CN104907076A - Coal carbon dioxide gasification catalyst and preparation method thereof - Google Patents
Coal carbon dioxide gasification catalyst and preparation method thereof Download PDFInfo
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- CN104907076A CN104907076A CN201510164215.1A CN201510164215A CN104907076A CN 104907076 A CN104907076 A CN 104907076A CN 201510164215 A CN201510164215 A CN 201510164215A CN 104907076 A CN104907076 A CN 104907076A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002309 gasification Methods 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 41
- 239000003245 coal Substances 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- -1 oxygen ions Chemical class 0.000 claims abstract description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000005283 ground state Effects 0.000 claims abstract description 3
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical group 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000003077 lignite Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002006 petroleum coke Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
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- Catalysts (AREA)
Abstract
The invention discloses a coal carbon dioxide gasification catalyst and a preparation method thereof. The catalyst is composed of carbon active site loaded on a carrier, the carrier can provide machinery support and can transfer the oxygen atoms or oxygen ions, the carrier contains CO2 active site; the carbon active site and CO2 active site in the carrier are taken as catalytic activity components, transfer for oxygen ions is realized by a oxidation reduction reaction; the carrier transfers the oxygen atoms or oxygen ions, CO2 is taken as an oxidizing agent, and then ground state carbon is gasified to CO. The catalyst has good catalytic activity, compared with a traditional catalyst, the catalyst in the invention has stronger catalysis performance, and the catalysis condition is more peaceful.
Description
The technical field is as follows:
the invention belongs to the technical field of coal gasification, and particularly relates to a coal carbon dioxide gasification catalyst and a preparation method thereof.
Background art:
according to literature reports, most of the catalysts used for gasifying coal work under the environment of water vapor or air, such as the Exxon company in the United states, which proposed K in the 70's of the 20 th century2CO3As a catalyst, a coal pressurized fluidized bed catalytic gasification process aiming at producing artificial natural gas is developed by using steam as a gasification agent under the conditions of 3MPa and 700 ℃, and Chinese patent CN103301865A also makes a further improvement. Carbon dioxide is a weaker oxidant than water vapor. Carbon dioxide is chemically very inert due to its own structural stability. Therefore, the catalytic activity of the existing coal gasification catalyst under the carbon dioxide atmosphere can be greatly reduced, so that the actual requirement of synchronously converting coal and carbon dioxide which cause greenhouse effect into high-value-added products in the application process can not be met. In addition, existing gasification catalysts are loaded onto carbon-based solid reactants using an impregnation process. The contact mode has the advantages of effectively realizing 'intimate' contact between the catalyst and the coal solid particles and greatly improving the catalytic area. However, this also causes a problem that the catalyst is difficult to be completely recycled due to strong interaction (e.g., chemical bond) with the carbon-based solid reactant particle residue after the gasification reaction, and thus greatly reduces the recycling rate of the catalyst, and causes a great increase in the amount of the catalyst used, thereby resulting in a significant increase in the coal gasification cost.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides a coal carbon dioxide gasification catalyst and a preparation method thereof so as to solve the technical problems mentioned above. The catalyst prepared by the invention can reach extremely high catalytic activity under mild catalytic conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the coal carbon dioxide gasification catalyst consists of carbon active sites loaded on a carrier, wherein the carrier can provide mechanical support and can transfer oxygen atoms or oxygen ions, and the carrier contains CO2A carrier for the active site; the carbon active site and CO contained in the carrier2The active site is a catalytic active component, and oxygen ions are transferred through oxidation-reduction reaction;
the carrier transferring oxygen atoms or oxygen ions to CO2As an oxidizing agent, ground state carbon is gasified to CO.
The invention further improves the following steps: the carrier is a compound composed of a plurality of metal oxides, wherein the mass percentage of the carrier in the catalyst is 80-90%.
The invention further improves the following steps: a part of metal oxide in the carrier plays a role of providing mechanical support for active sites, and the part of metal oxide is Al2O3、SiO2、TiO2Or ZrO2Any one or more of them, and the mass percentage in the carrier is 30-70%;
the other part of the metal oxide in the carrier plays a role of transferring oxygen atoms or oxygen ions, and the part of the metal oxide is CeO2Or La2O3And the mass percentage in the carrier is 10-30%;
the rest part of the metal oxide in the carrier plays a role in activating CO2Is CO2Active site, the partial metal oxide is ZnO or SnO2、Fe2O3、Ga2O3、PbO、CuO、Bi2O3、CeO2Or La2O3Either or both of which are contained in the carrier in an amount of 20 to 60% by mass.
