CN113941326A - A kind of anti-carbon deposition supported Pt catalyst and its preparation method and application in catalytic hydrogen production - Google Patents
A kind of anti-carbon deposition supported Pt catalyst and its preparation method and application in catalytic hydrogen production Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims description 18
- 230000008021 deposition Effects 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 22
- 230000003197 catalytic effect Effects 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 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 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 42
- 238000005470 impregnation Methods 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 2
- 238000004939 coking Methods 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种抗积碳负载型Pt催化剂及其制备方法和在催化制氢中的应用。本发明采用表面原位生长技术，不仅可以实现初始载体Al2O3物理织构和表面物化性能等的调控，并引入碱土金属元素作为催化剂助剂，可以在Al2O3表面形成类网格状结构，为后续Pt金属的分散和稳定固载提供局部限域微负载空间，从而得到新型催化剂载体；进而，采用溶液浸渍制备技术，将Pt离子固载于该新型催化剂载体上；最后将催化剂中的铂还原。与传统溶液浸渍法相比，本发明所制得的Pt催化剂具有更高的制氢活性，得到的Pt催化剂分散度和稳定性高。将其应用于甲醇水蒸气重整制氢反应中，可以显著提高反应中的甲醇转化率、氢气选择性等性能参数。The invention discloses an anti-coking supported Pt catalyst, a preparation method thereof, and an application in catalytic hydrogen production. The invention adopts the surface in-situ growth technology, which can not only realize the regulation of the physical texture and surface physicochemical properties of the initial carrier Al 2 O 3 , but also introduce alkaline earth metal elements as catalyst assistants to form a grid-like grid on the surface of Al 2 O 3 . It provides a local confinement micro-load space for the subsequent dispersion and stable immobilization of Pt metal, so as to obtain a new catalyst carrier; then, the solution impregnation preparation technology is used to immobilize Pt ions on the new catalyst carrier; finally, the catalyst platinum reduction in . Compared with the traditional solution impregnation method, the Pt catalyst prepared by the present invention has higher hydrogen production activity, and the obtained Pt catalyst has high dispersion and stability. When it is applied to the hydrogen production reaction of methanol steam reforming, the performance parameters such as methanol conversion rate and hydrogen selectivity in the reaction can be significantly improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an anti-carbon-deposition supported Pt catalyst, a preparation method thereof and application thereof in catalytic hydrogen production.
Background
The supported catalyst is widely applied to energy and petrochemical processes due to the characteristics of excellent heat transfer and mass transfer performance, easy continuous reaction and the like, and particularly the usage amount of the supported catalyst accounts for more than 70 percent of the total usage amount of the catalyst in important reaction processes such as hydrogen production of fossil fuel, hydrocarbon conversion, selective oxidation of olefin, selective hydrogenation and the like.
Common supported catalysts mostly adopt methods such as an impregnation method, a spraying method or a coating method for active metals and auxiliary metals to be added into the catalysts, however, the active metals and the auxiliary metals are easily influenced by a solvation effect, a metal component clustering effect, subsequent high-temperature roasting and other heat treatments in the preparation process, and a metal component microcrystal coagulation phenomenon occurs, so that the metal component dispersibility is poor, the catalyst structure is unstable, and the results of high energy consumption, large precious metal consumption and the like in the preparation process are brought. In addition, in the reaction processes of hydrogen production, hydrocarbon conversion, selective hydrogenation and the like, because most of the catalysts are acidic materials, carbon deposition which is difficult to avoid exists in the actual use process.
Hydrotalcite-like compounds include Hydrotalcite (Hydrotalcite) and Hydrotalcite-like compounds (Hydrotalcite-like compounds), and the main body thereof is generally composed of hydroxides of two metals, and is also called Hydrotalcite-like compoundIs a Layered Double Hydroxide (LDH). Intercalated compounds of LDHs are known as intercalated hydrotalcites. Hydrotalcites, hydrotalcite-like compounds, and intercalated hydrotalcites are collectively referred to as hydrotalcite-like intercalation materials (LDHs). The chemical formula is [ M ]2+ 1-xM3+ x(OH)2]x+(An–)x/n·mH2And O, the material is in a hexagonal lamellar structure, and the lamellar structure has extremely high rigidity and is extremely difficult to prepare into a lamellar structure with controllable appearance. The material is an inorganic material with unique structural characteristics: such as the adjustable denaturation of element composition in a wider range, the adjustable denaturation of a pore structure, the designability of interlayer intercalation anion species and the like lays the foundation that the material can possibly become an industrial catalyst or a catalyst precursor with potential application prospect.
