mn doped iron base catalyst in embodiment 8 provided by the invention, it is found that should from SEM image
Ferrum-based catalyst is in microballoon by the nano particle cluster of spinel structure.
Specific embodiment
Inventor after extensive and in-depth study, has found a kind of ferrum-based catalyst in mono-dispersion microballoon shape, there is sharp crystalline substance
The nanometer primary grains cluster of stone structure forms.Nanometer primary grains are the ferroso-ferric oxide that doping metals enter lattice framework.
By introducing doping metals, the density of iron atom in the dispersion degree and unit cell that atomic scale improves iron atom is improved
Cloud density around iron atom, it is suppressed that carbochain increases, to improve the selectivity of low-carbon alkene.On this basis,
Complete the present invention.
Ferrum-based catalyst
As used herein, " ferrum-based catalyst of low-carbon alkene is prepared applied to coal based synthetic gas ", " ferrum-based catalyst " and
" catalyst provided by the invention " may be used interchangeably, and all refer to that a kind of doping metals atom occupies part two in spinel structure
More metal ferrum-based catalysts that the lattice position of valence iron is formed, the doping metals atom are one of Mn, Mg, Cu, Zn
Or two kinds (preferably Mn atom and/or Mg atom), the molar ratio of doping metals total atom and iron atom is (1-50): (99-50),
(preferably (5-33.3): (95-66.7)).
Ferrum-based catalyst provided by the invention is in mono-dispersion microballoon shape, have a nanometer primary grains cluster of spinel structure and
At.Nanometer primary grains are the ferroso-ferric oxide that doping metals enter lattice framework, and the partial size of the nanometer primary grains exists
Adjustable within the scope of 5-20nm, the partial size of the mono-dispersion microballoon is adjustable within the scope of 100-800nm.
Ferrum-based catalyst provided by the invention improves the dispersion degree of iron atom in atomic scale by introducing doping metals
With the density of iron atom in unit cell, the cloud density around iron atom is improved, it is suppressed that carbochain increases, and improves low
The selectivity of carbon olefin.Preferably, under doping metals of the present invention and dosage, the ionic radius of doping metals Mn with it is ferrous
Ionic radius is suitable, is easily accessible the position that lattice framework replaces part ferrous ion, and keep ferroso-ferric oxide spinelle
Structure.
The preparation method of ferrum-based catalyst
The preparation method of ferrum-based catalyst provided by the invention is included the following steps: using hot solvent method
Iron chloride and doped metal salt presoma are mixed with higher boiling organic alcohol solvent, are dissolved by the first step；
Second step is added the organic modifier containing carboxyl and is uniformly mixed；
Third step places 8-72 hours at 200 DEG C, obtains ferrum-based catalyst provided by the invention.
In the above-mentioned first step, the doped metal salt presoma includes the hydrochloride or nitrate of doping metals.
In the above-mentioned first step, the higher boiling organic alcohol solvent is by ethylene glycol, diethylene glycol, glycerine, butanediol
One or two kinds of compositions；Total concentration of the metal salt in higher boiling Organic Alcohol is 0.05-0.50M, preferably 0.10-0.25M.
In one embodiment of the invention, it is mixed and is dissolved by stirring in the above-mentioned first step, such as but not
Be limited to, the above-mentioned first step be will iron chloride and doped metal salt presoma be added stirring in higher boiling organic alcohol solvent make it is completely molten
Solution.
In above-mentioned second step, the organic modifier containing carboxyl is sodium acetate, in sodium acrylate, sodium citrate
One or two, the molar ratio of organic modifier and total metallic atom is 2-8, preferably 4-6.
In one embodiment of the invention, above-mentioned second step is the solution being completely dissolved in the above-mentioned first step
The organic modifier containing carboxyl is added afterwards, continuing stirring makes to be uniformly mixed.
In one embodiment of the invention, above-mentioned third step is to be uniformly mixed to be placed on baking oven 8- in above-mentioned second step
72 hours.
In the preferred embodiment of the present invention, it after above-mentioned third step is placed 8-72 hours at 200 DEG C, carries out certainly
It is so cooling, and with after ethyl alcohol and water washing, ferrum-based catalyst provided by the invention is obtained in 60 DEG C of vacuum drying.