The invention further improves the following steps: the carbon active site is alkali metal or a mixture of alkali metal and alkaline earth metal; wherein,
when the carbon active site is alkali metal, the mass percentage of the alkali metal in the catalyst is 10-20%;
when the carbon active site is a mixture of alkali metal and alkaline earth metal, the mass percent of the alkali metal in the catalyst is 5-15%, and the mass percent of the alkaline earth metal in the catalyst is 5-15%.
A preparation method of a coal carbon dioxide gasification catalyst comprises the following steps:
1) preparation of a catalyst containing CO by coprecipitation2Active site vector:
1-1) dissolving soluble salt into deionized water to prepare solution A with the total ion concentration of 0.1-2 mol/L, wherein the soluble salt is Zn (NO)3)2·6H2O、Ce(NO3)3·6H2O、La(NO3)3·6H2O、SnCl4、Fe(NO3)3·9H2O、Al(NO3)3·9H2O、Ga(NO3)3·xH2O、Pb(NO3)2、Cu(NO3)2·2.5H2O、Bi(NO3)3·5H2One or more of O;
1-2) taking an ammonia water solution as a B solution;
1-3) pumping the solution A into a precipitation tank containing deionized water at the temperature of 30-50 ℃ at the rate of 2.5 mL/min;
1-4) adjusting the adding rate of the solution B to maintain the pH value in the precipitation tank to be 8 +/-0.2;
1-5) when the solution A is completely pumped into the precipitation tank, sequentially closing the peristaltic pumps used for conveying the solution A and the solution B to obtain slurry;
1-6) stirring the slurry under the conditions that the pH value is 8 +/-0.2 and the temperature is 30-50 ℃, repeatedly washing and filtering by using water and methanol to obtain a filter cake;
1-7) putting the obtained filter cake into an oven, and drying for 12 hours at the temperature of 90-110 ℃;
1-8) calcining the filter cake under flowing air: heating to 120 deg.C for 0.3 hr, heating to 550 deg.C at a heating rate of 3 deg.C/min, and holding for 4 hr to obtain a product containing CO2A carrier for the active site;
2) introduction of carbon-based activation sites into the CO-containing product obtained in step 1) by impregnation2Preparing a coal carbon dioxide gasification catalyst on a carrier of an active site:
2-1) the CO-containing product obtained in step 1)2Grinding the carrier of the active site into A powder;
2-2) dissolving magnesium nitrate hexahydrate or calcium nitrate tetrahydrate in deionized water to prepare a C solution with the concentration of 2-6 mol/L;
2-3) dipping the solution C on the powder A while stirring;
2-4) putting the dipped powder A into a drying furnace, and drying for 12 hours at 90-110 ℃;
2-5) repeating the steps 2-3) and 2-4) until all the C solution is soaked on the surface of the A powder, wherein 0.65-2 mL of the C solution is soaked in each g of the A powder;
2-6) calcining the impregnated A powder under flowing air: heating to 120 ℃ and maintaining for 0.5 hour, then heating to 600 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-7) naturally cooling to room temperature, and collecting a calcined product, wherein the calcined product is the powder C;
2-8) dissolving potassium nitrate in ionic water to prepare a transparent D solution with the concentration of 2-6 mol/L;
2-9) dipping the D solution on the C powder while stirring;
2-10) putting the impregnated C powder into a drying furnace, and drying for 12 hours at 90-110 ℃;
2-11) repeating the steps 2-9) and 2-10) until all the D solution is soaked on the surface of the C powder, wherein 0.65-1.5 mL of the D solution is soaked in each g of the C powder;
2-12) calcining the impregnated C powder under flowing air: firstly heating to 120 ℃ and maintaining for 0.5 hour, then heating to 800 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-13) naturally cooling to room temperature to obtain the coal carbon dioxide gasification catalyst.
