CN115318332A - Preparation method and application of catalyst for hydrogen production by ammonia decomposition - Google Patents
Preparation method and application of catalyst for hydrogen production by ammonia decomposition Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 75
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 229910052750 molybdenum Inorganic materials 0.000 claims description 44
- 239000011733 molybdenum Substances 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 34
- 238000003825 pressing Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 241000080590 Niso Species 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000012018 catalyst precursor Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- -1 molybdenum ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalytic materials, and particularly relates to a catalyst for preparing hydrogen by decomposing ammonia and a preparation method thereof. The ammonia decomposition hydrogen production catalyst is prepared by an ion exchange method, and can show better ammonia decomposition low-temperature activity.
Description
Technical Field
The invention relates to the field of catalysts for hydrogen production by ammonia decomposition, in particular to a preparation method and application of a catalyst for hydrogen production by ammonia decomposition.
Background
The ammonia has high hydrogen content (17.6 wt%), easy liquefaction (normal temperature, 8 atm), non-flammability (ignition point is more than or equal to 650 ℃), and no COX emission; the ammonia industry has mature technology, storage and transportation cost (ammonia < hydrogen), and high intrinsic safety, and is an ideal hydrogen storage carrier. Therefore, the ammonia is used as a hydrogen storage carrier, and the hydrogen is produced by combining ammonia decomposition reaction, so that the development of the hydrogen energy industry is expected to be promoted, and the method has great economic value and practical significance.
The ammonia decomposition reaction is an endothermic reaction, and the increase of the reaction temperature is favorable for improving the conversion rate of ammonia, but has great significance for achieving the purposes of energy saving and consumption reduction and developing a low-temperature and high-efficiency catalyst for producing hydrogen by ammonia decomposition. The Ru-based catalyst has good low-temperature ammonia decomposition performance, but the popularization and application of the noble metal Ru are limited due to the high price of the noble metal Ru; therefore, it is important to develop a non-noble metal-based ammonia decomposition catalyst having good low-temperature performance.
CN110327957A provides a preparation method of an ammonia decomposition catalyst, said method comprising the steps of: 1) Dissolving a metal salt in deionized water to form a metal salt solution; 2) Adding a chelating agent into the metal salt solution, and stirring to form sol; 3) Aging the sol to form a gel; 4) Drying the gel, and roasting to form a catalyst precursor; 5) And nitriding the catalyst precursor to prepare the ammonia decomposition catalyst. The preparation method of the ammonia decomposition catalyst provided by the invention adopts a sol-gel method to prepare the catalyst precursor, the prepared catalyst precursor has high structural uniformity, and the ammonia decomposition catalyst prepared after nitridation has the temperature of 600-800 ℃ and high space velocity (15000 h) -1 ) And the pure ammonia gas has higher ammonia decomposition rate and high catalytic activity under the condition of taking the pure ammonia gas as raw material gas.
CN114100661A specifically relates to a catalyst for decomposing molybdenum amino to produce hydrogen and a preparation method thereof. The precursor of the catalyst for decomposing molybdenum amino to prepare hydrogen is prepared by adopting a sol-gel method, and the size of the particles of the precursor is adjusted by optimizing preparation parameters to obtain the precursor with proper structure and performance; the precursor is treated by nitridation-oxidation to obtain the catalyst, and Mo is formed after the activity evaluation of ammonia decomposition reaction 2 N and MoO 2 The mixture phase has two coexisting phases, so that more defect sites and phase interfaces are generated, and the number of active sites of the catalyst is increased, thereby showing better low-temperature activity of ammonia decomposition.
Although some researches on non-noble metal ammonia conversion catalysts exist in the prior art, some problems and defects still exist, such as few researches on molybdenum-based catalysts, high deactivation rate of the catalysts, short duration and the like. Therefore, it is urgently needed to provide a preparation method and an application technology of a catalyst for hydrogen production by ammonia decomposition.
Disclosure of Invention
The invention aims to provide a preparation method and an application technology of a catalyst for hydrogen production by ammonia decomposition, which solve the defects of easy inactivation, short duration and the like of a catalyst for hydrogen production by ammonia conversion in the prior art.
Specifically, the invention provides a preparation method of a catalyst for hydrogen production by ammonia decomposition, which is characterized by comprising the following steps: the method comprises the following steps:
(1) Respectively dissolving metal salt and citric acid in deionized water, and stirring until the metal salt and the citric acid are completely dissolved;
(2) Under the condition of stirring, putting a hydrogen type molecular sieve into the solution, and carrying out ion exchange at a certain temperature;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing;
(5) Roasting the dried product to obtain a catalyst;
in some preferred embodiments, the Fe salt, ni salt, mo salt in step (1).
