CN1903431A - Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use - Google Patents
Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use Download PDFInfo
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- CN1903431A CN1903431A CNA2006100527886A CN200610052788A CN1903431A CN 1903431 A CN1903431 A CN 1903431A CN A2006100527886 A CNA2006100527886 A CN A2006100527886A CN 200610052788 A CN200610052788 A CN 200610052788A CN 1903431 A CN1903431 A CN 1903431A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000001257 hydrogen Substances 0.000 title claims abstract description 79
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 25
- 238000002407 reforming Methods 0.000 title abstract description 6
- 239000002994 raw material Substances 0.000 title description 3
- 239000000292 calcium oxide Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 22
- 238000000629 steam reforming Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000007603 infrared drying Methods 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 32
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006057 reforming reaction Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 description 42
- 238000001179 sorption measurement Methods 0.000 description 41
- 239000001569 carbon dioxide Substances 0.000 description 33
- 239000003463 adsorbent Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 15
- 239000011575 calcium Substances 0.000 description 14
- 238000003795 desorption Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000012854 evaluation process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QEVHRUUCFGRFIF-UHFFFAOYSA-N 6,18-dimethoxy-17-[oxo-(3,4,5-trimethoxyphenyl)methoxy]-1,3,11,12,14,15,16,17,18,19,20,21-dodecahydroyohimban-19-carboxylic acid methyl ester Chemical compound C1C2CN3CCC(C4=CC=C(OC)C=C4N4)=C4C3CC2C(C(=O)OC)C(OC)C1OC(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101100533283 Dictyostelium discoideum serp gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 Hydrogen Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
A composite catalyst for preparing hydrogen by reforming the CO2 adsorbed and intensified methane vapor is proportionally prepared from CaO, NiO and Al2O3 as carrier. It features that the heat generated by reaction between calcium oxide and CO2 is used to promote said reforming reaction. Its preparing process is also disclosed.
Description
Technical Field
The invention provides a composite catalyst which is prepared by directly compounding a catalyst containing an active nickel component and an adsorbent containing CaO as a main component and has a catalytic function and a carbon dioxide adsorption function and is used for strengthening a methane steam reforming hydrogen production process.
Background
The Steam Reforming of Methane to produce hydrogen reaction (SMR for short) is a strong endothermic reaction. The catalyst for steam reforming reaction of methane is prepared with nickel as active component and alumina as carrier and certain amount of cocatalyst and through precipitation, impregnation and mixing. The catalyst is applied to a fixed bed reactor, the reaction conditions are that the water/carbon ratio is 2.5-4.5, the reaction pressure is 4.5MPa, the first-stage conversion temperature is 600-800 ℃, the second-stage conversion temperature is 1000-1250 ℃, the methane conversion rate is 86% after the first-stage and second-stage conversion, and the balanced gas-phase hydrogen content is 71-75%. The CO produced as a by-product is converted into CO by primary and secondary conversion2While the hydrogen concentration is further increased. The used shift catalyst is a catalyst mainly comprising iron oxide, the temperature of a water-vapor shift reactor is 300-2The gas phase content is 15-20%. The gas generated in the conventional methane steam hydrogen production process needs to be further purified by Pressure Swing Adsorption (PSA) to obtain high-purity hydrogen. Therefore, a reforming reactor and two shift reactors are needed, the flow is long, the investment is large, and high reaction energy consumption and separation energy consumption are needed. The main reasons are high energy consumption caused by the characteristics of high-temperature strong endothermic reaction, energy consumption of CO shift reaction and CO byproduct2High energy consumption for separating and purifying hydrogen.
Steam reforming hydrogen production process (reforming Enhanced) Enhanced by carbon dioxide adsorptionReaction Process, SERP for short) is that catalyst and adsorbent are filled into one reactor to adsorb and eliminate carbon dioxide produced in steam reforming Reaction timely, and the Reaction may be performed at about 500 deg.c to lower Reaction temperature greatly and produce hydrogen in purity up to 95% in one pass, so as to lower the power consumption of hydrogen purification. In addition, the high purity CO produced by desorption during regeneration of the adsorbent2Can be comprehensively utilized, and the like.
