CN115888754B - Preparation method of catalyst for preparing hydrogen by reforming methanol with low copper content - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000010949 copper Substances 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 238000002407 reforming Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000012691 Cu precursor Substances 0.000 claims abstract description 29
- 239000004927 clay Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 26
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001099 ammonium carbonate Substances 0.000 claims description 18
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 13
- 239000001095 magnesium carbonate Substances 0.000 claims description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 13
- 239000011656 manganese carbonate Substances 0.000 claims description 13
- 235000006748 manganese carbonate Nutrition 0.000 claims description 13
- 229940093474 manganese carbonate Drugs 0.000 claims description 13
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 13
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims 1
- XNSKKUNEEJOCLU-UHFFFAOYSA-N copper methanol Chemical compound [Cu+2].OC XNSKKUNEEJOCLU-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000012018 catalyst precursor Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000008247 solid mixture Substances 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 239000011701 zinc Substances 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 9
- 229910001919 chlorite Inorganic materials 0.000 description 8
- 229910052619 chlorite group Inorganic materials 0.000 description 8
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 241000907663 Siproeta stelenes Species 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 5
- 229940116318 copper carbonate Drugs 0.000 description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a catalyst for preparing hydrogen by reforming methanol with low copper content, belonging to the technical field of catalysis. The invention solves the problems of high cost and poor thermal stability caused by high copper content of the existing methanol reforming hydrogen production catalyst, and the preparation method comprises the following steps: uniformly mixing a low-copper precursor, clay and an auxiliary agent according to a certain proportion to obtain a solid mixture, adding a pore-forming agent and a proper amount of water into the solid mixture, grinding, and tabletting by using a die with the diameter of 5mm to obtain a catalyst precursor; and then roasting the precursor for 6 hours in an air atmosphere at 200-260 ℃ to obtain the catalyst for preparing hydrogen by reforming methanol with low copper content. The cost of the catalyst for preparing hydrogen by reforming methanol with low copper content is reduced by 50% compared with that of commercial catalyst, and the catalyst has the advantages of high mechanical strength, high catalytic activity and good heat resistance, and can be applied to the process of preparing hydrogen by reforming methanol and water vapor.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for preparing hydrogen by catalytic reforming of methanol and steam and a preparation method thereof.
Background
The hydrogen energy is a clean energy with high energy supply efficiency, and has wide development prospect in recent years under the large background of coping with global climate problems and promoting global green economy development.
Among various hydrogen production methods, the methanol reforming hydrogen production process gradually becomes one of the processes which are mainly developed in the hydrogen production field due to a series of advantages of easy storage and transportation of raw materials, low energy consumption, high hydrogen production rate and the like. The core of the methanol reforming hydrogen production process is a catalyst, and the copper-based catalyst has better activity and mature preparation process and is widely used for the catalytic reaction of the methanol reforming hydrogen production.
The copper-based catalyst for preparing hydrogen by reforming methanol used in the industry still has the problems of high preparation cost, poor thermal stability and the like. The literature (Broecker F.J, gruendler K.H, marosi L, et al, US:4436833,1984,03 13) adopts a coprecipitation method to obtain a mixed crystal of Cu 2.2Zn2.8(OH)6(CO3)2, and a copper-based precursor is obtained after calcination to prepare a copper-based catalyst, but a large amount of copper nitrate raw material is required to be input, so that the preparation cost is extremely high; the preparation method research of C306 methanol synthesis catalyst of south China (Hong Chuanqing, enemy winter, cao Jianping, et al) and the industrial effect [ J ]. Fuel chemistry report, 2001,29 (4): 5.) are also utilized to carry out coprecipitation by using a nitrate solution of copper and zinc to prepare a copper-zinc matrix, and then the copper-zinc matrix is mixed with an auxiliary agent and baked to obtain a copper-based precursor, so that the copper-based catalyst with the CuO of more than or equal to 54wt% and high copper content is prepared.