Compared with the traditional gasification catalyst, the invention has the following advantages:
1. the gasification activity of carbon dioxide is strong. The catalyst contains CO2Active sites and can effectively transfer oxygen atoms or oxygen ions generated in the reduction process of the carbon dioxide to carbon-based solid raw materials (such as lignite and the like) for partial oxidation. For this reason, the catalyst has at least one-fold higher activity than conventional catalysts under a carbon dioxide atmosphere.
2. The catalyst has high recovery and utilization rate. The catalyst is in a self-supporting structure, and is in contact with the carbon-based solid raw material only through physical collision so as to generate chemical reaction, rather than forming a certain form of chemical bond with the carbon-based solid raw material through a chemical impregnation method so as to realize 'close' contact as in the traditional catalyst. Through the change of the contact mode, the catalyst provided by the invention can fundamentally solve the practical application problems that the traditional catalyst cannot be effectively recovered due to the strong interaction caused by the fact that the traditional catalyst is diffused into a porous structure of residue generated after gasification of a carbon-based solid raw material, so that the catalyst is greatly lost, and the cost is greatly increased. Therefore, the wide application of the catalyst of the invention can be used for strongly promoting the coal gasification industrialization process.
3. And (4) no water washing recovery step. Compared with the traditional gasification catalyst, the catalyst prepared by the invention has strong mechanical strength, and can keep good physical form in the application process of the circulating fluidized bed, so that the effective separation of the residue generated after the carbon-based solid raw material is gasified in a cyclone separator can be effectively realized through the particle size difference, and the residue can be returned to the gasification furnace to participate in the reaction again. The traditional catalyst can be physically separated from the residue generated after the carbon-based solid raw material is gasified only by a water washing method after participating in the gasification reaction. This additional washing step not only causes an increase in production cost, but also inevitably brings a certain amount of minute residues back to the reaction system, increasing the burden of secondary separation. In addition, for carbon dioxide gasification, the water washing step can produce considerable industrial wastewater with an excessive alkali metal content. Further cost increases are associated with wastewater treatment.
4. The preparation method of the catalyst has the advantages of simple process, strong operability and high cost performance. The catalyst disclosed by the invention adopts a coprecipitation method to prepare the carrier, and metal oxides playing different functions in the carrier are organically fused together on a molecular level, so that the synergistic effect of each component in the catalyst carrier is promoted to the greatest extent, and a better catalytic effect is generated. The coprecipitation and impregnation methods used in the preparation process of the catalyst are means widely adopted in the actual application of the catalyst industry, the operation process is very mature, and the risk and the cost of industrial mass production of the catalyst can be greatly reduced.
Description of the drawings:
FIG. 1 is a schematic diagram of the catalytic principle of a coal carbon dioxide gasification catalyst according to the present invention;
FIG. 2 shows the gasification activity of petroleum coke in the presence of different catalysts in example 1 of the present invention;
FIG. 3 shows the gasification activity of lignite under different catalysts in example 1 of the present invention;
fig. 4 shows gasification activity of lignite for a long time using the catalyst prepared in example 1 according to the present invention.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
10％K-10％Mg/38％SnO2-29％Fe2O3-33％Al2O3The meaning of this formula is: the carrier is composed of 38% SnO229% Fe2O3And 33% of Al2O3And (4) forming. The carbon active sites consist of 10% K and 10% Mg by total weight of the catalyst.