In some preferred implementations, the Fe salt in step (1) is selected from FeCO 3 ，Fe(NO 3 ) 2 、FeCl 3 、 FeCl 2 One or more of (a); the Ni salt is selected from NiNO 3 、NiSO 4 One or more of the above; mo salt is selected from Mo 2 (O 2 CCF 3 ) 4 、Mo 2 (OAc) 4 、Mo(CO) 6 、H 8 MoN 2 O 4 、Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 ·4H 2 And one or more of O.
In some preferred embodiments, the molar ratio of the metallic Mo salt to citric acid in step (1) is 1.
In some preferred embodiments, the ion exchange temperature in step (2) is 50 to 100 ℃.
In some preferred embodiments, the drying temperature in step (4) is 100-160 ℃ and the drying time is 3-10h.
In some preferred embodiments, the calcination temperature in step (5) is 300-800 ℃ and the calcination time is 2-26h.
In some preferred embodiments, the pore volume of the ammonia decomposition hydrogen production catalyst ranges from 0.025 to 0.150cm 3 g-1, preferably 0.050-0.120cm 3 g-1, more preferably 0.065-0.100cm 3 g-1, more preferably 0.085-0.095cm 3 g-1。
In some preferred embodiments, in step 2), the hydrogen-type molecular sieve is a ZSM-5, SAPO-34, ZSM-11, ZSM-4, beta, MOR, ERI, ZK-5 hydrogen-type molecular sieve.
The second aspect of the invention provides an application of the catalyst for producing hydrogen by decomposing ammonia, which is prepared by the method, in the reaction of producing hydrogen by decomposing ammonia.
Advantageous effects
Compared with the prior art, the invention has the following technical effects:
the catalyst for preparing hydrogen by decomposing ammonia through an ion exchange method has the advantages of high activity, long duration and difficult inactivation, and the conversion rate obtained by ammonia conversion reaction is close to the equilibrium conversion rate.
The preparation method of the invention utilizes ion exchange, has simple and convenient steps, omits the complicated steps of a sol-gel method in the prior art, and simultaneously overcomes the defect that the catalyst prepared by the method in the prior art is easy to inactivate.
Meanwhile, the invention explores the influence of the catalytic rate and the pore volume rate on the final conversion rate of the catalyst, and achieves the effect of regulating and controlling the catalytic conversion rate by optimizing the pore volume.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the present invention.
Those skilled in the art will recognize that: the chemical reactions described herein may be used to suitably prepare a number of other compounds of the invention, and other methods for preparing the compounds of the invention are considered to be within the scope of the invention. For example, the synthesis of those non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art by modification, such as appropriate protection of interfering groups, by the use of other known reagents in addition to those described herein, or by some routine modification of reaction conditions. In addition, the reactions disclosed herein or known reaction conditions are also recognized as being applicable to the preparation of other compounds of the present invention.
Ammonia decomposition hydrogen production
The hydrogen production by ammonia decomposition is a chemical reaction, which means that liquid ammonia is heated to 800-850 ℃ and ammonia is decomposed under the action of a catalyst, so that the content of 75 percent H can be obtained 2 、25％N 2 Hydrogen-nitrogen mixed gas of (2).
The reaction formula is as follows:
in the ammonia decomposition hydrogen production process, the main principle is to improve the hydrogen yield by moving the reaction equilibrium to the positive direction.
Hydrogen production catalyst and performance evaluation
The hydrogen production catalyst is generally a metal-based catalyst, and particularly takes heavy metals of ruthenium and cobalt as the standard. The excellent activity of a general metal-based catalyst is evaluated in consideration of the efficiency of ammonia decomposition and the yield of hydrogen gas generated. The overall mechanism is that ammonia decomposition is initiated by adsorption of ammonia to the surface of the catalytically active sites, essentially undergoing a molecular breakdown of adsorbed ammonia through successive N-H bonds, releasing hydrogen atoms which can then combine to form molecular hydrogen, and finally involving the recombinant desorption of the nitrogen-adsorbing atoms to produce molecular nitrogen.
Therefore, the important factor affecting the whole hydrogen production efficiency is that ammonia molecules need to be adsorbed on the active metal sites which are mainly activated; on the other hand, the strongly adsorbed N-adsorbed atoms are bonded to metal ions, which poisons metal active sites and thus renders the catalyst ineffective. Therefore, during ammonia decomposition, surface nitrides are generally not desired to form, thereby reducing the reaction rate.