The reaction formula of adsorption enhanced hydrogen production is as follows:
from the above formula, it can be seen that if sufficient CaO is present, the reaction does not substantially provide more heat. The adsorbent may be regenerated by thermal decomposition, the reaction formula being as follows:
if nano and micron calcium carbonate is used as a precursor for preparing CaO by thermal decomposition, the regeneration temperature can be reduced by about 200 ℃.
The adsorbent which is firstly adopted is a hydrotalcite adsorbent, and has theadvantages that carbon dioxide is adsorbed by a physical and chemical method, and the adsorbent can be regenerated by a pressure swing desorption method, but the fatal defect is low adsorption capacity, and researches report that the adsorption capacity of the adsorbent after 6000 times of adsorption and desorption cycles is 0.45mol/kg, so that the requirement of industrial application cannot be met.
The calcium oxide as the high-temperature carbon dioxide adsorbent is used for removing carbon dioxide by a method of reacting calcium oxide with carbon dioxide to form stable calcium carbonate. The adsorption capacity is greatly higher than that of hydrotalcite adsorbents, and the method shows wide application prospect.
Chinese patent application CN1676210 discloses a high-activity calcium-based CO2The absorbent and the preparation method thereof use alcohols, distilled water, aluminum salt and calcium oxide as raw materials; calcining for 1-4 hours at 800-1000 ℃; adding alcohol and distilled water; calcining the dried sample at 500-700 ℃ for 3 hours, and grinding; adding distilled water, and drying; calcining the dried sample at 700-1100 ℃ for 1-3 hours; grinding and grinding to obtain high-activity calcium-based CO2An absorbent. The carbon dioxide absorbent prepared by the method reduces the carbon dioxide absorption capacity to 40 percent gCO after 50 times of adsorption regeneration reaction cycles2Per gram of adsorbent.
In chem.eng.sci., 1999, 54: 3543 entitled "Hydrogen from methanein a single-step Process "by Balasubramanian A, Ortiz B, Kaytakoglu A L, and Harrison D P2The results of hydrogen production reports that the adsorbent and the powder nickel-based catalyst are mixed and filled show that the hydrogen production process can generate more than 80 percent of hydrogen, but the hydrogen is generated by calcium oxide-based CO2The use of adsorbent regeneration cycles has not been reported.
Chinese patent application CN1762572 discloses a silicon-containing nano calcium oxide high-temperature carbon dioxide adsorbent made of nano CaCO3Coating SiO by sol-gel method2Or nano CaCO3Directly react with nano SiO2The powder is evenly mixed to prepare the silicon-containing nano CaCO3The powder is mixed with forming agent to form and is calcined at the temperature of 600-800 ℃.
WU Su Fang, T.H.Beum, J.I.Yang, J.N.Kim research in Chinese J.chem.Eng., 13(1)43-47(2005) article entitled "the characteristics of a Sound-enhanced Stem-Methane Reaction for the production of Hydrogen2As an adsorbent for carbon dioxide, the lower the concentration of carbon dioxide remaining in the product vapor, the higher the methane conversion and hydrogen concentration. Ca (OH)2Particle size versus carbon dioxide and hydrogen concentration. The results of the studies show that the catalyst and Ca (OH)2In the presence of the catalyst, the hydrogen concentration reaches 94 percent, which is close to the upper limit of a theoretical value of 96 percent and greatly exceeds the result that the hydrogen concentration is 67.5 percent under the same condition without using a carbon dioxide adsorbent.