The preparation process comprises the following steps:
1) synthesized from SnO2-Fe2O3-Al2O3The carrier of the composition is as follows:
1-1) weighing 12.79g of stannic chloride (SnCl)4) 28.12g of iron nitrate (Fe (NO)3)3) And 47.68g of aluminum nitrate (Al (NO)3)3) Dissolving the mixed solution into 200mL of deionized water to prepare a solution A;
1-2) measuring 400mL of ammonia water solution as a B solution;
1-3) pumping the solution A into a precipitation tank containing 200mL of initial deionized water at 40 ℃ at a rate of 2.5 mL/min;
1-4) while maintaining the pH value (pH) in the precipitation tank equal to 8. + -. 0.2 by adjusting the rate of addition of the solution B;
1-5) when the solution A is completely pumped into the precipitation tank, sequentially closing the peristaltic pumps for conveying the solution A and the solution B;
1-6) the resulting slurry was additionally stirred at the desired pH of 8 ± 0.2 and temperature of 40 ℃, and then immediately filtered repeatedly with water and methanol;
1-7) cleaning the filter cake until chloride ions are completely removed, and detecting the chloride ions by using silver nitrate;
1-8) then placing the washed filter cake into an oven to be dried for 12 hours at the temperature of 110 ℃;
1-9) calcining the filter cake under flowing air: heating to 120 deg.C for 0.3 hr, heating the filter cake to 550 deg.C at a heating rate of 3 deg.C/min, and holding for 4 hr to obtain 38% SnO2-29％Fe2O3-33％Al2O3The catalyst carrier of (1);
2) the synthesis is carried out by K-Mg/SnO2-Fe2O3-Al2O3Catalyst of composition:
2-1) weighing 16g of carrier material generated by the first-step coprecipitation method and grinding the carrier material into powder A;
2-2) 18.77g of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) and dissolving the mixed solution into 18mL of deionized water to prepare a solution C;
2-3) carefully dipping the solution C into the powder A with a dropper while stirring (taking care of the amount of solution C added each time to ensure that the support does not become excessively wet);
2-4) putting the soaked A powder into a drying furnace, and setting the temperature at 110 ℃ overnight for drying for 12 hours;
2-5) repeating the steps 2-3) and 2-4) until all the solution C is impregnated on the surface of the powder A;
2-6) calcining the impregnated A powder under flowing air: heating to 120 ℃ and maintaining for 0.5 hour, then heating the filter cake to 600 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-7) naturally cooling to room temperature, and then collecting calcined powder C;
2-8) weighing 5.46g potassium nitrate (KNO)3) Dissolving the D-type aqueous solution into 15mL of ionized water to prepare a transparent D solution with a certain concentration;
2-9) carefully dip the solution D into the powder C with a dropper while stirring (taking care of the amount of solution D added each time, to ensure that the support does not become excessively wet);
2-10) putting the impregnated C powder into a drying furnace, and setting the temperature at 110 ℃ overnight for drying for 12 hours;
2-11) repeating steps 2-9) and 2-10) until all of the solution D is impregnated onto the surface of the powder C;
2-12) calcining the impregnated C powder under flowing air: heating to 120 ℃ and maintaining for 0.5 hour, then heating the filter cake to 800 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-13) naturally cooling to room temperature to finally prepare the required catalyst.
Catalysts prepared according to this principle have shown good catalytic activity in laboratory-scale experiments. As shown in fig. 2, we chose to use petroleum coke (the carbon accretion formed on the surface of the cracking catalyst during crude oil refining) as the reference carbon-based solid feedstock because of its high inertness to participate in the gasification reaction due to its own high carbon content (94.8%). Among the series of carbonaceous solid feedstocks that we previously tested (including coal, biomass, and municipal solid waste), petroleum coke is the least active for gasification. Thus, the catalytic activity of the developed catalyst can be better evaluated by using it as a reference. As shown in fig. 2, the petroleum coke had little gasification activity prior to the addition of the catalyst, as previously predicted. When a traditional optimized catalyst prepared according to literature reported methods [ Wang, j.; yao, y.; cao, j.; jiang, m.fuel,2010,89,310-317]Post (K-Ca/Al)2O3) The gasification activity of the carbon-based solid raw material is obviously improved. When using the novel catalyst (K-Mg/SnO) prepared by us2-Fe2O3-Al2O3) Then, the gasification activity is further improved. As shown in fig. 2, the CO production rate of petroleum coke increased nearly 100-fold with the addition of the optimized new catalyst. Compared with the traditional catalyst, the catalyst of the invention can further improve the gasification activity of the petroleum coke by more than one time. Meanwhile, lignite is selected as a representative coal, and is not suitable for combustion power generation due to low combustion value caused by high oxygen content. And it releases more pollutants than other high-grade coals in the combustion process, causing serious environmental problems and further limiting its simple combustion utilization. Chinese lignite has huge reserves (proven reserves: 1300 hundred million tons) accounting for 13.3% of world coal reserves, which is second only to America and Russia and third in the world. Therefore, a way for cleanly and efficiently utilizing the lignite is found, and the important role is played in the sustainable development of domestic economy. Researches show that the preparation of fuel oil or chemicals with high added value by gasifying (controllable oxidizing) lignite and combusting or liquefying the prepared synthesis gas is an effective way for clean and efficient utilization of the fuel oil or chemicals. As shown in FIG. 3, the conventional catalyst (K-Ca/Al) is added2O3) Then, the gasification activity of the lignite is increased by more than 2 times. Even so, after addition of the optimized novel catalyst (K-Mg/SnO)2-Fe2O3-Al2O3) And the gasification activity of the lignite is further improved by nearly 2 times.