Meanwhile, literature (Ki-Won Jun, wen-Jie Shen1, K.S Rama Rao, et al applied CATALYSIS A: general,1998,174 (1-2): 231-238) shows that Cu Hu ttig temperature is low and that the thermal stability is poor; if the copper component cannot be well dispersed in the catalyst, the active component Cu is easy to sinter and grow up in the reaction process, so that the active surface area is reduced, the catalytic performance is reduced, and the precursor prepared industrially contains a large amount of malachite, so that CuO crystal grains formed after the malachite is roasted and decomposed are easy to migrate and agglomerate, and the catalytic performance is also reduced. The above all become the main reasons for poor heat stability of the catalysis of the industrial copper-based catalyst with high copper content. Thus, there is currently a lack of a copper-based catalyst with low copper content and high stability.
In addition, industrial catalysts are mostly formed by tabletting, and higher tabletting pressure is adopted to improve the strength of the catalyst. However, catalyst tableting has a problem such as the effect of pore structure on selectivity for low pressure synthesis of gas to methanol [ J ]. University chemical engineering report, 2015,29 (05): 1114-1119.) studied the influence relationship of catalyst tableting and catalyst pore structure, and the results showed that the tableting pressure was increased, the catalyst pore volume and pore diameter were decreased, and the internal diffusion resistance was increased, resulting in a decrease in reaction conversion. Therefore, how to ensure a higher reaction conversion rate of the catalyst after tabletting under a higher pressure while maintaining a higher mechanical strength is a big problem to be solved in the current industrial catalyst production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a catalyst for preparing hydrogen by reforming methanol with low copper content. The invention mixes a low copper precursor, clay and auxiliary agent, adds pore-forming agent, and forms by tabletting, and prepares the catalyst for preparing hydrogen by reforming methanol with low copper content after roasting; the copper oxide content in the catalyst prepared by the method is 23-28 wt%, which is far lower than the copper oxide content in the industrial catalyst of 60-65 wt%, so that the raw material cost is obviously reduced; the low copper precursor of the catalyst is a CuO/ZnO mixture, and copper and zinc are highly dispersed and have synergistic effect, so that the catalytic activity and stability of the catalyst are improved; according to the invention, by adding a proper auxiliary agent and improving the condition of tabletting pressure, the negative influence caused by tabletting pressure is solved, meanwhile, the mechanical strength of the catalyst is synergistically improved by adding clay, and the performance of the catalyst pore structure is improved by adding a pore-forming agent; the catalyst for preparing hydrogen by reforming methanol with low copper content is suitable for a system for preparing hydrogen by reforming methanol and water vapor.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a catalyst for preparing hydrogen by reforming methanol with low copper content comprises the following steps:
Firstly, a low copper precursor, clay and an auxiliary agent are mixed according to the mass percentage of 75% -85%:10% -20%: uniformly mixing 5% -10% to obtain catalyst powder, wherein the sum of the weight percentages of all components in the catalyst powder is 100%; adding pore-forming agent and proper amount of water into the catalyst powder, grinding, transferring into a tablet press, using a die with the diameter of 5mm, and tabletting under the pressure of 10-15 MPa to obtain a precursor of the catalyst; the low-copper precursor is a CuO/ZnO mixture obtained by roasting pure copperas Cu 2Zn3(OH)6(CO3)2 at 350 ℃; the auxiliary agent is a mixture of manganese carbonate, magnesium carbonate and active carbon; the pore-forming agent is one or any combination of ammonium carbonate and ammonium bicarbonate.
And secondly, transferring the precursor of the catalyst to a muffle furnace, and roasting for 6 hours in an air atmosphere at 200-260 ℃ to obtain the catalyst for preparing the hydrogen by reforming the methanol with low copper content. By roasting under certain conditions, the pore-forming agent in the catalyst can be decomposed, and the clay can be promoted to improve the strength of the catalyst.