An adsorption separation enhanced automatic control process for methane steam reforming hydrogen production is disclosed in US 2004081614. The process comprises the following steps: introducing raw material gas containing hydrogen, water vapor, carbon monoxide and carbon dioxide into an adsorption-enhanced reactor containing a first adsorbent, a catalyst and a second adsorbent; contacting the feed gas with a first adsorbent to obtain CO2Reduced feed gas; obtained CO2Reduced feed gas to catalyst contact to produce CO2And H2A mixture of (a); themixture gas and the second adsorbent are mixed with catalystContacting the agent to produce a product gas, wherein H2Is greater than 50% by volume, CO2The percentage of the total volume of CO is less than 5%. The high-temperature adsorbent for preparing hydrogen by reforming methane steam with enhanced adsorption and separation is K2CO3Promoted hydrotalcite and the like.
However, in the existing technology for producing hydrogen by reforming water vapor with enhanced carbon dioxide adsorption, the catalyst and the adsorbent are simply filled in the same reactor, and are not integrated into a whole, so that the synergistic effect of the catalyst and the adsorbent is fully exerted.
Disclosure of Invention
The invention provides a composite catalyst which has both catalytic function and carbon dioxide adsorption function and is prepared by directly compounding a catalyst containing an active nickel component and an adsorbent containing a CaO main component.
A composite catalyst for methane steam reforming hydrogen production is mainly compounded by CaO taking micron-sized and/or nano-sized calcium carbonate and/or calcium hydroxide powder as a precursor, an active nickel component taking nickel carbonate, nickel oxide or nickel nitrate as a precursor and an alumina carrier, wherein the molar ratio of each component is as follows:
CaO∶NiO∶Al2O3＝1∶(0.1-2.0)∶(0.1-3.0)
the composite catalyst can also contain 0.01 to 0.2 mole of rectorite and/or 0.1 to 1.5 mole of SiO in terms of the mole number of CaO being 12Wherein SiO is2The precursor of (2) is silica sol with solid content of 5-40%.
Rectorite is a compound containing a plurality of metal oxide components such as: al (Al)2O3，SiO2，Na2O，MgO，K2O，Fe2O3，ZnO，TiO2，ZrO2，NbO，SrO，Y2O3The laminated pillar structure material of (1). Rectorite is a regular interlayer mineral of dioctahedral mica and dioctahedral montmorillonite 1: 1, and has a chemical general formula: kx(H2O){Al2[AlxSi4-xO10}(OH)2}, general structural formula is micaThe layer and the montmorillonite layer. Mica layer (Na)0.79K0.39Ca0.26)1.14Al4[Si6Al2]8O22Montmorillonite layer (Ca)0.55Na0.02K0.01Mg0.03)0.61(Al4.1Fe2+ 0.09Mg0.07)4.26[Si6.46Al1.54]8O22Currently, there are several companies that sell as commodities.
The preparation method of the composite catalyst comprises the steps of uniformly mixing all the components in proportion, and calcining after infrared drying, forming and drying or calcining after spray drying granulation.
Another preparation method of the composite catalyst comprises the steps of preparing components except the active nickel component precursor into particles, and using Ni (NO) with the mass percentage concentration of 1-50%3)2Impregnating the granules with the solution, calcining, or adding Ni (NO) with concentration of 1-50 wt%3)2In the aqueous solution, adjusting the pH value to 7-10 with saturated ammonia water solution to generate Ni (OH) on the particle surface2Precipitating and then bakingAnd (4) drying and calcining.
In the preparation process, alumina hydrosol with the solid content of 1-20 percent is used as a precursor of the alumina carrier.
The invention also provides the application of the composite catalyst in the hydrogen production by methane steam reforming. After the composite catalyst is filled into a reactor, methane, nitrogen, hydrogen and water vapor are introduced into the reactor to carry out single and multiple circulation hydrogen production, wherein the reactor is a fixed bed, a fluidized bed or a moving bed.
The process conditions are as follows:
methane space velocity (h)-1) 1-100
Water-carbon ratio of 2-6
Temperature (. degree. C.) 450-650
Pressure (MPa) 0.1-2.0
The composite catalyst is characterized by transmission electron microscope TEM analysis, and the result shows that the composite catalyst has obvious deep micropores after thermal decomposition pretreatment, and calcium carbonate generated by adsorbing carbon dioxide after thermal decomposition pretreatment has a spherical structure.