The following examples were also obtained, on the basis of the preparation method disclosed in example 1, by varying the parameters during the preparation, and systematic studies on their catalytic properties were carried out. The parameters used in the catalyst preparation and their associated catalytic activities are detailed in table 1 (the parameters not listed are the same as in example 1).
TABLE 1 catalyst 10% K-10% Mg/38% SnO2-29％Fe2O3-33％Al2O3Preparing ginsengThe reaction temperature and gasification activity are listed (800 deg.C, reaction pressure 1atm, gas space velocity 2.36 hr)-1)
The following examples were also obtained and systematically studied the catalytic performance of the catalysts according to the present disclosure, by varying the formulation of the catalysts. Some of the novel catalysts prepared up to now and their associated catalytic activities are listed in detail in table 2.
TABLE 2 catalyst and gasification Activity List (reaction temperature 800 deg.C, reaction pressure 1atm, gas space velocity 2.36hr-1)
From the above examples, it can be seen that, when a catalyst support is used, only one metal oxide is used and no CO is contained2In the active site, as in examples 32-43, the maximum CO production rate and CO of the vast majority of catalysts2The conversion decreases sharply, the reason for which is known from the action of the components and from the principle of catalysis.
In addition to testing the reactivity of the above-described preparation of the novel catalysts, the reaction stability was also determined on a laboratory scale for its potential industrial application. Fig. 4 shows lignite gasification activity within 100 hours by using the catalyst prepared in example 1 of the present invention. As shown, the CO production rate and CO2The conversion showed a certain fluctuation over the test period of 100 hours. But both remain approximately steady state on average. So as to get fromIn general, the catalysts exhibit good catalytic stability under reaction conditions, paving the way for their use on a larger scale.
The CO generation rate used in the present invention is calculated as follows:
in the formula (1), FCORepresents the volumetric generation flow rate, W, of CO at standard conditions0Representing the initial mass of carbon-based feedstock placed into the reactor.
CO2The conversion was calculated as follows:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A coal carbon dioxide gasification catalyst characterized by: is composed of carbon active sites supported on a carrier which is capable of providing mechanical support and transferring oxygen atoms or oxygen ions and contains CO2A carrier for the active site; the carbon active site and CO contained in the carrier2The active site is a catalytic active component, and oxygen ions are transferred through oxidation-reduction reaction;
the carrier transferring oxygen atoms or oxygen ions to CO2As an oxidizing agent, ground state carbon is gasified to CO.
2. The coal carbon dioxide gasification catalyst of claim 1, wherein: the carrier is a compound composed of a plurality of metal oxides, wherein the mass percentage of the carrier in the catalyst is 80-90%.
3. The coal carbon dioxide gasification catalyst of claim 2, wherein: a part of metal oxide in the carrier plays a role of providing mechanical support for active sites, and the part of metal oxide is Al2O3、SiO2、TiO2Or ZrO2Any one or more of them, and the mass percentage in the carrier is 30-70%;
the other part of the metal oxide in the carrier plays a role of transferring oxygen atoms or oxygen ions, and the part of the metal oxide is CeO2Or La2O3And the mass percentage in the carrier is 10-30%;
the rest part of the metal oxide in the carrier plays a role in activating CO2Is CO2Active site, the partial metal oxide is ZnO or SnO2、Fe2O3、Ga2O3、PbO、CuO、Bi2O3、CeO2Or La2O3Either or both of which are contained in the carrier in an amount of 20 to 60% by mass.
4. The coal carbon dioxide gasification catalyst of claim 1, wherein: the carbon active site is alkali metal or a mixture of alkali metal and alkaline earth metal; wherein,
when the carbon active site is alkali metal, the mass percentage of the alkali metal in the catalyst is 10-20%;
when the carbon active site is a mixture of alkali metal and alkaline earth metal, the mass percent of the alkali metal in the catalyst is 5-15%, and the mass percent of the alkaline earth metal in the catalyst is 5-15%.