Further, the preparation method of the low copper precursor in the step (one) comprises the following steps: the mass ratio is 1:1.2:1, weighing basic zinc carbonate, 28% concentrated ammonia water and ammonium carbonate, adding a proper amount of water, stirring and dissolving to prepare a zinc ammonia complex solution with C Zn =2.0 mol/L; transferring zinc ammonia complex liquid into a reactor, heating the reactor to 85 ℃ in a water bath under stirring, controlling the vacuum degree in the reactor to 8kpa, and firstly, according to the molar ratio of zinc to copper in the zinc ammonia complex liquid of 2:1 adding basic copper carbonate for reaction, sampling and analyzing the concentration (mol/L) of copper and zinc in the solution every 10min, and supplementing the basic copper carbonate to ensure that the molar ratio of copper to zinc in the solution is 0.7:1, carrying out precipitation reaction, after zinc ion precipitation is finished, carrying out suction filtration on the precipitate, eluting with water to remove residual ammonia complex, and drying at 85 ℃ for 15 hours to obtain a product of pure copperas; and roasting the pure copperzinc ore for 3 hours in an air atmosphere at 350 ℃ to obtain a CuO/ZnO mixture, namely a low copper precursor.
Further, the CuO/ZnO mixture has a CuO content of 31wt% to 32wt%. According to the invention, the pure copperzinc ore is self-made by controlling the proportion of the reaction raw materials and the reaction conditions, and the low-copper precursor with low copper content can be obtained after roasting under certain conditions, so that a foundation is laid for the subsequent preparation of the catalyst with low copper content.
Further, the clay is metakaolin.
Further, the auxiliary agent is a mixture of manganese carbonate, magnesium carbonate and active carbon, and the mass ratio of the manganese carbonate to the magnesium carbonate to the active carbon in the auxiliary agent is 1: (0.5-1): (0.15-0.2), wherein the addition agent accounts for 5-10% of the mass of the catalyst powder. The manganese carbonate is used as an auxiliary agent of the catalyst, so that the catalytic activity can be improved, the strength of the catalyst can be enhanced by the cooperation of the magnesium carbonate and clay, the specific surface area of the catalyst can be improved by the activated carbon, and the comprehensive performance of the catalyst is improved by the cooperation of the components.
Further, the pore-forming agent is one or any combination of ammonium carbonate and ammonium bicarbonate, and the dosage of the pore-forming agent is 0.05-0.08 times of the mass of the catalyst powder. The ammonium carbonate and the ammonium bicarbonate are used for the pore-forming agent of the catalyst, and after being pressed into tablets, the pore-forming agent is decomposed into a certain pore structure by roasting, so that the internal diffusion performance of the catalyst is improved, and the catalytic performance of the catalyst is improved.
The copper oxide content of the catalyst for preparing hydrogen by reforming methanol with low copper content prepared by the preparation method is 23-28 wt%.
The low copper content catalyst for preparing hydrogen by reforming methanol prepared by the preparation method is applied to the hydrogen preparation process by reforming methanol and steam, and the operation conditions used are as follows: the reaction temperature is 200-280 ℃, the pressure is 0.1-3.0MPa, the mass airspeed is 1.0-4.0H -1, and the raw material is H 2O/CH3OH(CH3 OH:50 wt%) of the solution.
The invention has the following beneficial effects:
(1) The catalyst for reforming methanol prepared by mixing and tabletting the low copper precursor, clay and auxiliary agent has the copper oxide content of 23-28 wt%, and solves the problems of high copper raw material input cost and poor catalytic heat-resistant stability of the catalyst caused by high copper content in the process of preparing the industrial catalyst for reforming methanol to prepare hydrogen by using 60-65 wt% of copper oxide.
(2) The catalyst for preparing hydrogen by reforming methanol with low copper content has high mechanical strength, good thermal stability and activity, and is not easy to sinter at high temperature, thus prolonging the service life of the catalyst.