The catalyst is characterized by XRD, and the result shows that the catalytic components in the composite catalyst exist in the form of nickel andor nickel oxide, and the activity is better. CaCO as calcium3And part of Ca (OH)2In the presence of Ca, some of the calcium forms with the aluminum12Al14O33The structure of the catalyst enhances the strength of the catalyst and increases the stability of the adsorption and desorption recycling process.
By summarizing the trend of the composition of the reaction product gas over time, it was shown that the maximum content of hydrogen production was greater than 94% and the methane conversion was calculated to be greater than 92%.
The invention has the advantages that:
1. the composite catalyst prepared by the invention, which is characterized by containing calcium oxide and nickel, can effectively utilize heat generated by the reaction of calcium oxide and carbon dioxide to promote the strongly endothermic steam reforming hydrogen production reaction. The composite catalyst is beneficial to the release and absorption of heat inside the composite catalyst, the internal diffusion and heat transfer obstruction is reduced to the maximum extent, and the heat transfer loss is reduced.
2. The composite catalyst prepared by the invention, which is characterized by containing calcium oxide and nickel, can avoid density difference caused by mixed filling of an adsorbent and the catalyst, and can be used for producing hydrogen in a fixed bed, a fluidized bed and a moving bed reactor, so that the process flow design is simple and the process operation is stable.
3. The composite catalyst simultaneously keeps high catalytic activity and high carbon dioxide adsorption rate, and has the recycling stability of carbon dioxide adsorption and desorption regeneration.
4. The composite catalyst is not only used in the single cycle process of hydrogen production by methane steam reforming and carbon dioxide desorption regeneration through carbon dioxide adsorption enhancement, but also can be used in the multiple cycle process of hydrogen production by methane steam hydrogen production and carbon dioxide desorption regeneration through carbon dioxide adsorption enhancement.
Drawings
TEM (Transmission Electron microscope) photograph of composite catalyst (CA-1) in FIG. 1 without regeneration
FIG. 2 TEM photograph of 20 cycles of reaction of CA-1-numbered composite catalyst
XRD spectrum of composite catalyst numbered CA-1 in figure 3
XRD spectrum of composite catalyst numbered CA-2 in figure 4
In fig. 3 and 4:
1 represents Ca12Al14O33Diffraction peak
2 represents CaCO3Diffraction peak
3 represents Al2O3Diffraction peak
4 represents a Ni diffraction peak
5 represents Ca (OH)2Diffraction peak
FIG. 5 shows the results of the adsorption rate and the number of cycles of the CA-3 composite catalyst measured by a fixed bed evaluation apparatus.
X-axis represents cycle number of 600 ℃ adsorption and 830 ℃ desorption
Y-axis represents the carbon dioxide adsorption rate of the composite catalyst
The composite catalyst contains CaO 63.7%, Al2O332.5％，NiO 1.0％。
FIG. 6 shows the cyclic adsorption rates of three different composite catalysts TG of the CAN series.
X-axis represents cycle number of 600 ℃ adsorption and 830 ℃ desorption
Y-axis represents the carbon dioxide adsorption rate of the composite catalyst
e-line represents the composite catalyst CAN-1
Line f represents the composite catalyst CAN-2
g line represents composite catalyst CAN-3
FIG. 7 is a schematic diagram of an evaluation process for hydrogen production
FIG. 8 is a time-dependent trend graph of various components in the outlet gas of the hydrogen plant
Detailed Description
Example 1 composite catalyst preparation
Firstly, adding 15g of nano calcium carbonate powder into a beaker, then adding 70ml of alumina-hydrosol with the solid content of 10%, adding a small amount of water, stirring and mixing uniformly, adding 15g of nickel carbonate powder, mixing uniformly, drying by infrared, extruding into strips, forming, drying and calcining to prepare the composite catalyst CA-1. Referring to fig. 1 and 2, the catalyst is characterized by TEM analysis of a transmission electron microscope, and the result shows that the composite catalyst after the thermal decomposition pretreatment has obvious deep micropores, and calcium carbonate generated by absorbing carbon dioxide with CaO after the thermal decomposition pretreatment has a spherical structure.
