CN104907080A - Iron-based catalyst, and preparation method and application thereof - Google Patents
Iron-based catalyst, and preparation method and application thereof Download PDFInfo
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- CN104907080A CN104907080A CN201510253235.6A CN201510253235A CN104907080A CN 104907080 A CN104907080 A CN 104907080A CN 201510253235 A CN201510253235 A CN 201510253235A CN 104907080 A CN104907080 A CN 104907080A
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- ferrum
- based catalyst
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- atom
- iron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 239000003245 coal Substances 0.000 claims abstract description 14
- 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
- 239000002245 particle Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 22
- 150000002739 metals Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 239000011029 spinel Substances 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 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
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 hydrogen compound Chemical class 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 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
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000013019 agitation Methods 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000007942 carboxylates Chemical group 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 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
- 239000002028 Biomass Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000009466 transformation Effects 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 an iron-based catalyst, and a preparation method and application thereof. The iron-based catalyst is monodisperse microspheres formed by clustering metal-doped spinel-structural ferriferrous oxide primary nanometer grains, wherein the mol ratio of total doped-metal atoms to iron atoms is 1-50: 99-50. The iron-based catalyst can be prepared by using a solvothermal method; meanwhile, the obtained iron-based catalyst can be applied in preparation of low-carbon olefin from coal-based synthesis gas.
Description
Technical field
The present invention relates to one to be applied to F-T synthesis and to prepare low-carbon alkene, especially relate to and be a kind ofly applied to coal based synthetic gas ferrum-based catalyst preparing low-carbon alkene and preparation method thereof.
Background technology
Low-carbon alkene (ethene, propylene) is important Organic Chemicals.One of optimal paths realizing clear energy sources by the indirect reformer route production of chemicals of coal, natural gas and living beings.First natural gas, coal and biomass conversion are synthesis gas (CO and H by this process
2), be then raw material production chemical products with high added-value with synthesis gas.Carbon monoxide (CO) catalytic hydrogenation is one of more complicated reaction system, under differential responses condition, can produce from methane to paraffin, alkene and various oxide.It is very complicated that synthesis gas directly prepares low-carbon alkene (F-T synthesis prepares low-carbon alkene FTO) product composition, and accessory substance is as inevitable in the generation of CH4, CO2, and the generation of a large amount of C5+ also has a strong impact on total yield of light olefins.In addition the raising that also limit olefine selective is reacted in secondary response such as hydrogenation, disproportionation, the polymerization etc. of Primary product alkene.The key problem that current needs solve is improving olefine selective while, and the effective product that controls distributes.
Summary of the invention
The present invention aims to provide a kind of Catalysts and its preparation method improving coal based synthetic gas and prepare the low olefine selective of low-carbon alkene.
In a first aspect of the present invention, provide a kind of ferrum-based catalyst being applied to coal based synthetic gas and preparing low-carbon alkene, this ferrum-based catalyst is the mono-dispersion microballoon of metal-doped spinel structure ferriferrous oxide nano primary grains cluster, and wherein the mol ratio of doping metals total atom and iron atom is (1-50): (99-50).
In another preference, there is the lattice position of ferrous ion to be doped metallic atom in described spinel structure and occupy.
In another preference, the particle diameter of described nanometer primary grains is adjustable within the scope of 5-20nm, and the particle diameter of described mono-dispersion microballoon is adjustable within the scope of 100-800nm.
In another preference, the mol ratio of doping metals total atom and iron atom is (5-33.3): (95-66.7).
In another preference, described doping metals atom is one or both in Mn, Mg, Cu, Zn; More preferably manganese atom and/or magnesium atom.
In a second aspect of the present invention, provide a kind of preparation method of ferrum-based catalyst provided by the invention as above, described method comprises step:
Iron chloride, doped metal salt presoma are dissolved in alcoholic solvent, add the organic modifier containing carboxyl, after mixing, in 200 DEG C, place 8-72 hour, obtain ferrum-based catalyst provided by the invention as above.