The present invention uses hot solvent method, and molysite, doped metal salt presoma are dissolved into higher boiling organic alcohol solvent,
The case where organic carboxylate coexists forms the mono-dispersion microballoon that the nanocrystal of spinel structure assembles.Higher boiling Organic Alcohol
Not only play the role of solvent, but also there is week reduction, in the mild alkaline conditions that organic carboxylate is formed, slow oxygen occurs with molysite
Change reduction reaction and forms iron-based nano-oxide crystal grain.The week reduction of Organic Alcohol advantageously forms uniform crystal grain, and excessive
Organic carboxylate make crystal grain with partial negative charge, electrostatic repulsion prevents crystal grain fast growth, so that effectively control is brilliant
Grain is uniformly distributed in smaller range.
The application of ferrum-based catalyst
Ferrum-based catalyst provided by the invention can be applied to coal based synthetic gas and prepare low-carbon alkene.Synthesis gas is in reaction temperature
250-350 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1000-16000h-1Under conditions of iron-based urged with provided by the invention
Agent haptoreaction generates hydrocarbon.
The feature that the features described above or embodiment that the present invention mentions are mentioned can be in any combination.Disclosed in this case specification
All features can be used in combination with any composition form, each feature disclosed in specification, any can provide it is identical,
The alternative characteristics of impartial or similar purpose replace.Therefore except there is special instruction, revealed feature is only impartial or similar spy
The general example of sign.
Main advantages of the present invention are:
1, ferrum-based catalyst primary grains and second level microspherulite diameter provided by the invention are evenly distributed, and size is controllable.
2, from the mechanism of preparing low-carbon olefin, the mistake for preparing ferrum-based catalyst provided by the invention of design
Journey is simple, and the period is short, and cost is very cheap, evaluates catalyst activity under conditions of close to industry amplification, shows very high
Low-carbon selectivity and high carbon utilisation rate.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number is pressed
Poidometer.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to
The weight of solute in 100 milliliters of solution.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Embodiment 1
By 2.5333g FeCl3·6H2O and 0.9273gMnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic force stirs
It mixes and makes it completely dissolved, 9.6g NaAc is added later, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steels
Crystallizing kettle is put into baking oven, and after 200 DEG C of placement 72h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C later
It is dried in vacuo 6h, obtains ferrum-based catalyst, primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 2
By 2.5333g FeCl3·6H2O and 0.9273gMnCl2·4H2The mixed of 134mL ethylene glycol and diethylene glycol is added in O
(volume ratio of ethylene glycol and diethylene glycol is 1:3) is closed in solution, and magnetic agitation makes it completely dissolved, and 9.6g is added later
NaAc, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steel crystallizing kettles, is put into baking oven, and place in 200 DEG C
After 8h, natural cooling is taken out.And for several times with ethyl alcohol and water washing, 60 DEG C of vacuum drying 6h later, obtain ferrum-based catalyst, at the beginning of
Grade size of microcrystal and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 3
By 3.7865gFe (NO3)3·9H2O and 0.9273gMnCl2·4H2O is added in 134mL ethylene glycol, and magnetic agitation makes
It is completely dissolved, and 9.6g NaAc is added later, and continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steel crystallization
Kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C of vacuum later
Dry 6h, obtains ferrum-based catalyst, primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 4
By 3.7865gFe (NO3)3·9H2O and 0.9273gMnCl2·4H2O is added in 134mL ethylene glycol, and magnetic agitation makes
It is completely dissolved, and 4.8g NaAc and 5.5g acrylic acid is added later and receives, and continuing stirring is uniformly mixed it, is then transferred to 2
100mL stainless steel crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And with ethyl alcohol and water washing number
Secondary, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst later, and primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 5
By 3.7865gFe (NO3)3·9H2O and 0.9273gMnCl2·4H2O is added in 134mL ethylene glycol, and magnetic agitation makes
It is completely dissolved, and 4.8g NaAc and 6.5g sodium citrate is added later, and continuing stirring is uniformly mixed it, is then transferred to 2
100mL stainless steel crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And with ethyl alcohol and water washing number
Secondary, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst later, and primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 6
By 7.5g FeCl3·6H2O is added in 134mL ethylene glycol solution, and magnetic agitation makes it completely dissolved, and is added later
9.6g NaAc, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steel crystallizing kettles, is put into baking oven, and in 200
DEG C place 8h after, take out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C of vacuum drying 6h later, obtain iron-based catalysis
Agent, primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
Embodiment 7
By 3.7626g FeCl3·6H2O and 0.0284gMnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic force stirs
It mixes and makes it completely dissolved, 9.6g NaAc is added later, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steels
Crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C later
It is dried in vacuo 6h, manganese is obtained and accounts for the catalyst that the mole percent of total metal is 1%, be labeled as Mn0.03Fe2.97O4, primary brilliant
Grain partial size and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1, certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 8
By 3.6100g FeCl3·6H2O and 0.1394gMnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic force stirs
It mixes and makes it completely dissolved, 9.6g NaAc is added later, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steels
Crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C later
It is dried in vacuo 6h, manganese is obtained and accounts for the catalyst that the mole percent of total metal is 5%, be labeled as MnFe2O4, primary grains grain
Diameter and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 9
By 2.5333g FeCl3·6H2O and 0.9273gMnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic force stirs
It mixes and makes it completely dissolved, 9.6g NaAc is added later, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steels
Crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C later
It is dried in vacuo 6h, manganese is obtained and accounts for the catalyst that the mole percent of total metal is 33.3%%, be labeled as MnFe2O4, primary brilliant
Grain partial size and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 10
By 0.7601g FeCl3·6H2O and 2.2257g MnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic force stirs
It mixes and makes it completely dissolved, 9.6g NaAc is added later, continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steels
Crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C later
It is dried in vacuo 6h, manganese is obtained and accounts for the catalyst that the mole percent of total metal is 80%, be labeled as Mn2.4Fe0.6O4, primary brilliant
Grain partial size and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO gaseous mixture, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 11
By 2.5333g FeCl3·6H2The MgCl of O and 0.9527g2·6H2O is added in 134mL ethylene glycol solution, magnetic force
Stirring makes it completely dissolved, and 9.6g NaAc is added later, and continuing stirring is uniformly mixed it, and it is stainless to be then transferred to 2 100mL
Steel crystallizing kettle is put into baking oven, and after 200 DEG C of placement 8h, takes out natural cooling.And for several times with ethyl alcohol and water washing, later 60
DEG C vacuum drying 6h, obtain magnesium account for total metal mole percent be 33.3%% catalyst, be labeled as MgFe2O4, primary
Size of microcrystal and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 12
By 3.7626g FeCl3·6H2O、0.4637gMnCl2·4H2The MgCl of O and 0.4763g2·6H2O is added
In 134mL ethylene glycol solution, magnetic agitation is made it completely dissolved, and 9.6g NaAc is added later, and continuing stirring keeps its mixing equal
It is even, 2 100mL stainless steel crystallizing kettles are then transferred to, are put into baking oven, and after 200 DEG C of placement 8h, take out natural cooling.It is used in combination
Ethyl alcohol and water washing for several times, 60 DEG C of vacuum drying 6h later, obtain magnesium and manganese to account for the mole percent of total metal be 33.3%%
Catalyst, be labeled as Mg0.5Mn0.5Fe2O4, primary grains partial size and mono-dispersion microballoon partial size are listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Embodiment 13
By 3.7626g FeCl3·6H2O、0.4637gMnCl2·4H2The MgCl of O and 0.4763g2·6H2134mL is added in O
In ethylene glycol solution, magnetic agitation is made it completely dissolved, and 9.6g NaAc is added later, and continuing stirring is uniformly mixed it, then
2 100mL stainless steel crystallizing kettles are transferred to, are put into baking oven, and after 200 DEG C of placement 8h, take out natural cooling.And with second alcohol and water
For several times, 60 DEG C of vacuum drying 6h, then weigh a certain amount of desciccate later for washing, using wet impregnation method preparation 1%
Then KCl solution is dried in vacuum overnight with 60 DEG C, the catalyst of K modification is prepared, obtains magnesium and manganese accounts for mole of total metal
Percentage is the catalyst of 33.3%%, K atom modification, is labeled as K/Mg0.5Mn0.5Fe2O4, primary grains partial size and single point
Scattered microspherulite diameter is listed in table 1.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
In order to highlight the advantage of multicomponent catalyst of the present invention, which is prepared for ferriferous oxide respectively and Mn oxide is made
To compare.
Comparative example 1
By 3.8g FeCl3·6H2O and 134mL ethylene glycol is added in 250mL polypropylene vial, and magnetic agitation keeps it completely molten
9.6g NaAc is added in solution later, and continuing stirring is uniformly mixed it, is then transferred to 2 100mL stainless steel crystallizing kettles, is put into baking
Case, and after 200 DEG C of placement 8h, take out natural cooling.And for several times with ethyl alcohol and water washing, 60 DEG C of vacuum drying 6h later, obtain
To pure iron catalyst.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Comparative example 2
By 2.7826gMnCl2·4H2O is added in 134mL ethylene glycol solution, and magnetic agitation makes it completely dissolved, Zhi Houjia
Enter 9.6g NaAc, continuing stirring is uniformly mixed it, and 2 100mL stainless steel crystallizing kettles are then transferred to, are put into baking oven, and in
After 200 DEG C of placement 8h, natural cooling is taken out.Using centrifuge separation mode, and for several times with ethyl alcohol and water washing, 60 DEG C of vacuum later
Dry 6h, obtains pure Mn catalyst.