The catalyst is characterized by XRD, and the result shows that the catalytic components in the composite catalyst exist in nickel and nickel oxide, so that the activity is better. CaCO as calcium3And part of Ca (OH)2In the presence of Ca, some of the calcium forms with the aluminum12Al14O33The structure of the catalyst enhances the strength of the catalyst and increases the stability of the adsorption and desorption recycling process.
Example 2 composite catalyst preparation
Firstly, 10g of micron calcium hydroxide powder is added into a beaker, and then 70ml of alumina hydrosol with the solid content of 8 percent is added into the beaker, and the mixture is stirred and mixed evenly. Adding nickel carbonate powder with a particle size less than 100 meshes, uniformly mixing, carrying out infrared drying, extruding into strips, forming, drying and calcining to obtain the composite catalyst CA-2.
Example 3 composite catalyst preparation
Firstly, adding 5g of nano calcium carbonate powder into a beaker, then adding 35ml of alumina hydrosol with the solid content of 10%, adding a small amount of water, stirring and uniformly mixing, adding 10ml of saturated nickel nitrate salt solution, uniformly mixing, and then carrying out spray drying granulation and calcination to obtain the composite catalyst powder CA-3 with the particle size of 20-100 microns.
The catalyst is characterized by XRD, and the result shows that the catalytic component in the composite catalyst exists in nickel and has better activity. CaCO as calcium3And part of Ca (OH)2In the presence of Ca, some of the calcium forms with the aluminum12Al14O33The structure of the catalyst enhances the strength of the catalyst and increases the stability of the adsorption and desorption recycling process.
Example 4 composite catalyst preparation
Firstly, adding 15g of nano calcium carbonate powder, 25g of silica sol with the solid content of 20 percent into a beaker, adding a proper amount of water, uniformly mixing after stirring, carrying out infrared drying, extruding, forming and drying to obtain columnar particles. Mixing 10g of Ni (NO)3)2.6H2Dissolving O in 10ml water, dripping the formed particles, soaking at normal temperature for 24 hours, filtering, drying, calcining at 550 ℃ for 5 hours, and cooling to room temperature for later use.
Example 5 composite catalyst preparation
Firstly, adding 5g of nano calcium carbonate powder into a beaker, then adding 30g of alumina hydrosol with the solid content of 10%, adding a small amount of water, stirring and mixing uniformly, adding 5g of nickel carbonate powder, adding 1g of rectorite powder, mixing uniformly, carrying out infrared drying, and preparing into a spherical, dried and calcined composite catalyst CAN-1.
Example 6 composite catalyst preparation
Adding 3g of nano calcium carbonate powder and 2g of calcium hydroxide powder into a beaker, then adding 30g of alumina hydrosol with the solid content of 10%, adding a small amount of water, stirring and uniformly mixing, adding 5g of nickel oxide powder, adding 1g of rectorite powder, uniformly mixing, carrying out infrared drying, extruding, forming, drying and calcining to obtain the composite catalyst CAN-2.
Example 7 composite catalyst preparation
Adding 3.8g of calcium hydroxide powder into a beaker, then adding 30g of alumina hydrosol with the solid content of 10%, adding a small amount of water, stirring and uniformly mixing, then adding 5g of powder containing nickel carbonate, adding 1g of rectorite powder, uniformly mixing, carrying out infrared drying, balling, drying and calcining to obtain the composite catalyst CAN-3.