In another preference, described doped metal salt presoma is selected from hydrochloride or the nitrate of doping metals; Described alcoholic solvent be selected from ethylene glycol, diethylene glycol, glycerine, butanediol one or both; The described organic modifier containing carboxyl be selected from sodium acetate, PAA, natrium citricum one or both.
In another preference, the concentration of total slaine in alcoholic solvent is 0.05-0.50M, more preferably 0.10-0.25M;
In another preference, the mol ratio of organic modifier and total metallic atom is 2-8, more preferably 4-6.
In a third aspect of the present invention, provide a kind of ferrum-based catalyst provided by the invention as above and prepare application in low-carbon alkene at coal based synthetic gas.
In a fourth aspect of the present invention, provide a kind of coal based synthetic gas prepare low-carbon alkene method, at reaction temperature 250-350 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1000-16000h
-1condition under, synthesis gas and ferrum-based catalyst haptoreaction Formed hydrogen compound provided by the invention as above.
Accordingly, the invention provides a kind of Catalysts and its preparation method improving coal based synthetic gas and prepare the low olefine selective of low-carbon alkene.
Accompanying drawing explanation
Fig. 1 shows the XRD collection of illustrative plates of Mn doped iron base catalyst in embodiment 8 provided by the invention, and scheming known metal-doped ferrum-based catalyst from XRD is spinel structure, calculates average grain diameter and is about 12.2nm.
Fig. 2 shows the SEM of Mn doped iron base catalyst in embodiment 8 provided by the invention, and from SEM image, this ferrum-based catalyst is microballoon by the nano particle cluster of spinel structure.
Detailed description of the invention
Inventor, through extensive and deep research, finds a kind of ferrum-based catalyst in mono-dispersion microballoon shape, has the nanometer primary grains cluster of spinel structure to form.Nanometer primary grains is the tri-iron tetroxide that doping metals enters lattice framework.By introducing doping metals, improve the density of iron atom in the decentralization of iron atom and unit cell at atomic scale, improve the cloud density around iron atom, inhibit carbochain to increase, thus raising low-carbon alkene is selective.On this basis, the present invention is completed.
Ferrum-based catalyst
As used herein, " be applied to the ferrum-based catalyst that coal based synthetic gas prepares low-carbon alkene ", " ferrum-based catalyst " and " catalyst provided by the invention " can exchange use, all refer to a kind of doping metals atom occupy the ferrous lattice position of part in spinel structure formed many metallic irons catalyst based, described doping metals atom is Mn, Mg, Cu, one or both (preferred Mn atom and/or Mg atoms) in Zn, the mol 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 mono-dispersion microballoon shape, has the nanometer primary grains cluster of spinel structure to form.Nanometer primary grains is the tri-iron tetroxide that doping metals enters lattice framework, and the particle diameter of described nanometer primary grains is adjustable within the scope of 5-20nm, and the particle diameter of described mono-dispersion microballoon is adjustable within the scope of 100-800nm.
Ferrum-based catalyst provided by the invention is by introducing doping metals, the density of iron atom in the decentralization of iron atom and unit cell is improve at atomic scale, improve the cloud density around iron atom, inhibit carbochain to increase, improve the selective of low-carbon alkene.Preferably, under doping metals of the present invention and consumption, the ionic radius of doping metals Mn is suitable with ferrous ionic radius, easily enters the position that lattice framework replaces part ferrous ion, keeps tri-iron tetroxide spinel structure again.
The preparation method of ferrum-based catalyst
The preparation method of ferrum-based catalyst provided by the invention adopts hot solvent method, comprises the steps:
The first step, mixes iron chloride and doped metal salt presoma with higher boiling organic alcohol solvent, dissolves;
Second step, adds the organic modifier containing carboxyl and mixes;
3rd step, places 8-72 hour at 200 DEG C, obtains ferrum-based catalyst provided by the invention.
In the above-mentioned first step, described doped metal salt presoma comprises hydrochloride or the nitrate of doping metals.