The performance of catalyst and kinetics test carry out in micro fixed-bed reactor in this experiment, for closing
At the application process of the catalyst of gas preparing low-carbon olefins are as follows: it weighs 25mg catalyst and is diluted with 75mgSiC, before starting reaction,
The first original position 5h at a temperature of 350 DEG C under normal pressure by catalyst, then the temperature was then adjusted to 260 DEG C, H is passed through in 1:1 ratio2/
CO, air speed 4000h-1Certain time length is reacted at 2M, reaction result is shown in Table 2.
Above said content is only the basic explanation under present inventive concept, and that is done according to the technique and scheme of the present invention appoints
What equivalent transformation, is protection scope of the present invention.
The primary grains partial size and mono-dispersion microballoon partial size of the ferrum-based catalyst provided by the invention of table 1
The catalytic performance of the part ferrum-based catalyst provided by the invention of table 2
The result shows that on the basis of ferrum-based catalyst, introducing doping gold compared to pure iron catalyst and pure Mn catalyst
Belong to, the performance of catalyst can be significantly improved, not only increase the selectivity of low-carbon alkene in product, and CO2And CH4Content
It is lower, substantially increase the utilization rate of CO.The catalyst of phase homogenous quantities, with the increase of doping metals relative amount, iron atom
Relative amount reduce, however the conversion ratio of CO is not substantially reduced, therefore the introducing of doping metals, significantly improves iron atom
Dispersion degree, improve the surface utilisation of iron atom.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the invention
It encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people complete
Entity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of application
It is considered as being covered by among the scope of the claims.
Claims (8)
1. a kind of method that coal based synthetic gas prepares low-carbon alkene, which is characterized in that at 250-260 DEG C of reaction temperature, reaction pressure
Power 1.5-2.5MPa, volume space velocity 1000-16000h-1Under conditions of, synthesis gas generates hydrocarbon with ferrum-based catalyst haptoreaction
Compound；
The ferrum-based catalyst is the mono-dispersion microballoon of metal-doped spinel structure ferriferrous oxide nano primary grains cluster,
Wherein the molar ratio of doping metals total atom and iron atom is (1-50): (99-50)；
The ferrum-based catalyst is prepared by following step: iron chloride, doped metal salt presoma is dissolved into alcoholic solvent,
The organic modifier containing carboxyl is added, is placed 8-72 hours in 200 DEG C after mixing；Described contains the organic of carboxyl
Dressing agent is selected from one or both of sodium acetate, sodium acrylate, sodium citrate；
There is the lattice position of ferrous ion to be doped metallic atom in the spinel structure to occupy；
The doping metals atom is one or both of Mn, Mg, Cu, Zn.
2. the method as described in claim 1, which is characterized in that the partial size of the nanometer primary grains can within the scope of 5-20nm
It adjusts, the partial size of the mono-dispersion microballoon is adjustable within the scope of 100-800nm.
3. the method as described in claim 1, which is characterized in that the molar ratio of doping metals total atom and iron atom is (5-
33.3): (95-66.7).
4. the method as described in claim 1, which is characterized in that the doping metals atom is manganese atom and/or magnesium atom.
5. the method as described in claim 1, which is characterized in that the doped metal salt presoma is selected from the salt of doping metals
Hydrochlorate or nitrate；The alcoholic solvent is selected from one or both of ethylene glycol, diethylene glycol, glycerine, butanediol；.
6. method as claimed in claim 5, which is characterized in that total concentration of the metal salt in alcoholic solvent is 0.05-0.50M；
The molar ratio of organic modifier and total metallic atom is 2-8.
7. method as claimed in claim 6, which is characterized in that total concentration of the metal salt in alcoholic solvent is 0.10-0.25M.
8. method as claimed in claim 6, which is characterized in that the molar ratio of organic modifier and total metallic atom is 4-6.
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| CN1645530A (en) * | 2004-11-12 | 2005-07-27 | 清华大学 | Method for synthesizing series single-dispersed ferrite nanometer magnetic beads |
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| 溶胶-凝胶法和共沉淀法制备的K/Mn/Fe 复合氧化物催化剂在CO 加氢反应中的对比研究;王翀等;《天然气化工》;20040831;第29卷(第4期);第16页 |
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