Example 8 carbon dioxide adsorption with composite catalyst for enhanced methane steam reforming to produce hydrogen
After the composite catalyst is filled into a reactor, methane, nitrogen, hydrogen and water vapor are introduced into the reactor to produce hydrogen, the flow rate of the methane is 20ml/min, the water-carbon ratio is 5, the temperature is 600 ℃, the pressure is 0.2MPa, the mass of the composite catalyst CA-1 is 23.3g, the content of the prepared hydrogen is up to 94.9 percent, the concentration of CO is 0.13 percent, and the CO content is up to 0.13 percent2The concentration is 2.99%, after the adsorbent is saturated, the hydrogen concentration is 74.51%, the CO concentration is 4.10%, and the CO concentration is2The concentration was 14.87%.
Example 9 carbon dioxide adsorption enhanced methane steam reforming with composite catalyst to produce hydrogen
After the composite catalyst is filled into a reactor, methane, nitrogen, hydrogen and water vapor are introduced into the reactor to produce hydrogen, the flow rate of the methane is 20ml/min, the water-carbon ratio is 4, the temperature is 650 ℃, the pressure is 0.2MPa, the mass of the composite catalyst CA-2 is 20.1g, the content of the prepared hydrogen is up to 94.6 percent, the concentration of CO is 0.03 percent, and the CO content is 0.03 percent2Concentration 4.39%, concentration of hydrogen after adsorption equilibrium 76.01%, concentration of CO 1.66%, CO2The concentration was 15.18%.
Example 10 carbon dioxide adsorption with composite catalyst for enhanced methane steam reforming to produce hydrogen
After the composite catalyst is filled into a reactor, methane, nitrogen, hydrogen and water vapor are introduced into the reactor to produce hydrogen, the flow rate of the methane is 30ml/min, the water-carbon ratio is 3, the temperature is 600 ℃, the pressure is 0.2MPa, the mass of the composite catalyst CA-3 is 17.8g, the content of the prepared hydrogen is 88.07% at most, the concentration of CO is 3.51%, and the CO content is 3.51%2Concentration 4.54%, concentration of hydrogen 73.52%, concentration of CO 2.84%, and concentration of CO after adsorption equilibrium2The concentration was 14.75%.
Example 11 carbon dioxide adsorption enhanced methane steam reforming with composite catalyst to produce hydrogen
After the composite catalyst is filled into a reactor, methane, nitrogen, hydrogen and water vapor are introduced into the reactor to produce hydrogen, the flow rate of the methane is 20ml/min, the water-carbon ratio is 6, the temperature is 600 ℃, the pressure is 0.2MPa, the mass of the composite catalyst CA-1 is 15g, the content of the prepared hydrogen is 91.31 percent at most, the concentration of CO is 0.12 percent, and the CO content is 15 percent at most2Concentration 3.51%, concentration of hydrogen after adsorption equilibrium 74.56%, concentration of CO 2.56%, and CO2The concentration was 14.80%.
Example 12 evaluation of the performance of adsorption and desorption cycles of a composite catalyst by a fixed bed
The evaluation method comprises the following steps: 15g of the composite catalyst CA-3 was charged into a fixed bed reactor having an inner diameter of 15mm, and N was introduced at 40/min2Controlling the temperature rise rate of the reactor, desorbing at the constant temperature of 830 ℃ for 20min, keeping the temperature of the desorbed adsorbent at 600 ℃, and introducing CO at 20ml/min2Gas until adsorption is saturated. The calculation formula is as follows:
the evaluation results are shown in FIG. 5, which shows the relationship between the number of adsorption cycles and the adsorption rate of the CA-3 composite catalyst.
Example 13 evaluation of Performance of adsorption/desorption cycle of composite catalyst by TG
The evaluation method comprises the following steps: respectively taking 5mg of composite catalysts CAN-1, CAN-2 and CAN-3, filling the compositecatalysts CAN-1, CAN-2 and CAN-3 into a TG sample basket, and introducing N at the rate of 20ml/min2Controlling the temperature rise rate of the reactor, desorbing at 830 deg.C for 5min, keeping the desorbed adsorbent at 600 deg.C, and introducing CO at 20ml/min2And adsorbing the gas for 30min until the adsorption is saturated. The calculation formula is as follows:
the evaluation results are shown in the relation between the circulating adsorption times and the adsorption rates of three different composite catalysts, namely CAN-1, CAN-2 and CAN-3 in figure 6.