In the above-mentioned first step, described higher boiling organic alcohol solvent is made up of one or both in ethylene glycol, diethylene glycol, glycerine, butanediol; The concentration of total slaine in higher boiling Organic Alcohol is 0.05-0.50M, preferred 0.10-0.25M.
In one embodiment of the invention, undertaken mixing by stirring in the above-mentioned first step and dissolve, such as but not limited to, the above-mentioned first step iron chloride and doped metal salt presoma is added in higher boiling organic alcohol solvent to stir to make to dissolve completely.
In above-mentioned second step, the described organic modifier containing carboxyl is one or both in sodium acetate, PAA, natrium citricum, and the mol ratio of organic modifier and total metallic atom is 2-8, preferred 4-6.
In one embodiment of the invention, above-mentioned second step is the organic modifier added after the above-mentioned first step obtains consoluet solution containing carboxyl, continues stirring and makes to mix.
In one embodiment of the invention, above-mentioned 3rd step mixes at above-mentioned second step to be placed on baking oven 8-72 hour.
In the preferred embodiment of the present invention, after above-mentioned 3rd step places 8-72 hour at 200 DEG C, carry out nature cooling, and with after ethanol and water washing, obtain ferrum-based catalyst provided by the invention 60 DEG C of vacuum drying.
The present invention adopts hot solvent method, is dissolved in higher boiling organic alcohol solvent by molysite, doped metal salt presoma, the mono-dispersion microballoon that the nanocrystal that situation about coexisting at organic carboxylate forms spinel structure assembles.Higher boiling Organic Alcohol had both played the effect of solvent, had week reduction again, in the mild alkaline conditions that organic carboxylate is formed, formed iron-based nano-oxide crystal grain with molysite generation eremacausis reduction reaction.The week reduction of Organic Alcohol is conducive to forming uniform crystal grain, and excessive organic carboxylate makes crystal grain with partial negative charge, and electrostatic repulsion prevents crystal grain fast growth, thus effectively control crystal grain is evenly distributed on more among a small circle.
The application of ferrum-based catalyst
Ferrum-based catalyst provided by the invention can be applicable to coal based synthetic gas and prepares low-carbon alkene.Synthesis gas at reaction temperature 250-350 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1000-16000h
-1condition under with ferrum-based catalyst haptoreaction Formed hydrogen compound provided by the invention.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can be combined.All features that this case description discloses can with any composition forms and use, each feature disclosed in description, anyly can provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Major advantage of the present invention is:
1, ferrum-based catalyst primary grains provided by the invention and secondary microspherulite diameter are evenly distributed, and size is controlled.
2, from the mechanism of preparing low-carbon olefin, the process of the preparation ferrum-based catalyst provided by the invention of design is simple, and the cycle is short, and cost is very cheap, evaluation of catalyst activity under the condition of amplifying close to industry, demonstrates very high low carbon selectivity and high carbon utilisation rate.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or number by weight.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Embodiment 1
By 2.5333g FeCl
36H
2o and 0.9273gMnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 72h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 2
By 2.5333g FeCl
36H
2o and 0.9273gMnCl
24H
2o adds (volume ratio of ethylene glycol and diethylene glycol is 1:3) in the mixed solution of 134mL ethylene glycol and diethylene glycol, magnetic agitation makes it dissolve completely, add 9.6g NaAc afterwards, continuing stirring makes it mix, then 2 100mL stainless steel crystallizing kettles are proceeded to, put into baking oven, and after placing 8h in 200 DEG C, take out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 3
By 3.7865gFe (NO
3)
39H
2o and 0.9273gMnCl
24H
2o adds in 134mL ethylene glycol, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 4
By 3.7865gFe (NO
3)
39H
2o and 0.9273gMnCl
24H
2o adds in 134mL ethylene glycol, and magnetic agitation makes it dissolve completely, adds 4.8g NaAc afterwards and 5.5g acrylic acid is received, continuing stirring makes it mix, and then proceeds to 2 100mL stainless steel crystallizing kettles, puts into baking oven, and after placing 8h in 200 DEG C, take out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 5
By 3.7865gFe (NO
3)
39H
2o and 0.9273gMnCl
24H
2o adds in 134mL ethylene glycol, and magnetic agitation makes it dissolve completely, adds 4.8g NaAc and 6.5g natrium citricum afterwards, continuing stirring makes it mix, and then proceeds to 2 100mL stainless steel crystallizing kettles, puts into baking oven, and after placing 8h in 200 DEG C, take out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 6
By 7.5g FeCl
36H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain ferrum-based catalyst afterwards, and its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
Embodiment 7
By 3.7626g FeCl
36H
2o and 0.0284gMnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that manganese accounts for total metal is the catalyst of 1%, is labeled as Mn
0.03fe
2.97o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1, under 2M, react certain time length, reaction result is in table 2.