Drawings
Fig. 1 shows XRD diffractogram of the prepared chlorite according to the present invention, wherein ∈is the chlorite, and the diffraction characteristics of no malachite are shown in the chlorite.
Fig. 2 shows XRD diffractograms of low copper precursors of the present invention, ■ being copper oxide and +.i. zinc oxide, as can be seen, the precursors conform to the diffraction characteristics of CuO and ZnO.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples.
Example 1
150.0G of basic zinc carbonate, 180.0g of concentrated ammonia water with the mass concentration of 28% and 150.0g of ammonium carbonate are weighed, zinc ammonia complex solution with the concentration of C Zn =2.0 mol/L is prepared by stirring and dissolving, the zinc ammonia complex solution is added into a reactor, the temperature is raised to 85 ℃ in a water bath under stirring, after the vacuum degree in the reactor is controlled to be 8kpa, 48.6g of basic copper carbonate is added for reaction, and the concentration (mol/L) of the copper and the zinc in the solution is sampled and analyzed every 10min in the process, so that the basic copper carbonate is supplemented to ensure that the molar ratio of the copper to the zinc in the solution is 0.7:1, carrying out precipitation reaction, after zinc ion precipitation is finished, carrying out suction filtration on the precipitate, washing the precipitate with water to remove residual copper ammonia complex, and drying the precipitate at 85 ℃ for 15 hours to obtain a product of copperas; to confirm that the precipitated phases were consistent with the chlorite, the products were subjected to XRD diffractometry and the results are shown in figure 1. The CuO/ZnO mixture obtained by roasting the above-mentioned green copper zinc ore for 3 hours in an air atmosphere at 350 ℃, namely a low copper precursor, is subjected to XRD diffraction characterization, and the result is shown in figure 2.
Weighing 102.0g of the low copper precursor, 12.0g of clay, 3.64g of manganese carbonate, 1.82g of magnesium carbonate and 0.54g of activated carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a precursor of the catalyst with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-1 for preparing the hydrogen by reforming the methanol with low copper content.
Comparative example 1
For comparison with commercial catalysts for producing hydrogen by reforming methanol in the market, commercial CuZnAl catalysts widely used in the market are purchased from a large-scale company in China, and product inspection reports show that copper oxide accounts for 64%, auxiliaries such as ZnO, al 2O3 and the like account for 36%, the size is phi 5 multiplied by 4 to 6mm, and the catalyst is marked as CuZnAl.
The related test results are shown in Table 1, and it can be seen that the low copper content methanol reforming hydrogen production catalyst prepared in example 1 has significantly better mechanical strength and heat resistance stability than the commercial CuZnAl catalyst widely used in the market at present; meanwhile, the cost of the catalyst for preparing hydrogen by reforming methanol with low copper content prepared by the invention is reduced by 50 percent compared with that of a commercial catalyst. In order to show the influence of the proportion of clay on the catalyst performance, specific example 2 is shown, and the catalyst prepared without clay is shown in example 3.
Example 2
Preparation of low copper precursor the same as in example 1; weighing 90.0g of the low copper precursor, 24.0g of clay, 3.64g of manganese carbonate, 1.82g of magnesium carbonate and 0.54g of activated carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-2 for preparing the hydrogen by reforming the methanol with low copper content.
Example 3
Preparation of low copper precursor the same as in example 1; 114.0g of the low copper precursor, 3.64g of manganese carbonate, 1.82g of magnesium carbonate and 0.54g of active carbon are weighed and mixed for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-3 for preparing the hydrogen by reforming the methanol with low copper content.
The results are shown in Table 1, and it can be seen that the low copper catalyst prepared in example 2 has better mechanical strength and heat stability than the catalyst prepared in example 1 and the catalyst prepared in example 3 without clay addition; in order to show that the catalyst prepared from the low-copper precursor obtained after the chlorite containing the malachite is roasted at 350 ℃ has poor catalytic performance, and the catalyst is specifically shown in the example 4.