The LDHs has acid-base double functions, the most basic is alkalinity, and the laminate contains OH-Due to the small specific surface area (about 5-20 m)2/g) is a weakly basic compound, and the composite metal oxide LDO obtained by roasting the compound is strong in alkalinity due to the full exposure of the structural center, and the LDO generally has a high specific surface area (about 200- & lt 300 & gt m)2In terms of/g), base centers and acid centers of different strengths, are also an important class of supports and catalysts. When the temperature of the LDHs is lower than 220 ℃, only crystal water is lost, and the original structure is not damaged; at 250-450 ℃, the laminate hydroxyl shrinks and releases CO2(ii) a At 450-550 deg.c, stable bimetal oxide can be formed, and LDO can be used in certain humidity (or water) and CO2(or carbonate) can be recovered into LDH, namely has a memory function, the recovery is not complete recovery, and the crystallinity of the LDO is reduced in the recovery process, so that the performance of the LDO is maintained, and the LDO can stably exist in the environment and can not be changed back to LDHs; when the temperature exceeds 600 ℃, a spinel phase product is formed, and the mixture of metal oxides starts to sinter, so that the surface area is greatly reduced, the pore volume is reduced, and the basicity is weakened.
Disclosure of Invention
The invention aims to provide an anti-carbon deposition supported Pt catalyst, a preparation method thereof and application thereof in catalytic hydrogen production.
The preparation method of the carbon deposition resistant supported Pt catalyst comprises the following steps:
(1) mixing Al2O3Adding the carrier into alkalescent solution for activation, adding soluble divalent metal salt solution, standing at 70-150 deg.C for reaction for 12-48 hr, naturally cooling after reaction, washing with deionized water, filtering, and drying at 60-150 deg.C for 12-48 hr to obtain Al-doped aluminum oxide2O3Growing hydrotalcite precursor on the surface of the carrier; then roasting in air atmosphere;
(2) adding the roasted product obtained in the step (1) into a soluble platinum salt solution with the concentration of 0.01-0.3mol/L, oscillating and reacting for 6-48h at 50-90 ℃, washing and filtering with deionized water after the reaction is finished, drying the obtained solid at 60-130 ℃ for 4-24h, and roasting in an air atmosphere;
(3) and (3) reducing and roasting the roasted product obtained in the step (2) in a hydrogen atmosphere to obtain the carbon deposition resistant supported Pt catalyst.
The Al is2O3The crystal form of the carrier is one or more of delta, beta, gamma, theta and eta, and the shape is one or more of spherical, clover, sheet, honeycomb and columnar; the Al is2O3The particle size of the carrier is 10-100 meshes. The Al is2O3The addition amount of the carrier is 10-60 g/L.
The weak alkaline solution is urea solution or ammonia water solution, the pH value is 7-9, and the concentration is 0.2-2.0
mol/L。
The activation conditions are as follows: the mixture is stirred and reacted for 0.5 to 2 hours at the temperature of between 80 and 150 ℃, and then the mixture is placed in a closed normal pressure kettle and is kept stand and reacted for 12 to 48 hours at the temperature of between 70 and 150 ℃.
The soluble divalent metal salt is one or more of Be salt, Mg salt, Ca salt, Cs salt and Ba salt. After adding the soluble divalent metal salt solution, the concentration of the divalent metal ions in the solution is 0.001-1 mol/L.
The roasting temperature in the step (1) is 200-600 ℃, and the roasting time is 4-12 h.
The roasting temperature in the step (2) is 300-900 ℃, and the roasting time is 4-24 h.
The roasting temperature in the step (3) is 200-600 ℃, and the roasting time is 1-6 h.
The content of Pt in the carbon deposit resistant load type Pt catalyst is 0.01 wt% -3 wt%.
The prepared carbon deposit resistant load type Pt catalyst is applied to catalyzing methanol steam reforming to prepare hydrogen.