Embodiment 8
By 3.6100g FeCl
36H
2o and 0.1394gMnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that manganese accounts for total metal is the catalyst of 5%, is labeled as MnFe
2o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Embodiment 9
By 2.5333g FeCl
36H
2o and 0.9273gMnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that manganese accounts for total metal is the catalyst of 33.3%%, is labeled as MnFe
2o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Embodiment 10
By 0.7601g FeCl
36H
2o and 2.2257g MnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that manganese accounts for total metal is the catalyst of 80%, is labeled as Mn
2.4fe
0.6o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO gaseous mixture, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Embodiment 11
By 2.5333g FeCl
36H
2the MgCl of O and 0.9527g
26H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that magnesium accounts for total metal is the catalyst of 33.3%%, is labeled as MgFe
2o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Embodiment 12
By 3.7626g FeCl
36H
2o, 0.4637gMnCl
24H
2the MgCl of O and 0.4763g
26H
2o, add in 134mL ethylene glycol solution, magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, obtaining the mole percent that magnesium and manganese accounts for total metal is the catalyst of 33.3%%, is labeled as Mg
0.5mn
0.5fe
2o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Embodiment 13
By 3.7626g FeCl
36H
2o, 0.4637gMnCl
24H
2the MgCl of O and 0.4763g
26H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h afterwards, then a certain amount of desciccate is taken, adopt wet impregnation legal system for 1% KCl solution, then with 60 DEG C of dried in vacuo overnight, prepare the catalyst that K modifies, obtaining the mole percent that magnesium and manganese accounts for total metal is 33.3%%, the catalyst that K atom is modified, is labeled as K/Mg
0.5mn
0.5fe
2o
4, its primary grains particle diameter and mono-dispersion microballoon particle diameter list in table 1.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
In order to highlight the advantage of multicomponent catalyst of the present invention, this patent has prepared ferriferous oxide and Mn oxide respectively as comparing.
Comparative example 1
By 3.8g FeCl
36H
2o and 134mL ethylene glycol adds in 250mL polypropylene vial, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continuing stirring makes it mix, and then proceeds to 2 100mL stainless steel crystallizing kettles, puts into baking oven, and after placing 8h in 200 DEG C, take out nature cooling.And with ethanol and water washing for several times, 60 DEG C of vacuum drying 6h, obtain pure iron catalyst afterwards.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Comparative example 2
By 2.7826gMnCl
24H
2o adds in 134mL ethylene glycol solution, and magnetic agitation makes it dissolve completely, adds 9.6g NaAc afterwards, continues stirring and makes it mix, then proceed to 2 100mL stainless steel crystallizing kettles, put into baking oven, and after placing 8h in 200 DEG C, takes out nature cooling.Adopt centrifugation mode, and with ethanol and water washing several, 60 DEG C of vacuum drying 6h, obtain pure Mn catalyst afterwards.