Example 4
The preparation of the chlorite was the same as in example 1; weighing 95g of the copperzinc ore and 5g of malachite (basic copper carbonate), mechanically mixing uniformly, mechanically ball-milling for 30min, and roasting for 3h in an air atmosphere at 350 ℃ to obtain a CuO/ZnO mixture, namely a low copper precursor; weighing 96.0g of the low copper precursor, 18.0g of clay, 3.64g of manganese carbonate, 1.82g of magnesium carbonate and 0.54g of activated carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-4 for preparing the hydrogen by reforming the methanol with low copper content.
The results are shown in Table 1, and it can be seen that the catalyst prepared in example 4 uses a low copper precursor obtained by roasting the chlorite containing malachite, and the catalytic activity and the heat resistance stability of the catalyst are lower than those of the catalyst prepared in example 1; in order to show the influence of the proportion of the auxiliary agent on the catalyst performance, specific examples are shown in example 5 and example 6, and the catalyst prepared without the auxiliary agent is shown in example 7.
Example 5
Preparation of low copper precursor the same as in example 1; weighing 102.0g of the low-copper precursor, 12.0g of clay, 4.91g of manganese carbonate and 1.09g of active carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-5 for preparing the hydrogen by reforming the methanol with low copper content.
Example 6
Preparation of low copper precursor the same as in example 1; weighing 96.0g of the low copper precursor, 12.0g of clay, 5.58g of manganese carbonate, 5.58g of magnesium carbonate and 0.84g of activated carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-6 for preparing the hydrogen by reforming the methanol with low copper content.
Example 7
Preparation of low copper precursor the same as in example 1; weighing 108.0g of the low-copper precursor and 12.0g of clay, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 6.0g of ammonium carbonate, adding 12.0g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 12Mpa by using a die with the aperture of 5mm to obtain a catalyst precursor with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 200 ℃ to obtain the catalyst cat-7 for preparing the hydrogen by reforming the methanol with low copper content.
The results are shown in Table 1, and it can be seen that after the ratio of the auxiliary agent in the catalyst is increased, the mechanical strength and heat-resistant stability of the catalyst prepared in example 6 are better than those of the catalyst prepared in example 1, the auxiliary agent in example 5 is not added with magnesium carbonate, the mechanical strength and heat-resistant stability of the catalyst prepared in example 6 are lower than those of the catalyst prepared in example 7 without adding the auxiliary agent, and the mechanical strength and heat-resistant stability of the catalyst prepared in example 7 are lower than those of the catalyst prepared in examples 5 and 6.
Example 8
The preparation of the chlorite was the same as in example 1; weighing 102.0g of the low copper precursor, 12.0g of clay, 3.64g of manganese carbonate, 1.82g of magnesium carbonate and 0.54g of activated carbon, and mixing for 30min by a three-dimensional mixer to obtain uniform catalyst powder; weighing 9.6g of ammonium bicarbonate, adding 8.4g of distilled water to prepare a pore-forming agent solution, adding the pore-forming agent solution into the catalyst powder, mechanically mixing and grinding for 20min, transferring into a tablet press for tablet forming, and tabletting under the pressure of 15Mpa by using a die with the aperture of 5mm to obtain a precursor of the catalyst with phi of 5mm multiplied by 4 mm; transferring the precursor to a muffle furnace, and roasting for 6h in an air atmosphere at 260 ℃ to obtain the catalyst cat-8 for preparing the hydrogen by reforming the methanol with low copper content.
The results are shown in Table 1, and in example 8, the tabletting pressure, the pore-forming agent proportion and the roasting temperature are correspondingly improved within the setting range of the invention, the mechanical strength and the heat-resistant stability of the prepared catalyst are better than those of example 1.