Example 14 evaluation of hydrogen production by fixed bed composite catalyst
Hydrogen production evaluation process:
1. CaCO pretreated by thermal decomposition at 830 DEG C3To CaO
2. The NiO-containing catalyst is reduced into simple substance Ni by hydrogen
3. 600 ℃ adsorption-enhanced methane steam reforming hydrogen production reaction
Evaluation step: (refer to the schematic diagram of the evaluation flow of the hydrogen production plant in FIG. 7) the flow rates of methane, nitrogen and hydrogen were controlled by three mass flow meters, respectively. The water vapor is injected by a precise liquid phase pump, and the water is mixed with methane after being vaporized by a heating zone and enters a reaction fixed bed. The reactor consists of a heating device and a reaction tube, the length of the reaction tube is 590mm, the inner diameter of the reaction tube is 15mm, the composite catalyst is filled in the middle of the reaction tube, the upper part and the lower part ofthe reaction tube are filled with filler, the detection part mainly comprises an outlet gas flowmeter, and the reaction gas is analyzed by a gas chromatograph for the content of each component of the gas phase.
The conversion rate of the reaction can be calculated according to the methane content of the outlet gas (see the time-varying trend of each component in the outlet gas comprising hydrogen, methane and carbon dioxide in figure 8), and the selectivity of the hydrogen can be calculated according to the product gas content of the outlet gas.
Example 15 composite catalyst for hydrogen production evaluation
Adopts a balanced complexing agent (containing 22.5 percent of CaO and Al)2O321.3% and NiO 12.18%) of 8.5g, hydrogen production was evaluated under the operating conditions of a hydrogen production reaction temperature of 600 ℃, a reaction pressure of 0.2MPa, a methane flow rate of 20ml/min, a water-carbon ratio of 6 and a thermal decomposition regeneration temperature of 830 ℃ (see the schematic diagram of the evaluation flow of the hydrogen production apparatus in FIG. 7), and hydrogen production results of 93.5% hydrogen concentration, 0.13% CO concentration, and a CO concentration were obtained2The concentration is 2.99%.
Claims (6)
1. A composite catalyst for methane steam reforming hydrogen production is mainly compounded by CaO taking micron-sized and/or nano-sized calcium carbonate and/or calcium hydroxide powder as a precursor, an active nickel component taking nickel carbonate, nickel oxide or nickel nitrate as a precursor and an alumina carrier, wherein the molar ratio of each component is as follows:
CaO∶NiO∶Al2O3＝1∶(0.1-2.0)∶(0.1-3.0)
2. the composite catalyst of claim 1, wherein: based on the mol number of CaO as 1, the component also contains 0.01 to 0.2 mol of rectorite and/or 0.1 to 1.5 mol of SiO2Wherein SiO is2The precursor is silica sol with solid content of 5-40%。
3. The method for preparing a composite catalyst according to claims 1 and 2, wherein: the components are mixed uniformly according to a certain proportion, and then are calcined after infrared drying, forming and drying or calcined after spray drying granulation.
4. The method for preparing a composite catalyst according to claims 1 and 2, wherein: preparing the components except the active nickel component precursor into particles by using Ni (NO) with the mass percent concentration of 1-50%3)2Impregnating the granules with water solution, calcining, or adding Ni (NO) with concentration of 1-50 wt%3)2In the aqueous solution, adjusting the pH value to 7-10 with saturated ammonia water to generate Ni (OH) on the particle surface2And drying and calcining after precipitation.
5. Use of the composite catalyst of claims 1 and 2 in the production of hydrogen by steam reforming of methane.
6. The use of the composite catalyst of claim 5 in the production of hydrogen by steam reforming of methane, wherein: after the composite catalyst is filled into a reactor, introducing methane, nitrogen, hydrogen and water vapor into the reactor to carry out circular hydrogen production, wherein the reactor is a fixed bed, a fluidized bed or a moving bed.
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