In this experiment, the performance of catalyst and kinetics test are carried out in micro fixed-bed reactor, application process for the synthesis of the catalyst of gas preparing low-carbon olefins is: take 25mg catalyst 75mgSiC and dilute, before starting reaction, first by catalyst original position 5h at the temperature of 350 DEG C at ambient pressure, again temperature is adjusted to 260 DEG C, passes into H in 1:1 ratio
2/ CO, air speed is 4000h
-1under 2M, react certain time length, reaction result is in table 2.
Above said content be only the present invention conceive under basic explanation, and any equivalent transformation that technical scheme according to the present invention is done, is protection scope of the present invention.
The primary grains particle diameter of table 1 ferrum-based catalyst provided by the invention and mono-dispersion microballoon particle diameter
The catalytic performance of table 2 part ferrum-based catalyst provided by the invention
Result shows, compared to pure iron catalyst and pure Mn catalyst, on the basis of ferrum-based catalyst, introduces doping metals, significantly can improve the performance of catalyst, not only increase the selective of low-carbon alkene in product, and CO
2and CH
4content lower, substantially increase the utilization rate of CO.The catalyst of equal in quality, along with the increase of doping metals relative amount, the relative amount of iron atom reduces, but the conversion ratio of CO does not obviously reduce, therefore the introducing of doping metals, significantly improves the decentralization of iron atom, improves the surface utilisation of iron atom.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
Claims (10)
1. the ferrum-based catalyst being applied to coal based synthetic gas and preparing low-carbon alkene, it is characterized in that, this ferrum-based catalyst is the mono-dispersion microballoon of metal-doped spinel structure ferriferrous oxide nano primary grains cluster, and wherein the mol ratio of doping metals total atom and iron atom is (1-50): (99-50).
2. ferrum-based catalyst as claimed in claim 1, is characterized in that having the lattice position of ferrous ion to be doped metallic atom in described spinel structure and occupy.
3. ferrum-based catalyst as claimed in claim 1, it is characterized in that, the particle diameter of described nanometer primary grains is adjustable within the scope of 5-20nm, and the particle diameter of described mono-dispersion microballoon is adjustable within the scope of 100-800nm.
4. ferrum-based catalyst as claimed in claim 1, it is characterized in that, the mol ratio of doping metals total atom and iron atom is (5-33.3): (95-66.7).
5. the ferrum-based catalyst as described in any one of claim 1-4, is characterized in that, described doping metals atom is one or both in Mn, Mg, Cu, Zn; Preferred manganese atom and/or magnesium atom.
6. a preparation method for the ferrum-based catalyst as described in any one of claim 1-5, is characterized in that, described method comprises step:
Iron chloride, doped metal salt presoma are dissolved in alcoholic solvent, add the organic modifier containing carboxyl, after mixing, in 200 DEG C, place 8-72 hour, obtain the ferrum-based catalyst as described in any one of claim 1-5.
7. preparation method as claimed in claim 6, it is characterized in that, described doped metal salt presoma is selected from hydrochloride or the nitrate of doping metals; Described alcoholic solvent be selected from ethylene glycol, diethylene glycol, glycerine, butanediol one or both; The described organic modifier containing carboxyl be selected from sodium acetate, PAA, natrium citricum one or both.
8. preparation method as claimed in claim 6, it is characterized in that, the concentration of total slaine in alcoholic solvent is 0.05-0.50M, preferred 0.10-0.25M; The mol ratio of organic modifier and total metallic atom is 2-8, preferred 4-6.
9. the ferrum-based catalyst as described in any one of claim 1-5 prepares the application in low-carbon alkene at coal based synthetic gas.
10. coal based synthetic gas prepare low-carbon alkene a method, it is characterized in that, at reaction temperature 250-350 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1000-16000h
-1condition under, synthesis gas and ferrum-based catalyst haptoreaction Formed hydrogen compound as described in any one of claim 1-5.
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| CN107497437A (en) * | 2017-09-11 | 2017-12-22 | 华东理工大学 | One kind is used for CO2It is hydrogenated with ferrum-based catalyst and its application of preparing low-carbon olefins |
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