The invention adopts the surface in-situ growth technology, and not only can realize the initial carrier Al2O3Regulating physical texture and surface physical and chemical performance, introducing alkaline earth metal element as catalyst assistant, and adding Al as initial carrier2O3LDHs and derivatives thereof formed by in-situ growth on the surface can form a grid-like structure and can provide a local limited micro-loading space suitable for dispersion, stability and immobilization of metal particles, so that a novel catalyst carrier is obtained, and Pt ions are immobilized on the novel catalyst carrier by adopting a solution impregnation preparation technology; finally, platinum in the catalyst is reduced so as to be applied to hydrogen production reaction and can be a catalytic product H2The molecules provide a surface local confinement overflow space, which provides guarantee for the improvement and promotion of the reactivity and stability of the supported Pt metal catalyst. Under the roasting condition of the invention, partial MAL-LDHs in the precursor is converted into MAL-LDO, and the surface confinement space structure of the LDHs can be basically maintained in the conversion process, which not only shows that the catalyst has excellent material structure stability, but also is beneficial to the adsorption of raw material molecules in the surface confinement space of the catalyst and fully participates in the reaction, and the structure stability, water resistance and CO resistance of the LDO can be improved by selecting proper roasting temperature2And the like. Compared with the traditional solution impregnation method, the Pt catalyst prepared by the method has higher hydrogen production activity, and the obtained Pt catalyst has high dispersity and stability. The method can improve and improve the activity and stability of the hydrogen production reaction, reduce the loading amount of the noble metal Pt and reduce the cost. When the catalyst is applied to the reaction of hydrogen production by reforming methanol steam, the performance parameters such as methanol conversion rate, hydrogen selectivity and the like in the reaction can be obviously improved. After reaction of catalystThe agent was characterized and found to retain the characteristics of the LDO, and was characterized again over a period of storage and storage, and still did not become LDH structure.
Detailed Description
The invention is at the initial carrier Al2O3Synthesizing a precursor material containing a catalytic promoter metal component and an Al element on the surface in situ, and then drying, roasting and the like to realize the conversion of the precursor material to a corresponding metal oxide containing the promoter metal component so as to realize the isolation and high dispersion of the catalytic promoter elements and can be carried out on an initial carrier Al2O3Forming a grid-like confinement structure on the surface, then realizing the optimization of material composition and structural performance by regulating and controlling the introduction amount of a catalytic assistant, the surface in-situ synthesis of a corresponding precursor material and the subsequent conformation conversion process, and finally realizing the dispersion and immobilization of a catalytic active component Pt by adopting an impregnation method.
The method of the invention can realize M containing the catalytic promoter M2+Al-LDHs type hydrotalcite layered precursor in-situ growth on Al2O3A surface; according to the structural characteristics of LDHs, the metal element M and the Al element of the catalytic promoter can realize atomic-level dispersion immobilization and in-situ distribution under the effects of lattice constraint and directional isolation of an LDHs laminate, and meanwhile, although the subsequent treatment processes such as high-temperature roasting and the like are required, the dispersion immobilization state of the metal element M of the catalytic promoter can still be effectively maintained, and serious surface migration is not easy to occur; of particular note is that in Al2O3Surface in situ growth of the resulting M2+Al-LDHs can be in Al2O3The surface forms a latticed confinement microscopic confinement structure, and the structure is converted by subsequent heat treatment to form M2+Al-LDO/Al2O3The catalyst can still be effectively maintained, and can play an effective role in dispersing, isolating and stably immobilizing subsequent active metal components Pt, so that the stable immobilization and dispersion of the catalytic assistant metal element M and the catalytic active metal components Pt are achieved, the overall catalytic activity and stability of the material can be improved, and the purposes of improving the catalytic activity and improving the stability are achieved. Furthermore, from M2+Al-LDHs derived M2+Al-LDO compared to Al2O3All have stronger alkalinity, which leads the surface acidity of the finally obtained load type Pt catalyst to be effectively regulated and controlled, thereby having obvious inhibition effect on carbon deposition phenomenon in the hydrogen production reaction process, and the obtained M2+The Al-LDO has high stability, can maintain the LDO structure when stored in room temperature environment, and does not absorb water and CO2Back to the LDH material.
For ease of understanding, the present invention is described below with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Firstly, 3g of urea is weighed and dissolved in deionized water to prepare 70ml of solution, and 2.5g of spherical theta-Al with the granularity of 40 meshes2O3Adding into the above solution, stirring at 80 deg.C for 1 hr, placing into a sealed normal pressure autoclave, standing at 90 deg.C for 24 hr; then, 3g of Mg (NO) was weighed3)2·6H2Dissolving O in deionized water to prepare 18ml solution, adding into the mixture, standing at 120 deg.C for 24 hr, cooling, filtering, washing with deionized water, drying at 70 deg.C for 12 hr to obtain MgAl-LDHs/Al2O3(ii) a Then 0.04g of platinum chloride is weighed to prepare 5.0ml of aqueous solution, and the obtained MgAl-LDHs/Al is added2O3Placing in platinum chloride water solution, placing in 70 deg.C water bath shaker for 24 hr, filtering, washing the obtained solid with deionized water, and drying at 70 deg.C; finally, roasting at 450 ℃ for 8 hours, placing the roasted sample in a fixed bed microreflector, and reacting with H2And carrying out reduction treatment at the temperature of 300 ℃ for 2 hours to obtain the carbon deposition resistant supported Pt catalyst.