In the present invention, the catalytic activity test: the activity evaluation of the catalyst was carried out on a micro fixed bed reactor. The granularity of the catalyst is 20-40 meshes, and the loading amount is 5.0g; before the catalyst is used, H 2/N2 mixed gas containing 5%H 2 is used for in-situ reduction in a reactor, and the final reduction temperature is 230 ℃; the pressure is 0.3Mpa, the mass space velocity is 2.5h -1,H2O/CH3OH(CH3 OH:50wt percent of raw material reaction liquid, wherein the evaluation temperature is 260 ℃, and the initial performance is determined as a result after the reaction is stable for 12 hours; then heating to 305 ℃ and resisting heat for 8 hours, recovering to the initial activity evaluation condition, and stabilizing the measurement result after 10 hours to obtain the activity after high-temperature reaction, wherein the product is analyzed by gas-liquid chromatography; the evaluation results are shown in Table 1.
In the invention, the content of copper oxide in the catalyst is determined: accurately weighing 1.00g of catalyst, dissolving the catalyst by using 10% nitric acid solution, finally fixing the volume in a 1000ml volumetric flask, and calculating the copper concentration of the solution by ICP-MS, wherein the unit is: wt% (mass fraction); the evaluation results are shown in Table 1.
In the invention, the mechanical strength of the catalyst refers to the radial strength of the catalyst, and is measured by a particle strength tester, and the unit is: n/cm; the evaluation results are shown in Table 1.
Table 1 shows the mechanical strength of the catalyst and the results of performance evaluation in the methanol reforming hydrogen production reaction.
While the invention has been described with reference to the preferred embodiments, it is not intended to limit the invention thereto, and it is to be understood that other modifications and improvements may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. The preparation method of the catalyst for preparing hydrogen by reforming methanol with low copper content is characterized by comprising the following steps:
Firstly, a low copper precursor, clay and an auxiliary agent are mixed according to the mass percentage of 75% -85%:10% -20%: uniformly mixing 5% -10% to obtain catalyst powder, wherein the sum of the weight percentages of all components in the catalyst powder is 100%; adding pore-forming agent and proper amount of water into the catalyst powder, grinding, transferring into a tablet press, using a die with the diameter of 5mm, and tabletting under the pressure of 10-15 MPa to obtain a precursor of the catalyst; the low-copper precursor is a CuO/ZnO mixture obtained by roasting pure copperas Cu 2Zn3(OH)6(CO3)2 at 350 ℃, and the content of CuO in the CuO/ZnO mixture is 31-32 wt%; the auxiliary agent is a mixture of manganese carbonate, magnesium carbonate and active carbon, and the mass ratio of the manganese carbonate to the magnesium carbonate to the active carbon in the auxiliary agent is 1:0.5-1:0.15-0.2 percent, wherein the dosage of the auxiliary agent accounts for 5-10 percent of the mass of the catalyst powder; the pore-forming agent is one or any combination of ammonium carbonate and ammonium bicarbonate, and the dosage of the pore-forming agent is 0.05-0.08 times of the mass of the catalyst powder;
and secondly, transferring the precursor of the catalyst to a muffle furnace, and roasting for 6 hours in an air atmosphere at 200-260 ℃ to obtain the catalyst for preparing the hydrogen by reforming the methanol with low copper content.
2. The method for preparing the catalyst for preparing hydrogen by reforming methanol with low copper content according to claim 1, which is characterized in that: the clay is metakaolin.
3. The low copper methanol reforming hydrogen production catalyst of any one of claims 1-2, characterized in that: the copper oxide content of the catalyst for preparing hydrogen by reforming methanol with low copper content is 23-28 wt%.
4. Use of a low copper content methanol reforming hydrogen catalyst as in claim 3 in a methanol steam reforming hydrogen process under operating conditions of: the reaction temperature is 200-280 ℃, the pressure is 0.1-3.0MPa, the mass airspeed is 1.0-4.0H -1, the raw material is H 2O/CH3 OH solution, and the CH 3 OH content in the H 2O/CH3 OH solution is 50wt%.
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