5. The method of preparing a coal carbon dioxide gasification catalyst according to any one of claims 1 to 4, comprising the steps of:
1) preparation of a catalyst containing CO by coprecipitation2Active site vector:
1-1) dissolving soluble salt into deionized water to prepare solution A with the total ion concentration of 0.1-2 mol/L, wherein the soluble salt is Zn (NO)3)2·6H2O、Ce(NO3)3·6H2O、La(NO3)3·6H2O、SnCl4、Fe(NO3)3·9H2O、Al(NO3)3·9H2O、Ga(NO3)3·xH2O、Pb(NO3)2、Cu(NO3)2·2.5H2O、Bi(NO3)3·5H2One or more of O;
1-2) taking an ammonia water solution as a B solution;
1-3) pumping the solution A into a precipitation tank containing deionized water at the temperature of 30-50 ℃ at the rate of 2.5 mL/min;
1-4) adjusting the adding rate of the solution B to maintain the pH value in the precipitation tank to be 8 +/-0.2;
1-5) when the solution A is completely pumped into the precipitation tank, sequentially closing the peristaltic pumps used for conveying the solution A and the solution B to obtain slurry;
1-6) stirring the slurry under the conditions that the pH value is 8 +/-0.2 and the temperature is 30-50 ℃, repeatedly washing and filtering by using water and methanol to obtain a filter cake;
1-7) putting the obtained filter cake into an oven, and drying for 12 hours at the temperature of 90-110 ℃;
1-8) calcining the filter cake under flowing air: heating to 120 deg.C for 0.3 hr, heating to 550 deg.C at a heating rate of 3 deg.C/min, and holding for 4 hr to obtain a product containing CO2A carrier for the active site;
2) introduction of carbon-based activation sites into the CO-containing product obtained in step 1) by impregnation2Preparing a coal carbon dioxide gasification catalyst on a carrier of an active site:
2-1) the CO-containing product obtained in step 1)2Grinding the carrier of the active site into A powder;
2-2) dissolving magnesium nitrate hexahydrate or calcium nitrate tetrahydrate in deionized water to prepare a C solution with the concentration of 2-6 mol/L;
2-3) dipping the solution C on the powder A while stirring;
2-4) putting the dipped powder A into a drying furnace, and drying for 12 hours at 90-110 ℃;
2-5) repeating the steps 2-3) and 2-4) until all the C solution is soaked on the surface of the A powder, wherein 0.65-2 mL of the C solution is soaked in each g of the A powder;
2-6) calcining the impregnated A powder under flowing air: heating to 120 ℃ and maintaining for 0.5 hour, then heating to 600 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-7) naturally cooling to room temperature, and collecting a calcined product, wherein the calcined product is the powder C;
2-8) dissolving potassium nitrate in ionic water to prepare a transparent D solution with the concentration of 2-6 mol/L;
2-9) dipping the D solution on the C powder while stirring;
2-10) putting the impregnated C powder into a drying furnace, and drying for 12 hours at 90-110 ℃;
2-11) repeating the steps 2-9) and 2-10) until all the D solution is soaked on the surface of the C powder, wherein 0.65-1.5 mL of the D solution is soaked in each g of the C powder;
2-12) calcining the impregnated C powder under flowing air: firstly heating to 120 ℃ and maintaining for 0.5 hour, then heating to 800 ℃ at the heating rate of 3 ℃/min, and keeping for 3 hours;
2-13) naturally cooling to room temperature to obtain the coal carbon dioxide gasification catalyst.
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| CN113897224A (en) * | 2021-10-28 | 2022-01-07 | 河南工业大学 | Straw briquette fuel and carbon dioxide cooperative thermal conversion method |
| US11389787B2 (en) | 2019-02-20 | 2022-07-19 | Kara Technologies Inc. | Catalyst structure and method of upgrading hydrocarbons in the presence of the catalyst structure |
| US11725150B2 (en) | 2020-08-18 | 2023-08-15 | Kara Technologies Inc. | Method of light oil desulfurization in the presence of methane containing gas environment and catalyst structure |
| US12006475B2 (en) | 2020-08-26 | 2024-06-11 | Kara Technologies Inc. | Organic solid biomass conversion for liquid fuels/chemicals production in the presence of methane containing gas environment and catalyst structure |
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