The catalyst is used for methanol steam reforming hydrogen production reaction through a fixed bed type micro-reverse evaluation device, and the reaction conditions are as follows: the reaction temperature is 340 ℃, the normal pressure is realized, the water-carbon ratio is n (CH)3OH):n(H2O) 1:1.5, using N2As a carrier gas, the flow rate of methanol was 0.7ml/min, and the reaction time was 6 hours, resulting in a methanol conversion of 80% and a hydrogen yield of 0.92L/min.
To compare the catalytic performance of the samples, 3g Mg (NO) was weighed3)2·6H2O and 0.04g of platinum chloride were dissolved in 5.0ml of water, and prepared in Al by the co-impregnation method in the same manner as described above2O3The surface of the carrier was then calcined and reduced, and under the same evaluation conditions, the result was 60% conversion of methanol and 0.67L/min of hydrogen production. 0.04g of platinum chloride was weighed out and dissolved in 5.0ml of water, and prepared in Al by the co-impregnation method in the same manner as described above2O3The surface of the carrier was then calcined and reduced, and under the same evaluation conditions, the result was 45% conversion of methanol and 0.6L/min of hydrogen production.
Example 2
Firstly, 5ml of commercial concentrated ammonia water (the concentration is 25 percent, the molar concentration is 13.38mol/L) is weighed and prepared into 80ml of solution with deionized water, and 3.0g of spherical gamma-Al with the granularity of 80 meshes2O3Adding into the above solution, stirring at 70 deg.C for 0.5 hr, placing into a sealed normal pressure autoclave, and standing at 80 deg.C for 12 hr; then, 4.8g of Mg (NO) was weighed out3)2·6H2Dissolving O in deionized water to prepare 10ml solution, adding the solution into the mixture, standing for 24 hours at 110 ℃, cooling, filtering, washing with deionized water, and drying at 80 ℃ for 18 hours to obtain MgAl-LDHs/Al2O3(ii) a Then 0.3g of platinum chloride is weighed to prepare 6.0ml of aqueous solution, and the obtained MgAl-LDHs/Al is added2O3Placing in platinum chloride water solution, placing in 80 deg.C water bath shaker for 12 hr, filtering, washing the obtained solid with deionized water, and drying at 90 deg.C; finally, roasting at 400 ℃ for 6 hours, placing the roasted sample in a fixed bed microreflector, and reacting with H2Reducing at 400 deg.c for 2.5 hr to obtain carbon deposit resisting supported Pt catalyst.
The catalyst is used for methanol steam reforming hydrogen production reaction through a fixed bed type micro-reverse evaluation device, and the reaction conditions are as follows: the reaction temperature is 360 ℃, the normal pressure is realized, and the water-carbon ratio is n (CH)3OH):n(H2O) 1:1.5, using N2As carrier gas, methanol flow rate of 0.7ml/min, reaction time of 6h, and methanol conversion rate of 85%The hydrogen yield was 0.98L/min.
To compare the catalytic performance of the samples, we weighed 4.8g Mg (NO)3)2·6H2O and 0.04g of platinum chloride were dissolved in 6.0ml of water, and prepared in Al by the co-impregnation method in the same manner as described above2O3The surface of the carrier was then calcined and reduced, and under the same evaluation conditions, the result was 64% conversion of methanol and 0.7L/min of hydrogen production. 0.04g of platinum chloride is weighed and dissolved in 6.0ml of water, and prepared in Al by the co-impregnation method in the same way as the above method2O3The carrier surface was then calcined and reduced, and under the same evaluation conditions, the result was 48% methanol conversion and 0.56L/min hydrogen production.
Example 3
Firstly, 6g of urea is weighed and dissolved in deionized water to prepare 60ml of solution, and 3.0g of spherical delta-Al with the granularity of 60 meshes2O3Adding into the above solution, stirring at 70 deg.C for 1 hr, placing into a sealed normal pressure autoclave, and standing at 100 deg.C for 24 hr; then, 9g of CaCl was weighed2Dissolving in deionized water to obtain 60ml solution, adding into the above mixture, standing at 130 deg.C for 24 hr, cooling, filtering, washing with deionized water, and drying at 70 deg.C for 12 hr to obtain CaAl-LDHs/Al2O3(ii) a Then 0.13g of platinum chloride is weighed to prepare 6.0ml of aqueous solution, and the obtained CaAl-LDHs/Al2O3Placing in platinum chloride water solution, placing in 70 deg.C water bath shaker for 24 hr, filtering, washing the obtained solid with deionized water, and drying at 70 deg.C; finally, roasting at 400 ℃ for 8 hours, placing the roasted sample in a fixed bed micro-reactor, and reacting with H2And carrying out reduction treatment at the temperature of 300 ℃ for 3 hours to obtain the carbon deposition resistant supported Pt catalyst.
The catalyst was subjected to the application performance test under the same conditions as in example 1, and as a result, the methanol conversion was 90% and the hydrogen production was 1.04L/min.
To compare the catalytic performance of the samples, 9g of calcium chloride and 0.13g of platinum chloride were weighed out and dissolved in 6.0ml of water, and supported on Al by co-impregnation in the same manner as described above2O3The surface of the carrier is then calcined and reduced, and under the same reaction conditions, the result is that the conversion rate of methanol is 72% and the yield of hydrogen is 0.67L/min. 0.13g of platinum chloride was weighed out and dissolved in 6.0ml of water, and prepared in Al by the co-impregnation method in the same manner as described above2O3The carrier surface was then calcined and reduced, and under the same evaluation conditions, the result was 58% methanol conversion and 0.84L/min hydrogen production.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the carbon deposition resistant supported Pt catalyst is characterized by comprising the following specific steps:
(1) mixing Al2O3Adding the carrier into alkalescent solution for activation, adding soluble divalent metal salt solution, standing at 70-150 deg.C for reaction for 12-48 hr, naturally cooling after reaction, washing with deionized water, filtering, and drying at 60-150 deg.C for 12-48 hr to obtain Al-doped aluminum oxide2O3Growing hydrotalcite precursor on the surface of the carrier; then roasting in air atmosphere;
(2) adding the roasted product obtained in the step (1) into a soluble platinum salt solution with the concentration of 0.01-0.3mol/L, oscillating and reacting for 6-48h at 50-90 ℃, washing and filtering with deionized water after the reaction is finished, drying the obtained solid at 60-130 ℃ for 4-24h, and roasting in an air atmosphere;
(3) and (3) reducing and roasting the roasted product obtained in the step (2) in a hydrogen atmosphere to obtain the carbon deposition resistant supported Pt catalyst.
2. The method according to claim 1, wherein said Al is2O3The crystal form of the carrier is one or more of delta, beta, gamma, theta and eta, and the shape is spherical, clover, sheet, honeycomb or columnOne or more of the above shapes; the Al is2O3The granularity of the carrier is 10-100 meshes; the Al is2O3The addition amount of the carrier is 10-60 g/L.
3. The process according to claim 1, wherein the weakly alkaline solution is a urea solution or an aqueous ammonia solution, and has a pH of 7 to 9 and a concentration of 0.2 to 2.0 mol/L.
4. The method of claim 1, wherein the activation conditions are: the mixture is stirred and reacted for 0.5 to 2 hours at the temperature of between 80 and 150 ℃, and then the mixture is placed in a closed normal pressure kettle and is kept stand and reacted for 12 to 48 hours at the temperature of between 70 and 150 ℃.
5. The method according to claim 1, wherein the soluble divalent metal salt is one or more of Be salt, Mg salt, Ca salt, Cs salt and Ba salt; after adding the soluble divalent metal salt solution, the concentration of the divalent metal ions in the solution is 0.001-1 mol/L.
6. The preparation method as claimed in claim 1, wherein the calcination temperature in step (1) is 200-600 ℃ and the calcination time is 4-12 h.
7. The method as claimed in claim 1, wherein the calcination temperature in step (2) is 300-900 ℃ and the calcination time is 4-24 h.
8. The preparation method as claimed in claim 1, wherein the calcination temperature in step (3) is 200-600 ℃ and the calcination time is 1-6 h.
9. The preparation method according to claim 1, wherein the anti-carbon deposition supported Pt catalyst contains 0.01 wt% to 3 wt% of Pt.
10. Use of the carbon deposit resistant supported Pt catalyst prepared by the method of any one of claims 1-9 to catalyze methanol steam reforming to produce hydrogen.
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