The non-noble metal catalysts of the current state of the art, although relatively low in cost, are relatively low in activity and tend to cause excessive surface nitride formation in the catalytic reaction, thereby slowing the reaction rate and ultimately deactivating the catalyst through poisoning.
Non-noble metal based catalysts
The molybdenum-based catalyst is a non-noble metal catalyst which is common in the prior art at present. The usual preparation methods are generally sol-gel preparation of ammonia catalysts. Generally comprising the steps of:
(1) Respectively dissolving metal salt and citric acid in deionized water, and stirring until the metal salt and the citric acid are completely dissolved;
(2) Slowly adding the citric acid solution into a metal salt solution under the condition of stirring;
(3) Heating the mixed solution in an oil bath to a certain temperature, and reacting to obtain a gel product;
(4) Drying the gel at a certain temperature;
(5) Roasting the dried product under certain conditions to obtain a catalyst precursor;
(6) Nitriding the catalyst precursor at a certain temperature in a nitrogen-containing atmosphere;
(7) And oxidizing the nitriding product in an oxidizing atmosphere to obtain the catalyst.
The principle of the method is as follows: the precursor is nitrided in a nitrogen-containing atmosphere and then is roasted in an oxidizing atmosphere to obtain the catalyst. The ammonia decomposition reaction activity of the catalyst precursor is tested after the catalyst precursor is directly nitrided, and only Mo is observed in the activity evaluation product 2 N and MoO 2 Two phases. Mo 2 N and MoO 2 The formation of the mixture phase enables more defect sites and phase interfaces to be generated in the catalyst, and the number of catalytic active sites of the catalyst is increased, so that the catalyst shows more excellent ammonia decomposition reaction performance, and particularly improves the low-temperature ammonia decomposition reaction performance of the Mo-based catalyst.
The above-described methods of the prior art, however, have some disadvantages. The sol-gel method is complicated, and the distribution and the structure of active point positions of the catalyst are adjusted by adding nitridation and oxidation steps; meanwhile, when the molybdenum-based catalyst is prepared, the catalyst particles obtained by the sol-gel method often have the problems of insufficient dispersibility and particle agglomeration, which can also cause adverse effects on the active point sites required by the ammonia decomposition reaction, such as reduction of the surface area of the catalyst, blockage of the active point sites and the like.
Ion exchange process
In the technical scheme of the invention, the molybdenum-based decomposition hydrogen production catalyst is prepared by using an ion exchange method, and a hydrogen type molecular sieve is added into a citric acid solution containing molybdenum salt, and ion exchange is carried out at a certain temperature to obtain the molybdenum-containing molecular sieve.
The general preparation method for obtaining the hydrogen type molecular sieve uses a silicon source and an aluminum source as raw materials, obtains molecular sieve crystals by hydrothermal crystallization of a crystallization regulator under the combined action of a double template agent and a structure directing agent, and then obtains the hydrogen type molecular sieve by roasting and hydrogenation.
As the hydrogen type molecular sieve used in the present invention, ZSM-5, SAPO-34, ZSM-11, ZSM-4, beta, MOR, ERI, ZK-5 hydrogen type molecular sieves are generally used. Preferred hydrogen-form molecular sieves are ZSM-5 and ZSM-11.
In the invention, hydrogen type molecular sieve is used for ion exchange. Compared with a sol-gel method, the molybdenum-based catalyst obtained by the method has larger specific surface area, and the obtained active phase MoO3 has higher activity than that of the molybdenum-based catalyst in the prior art. The molybdenum-containing molecular sieve is obtained by directly exchanging with a hydrogen-type molecular sieve by utilizing ion exchange, and the steps are simple and convenient. The site position activity of the original hydrogen type molecular sieve is obtained, and meanwhile, after molybdenum ions enter the site position of the molecular sieve, secondary dislocation is formed, the defect density is increased, and the increase of the active site position is facilitated.
Therefore, the catalyst is obtained by using an ion exchange method, the active phase contains crystal boundaries and dislocation, and the vicinity of a large number of point and surface defects has high-position activity, so that during the ammonia catalytic decomposition reaction, nitrogen is easily adsorbed, the ammonia decomposition is promoted to move towards the positive balance direction, and the generation of hydrogen is promoted. The adsorbed nitrogen is on the surface of the catalyst, and because a large number of active sites exist in the catalyst phase, the nitrogen adsorbed on the surface of the catalyst cannot be directly bonded and converted into nitride, so that the problem that the activity is reduced and even the catalyst is invalid because the nitride blocks the sites of the sites on the surface of the catalyst is avoided.
The pore volume distribution of the molybdenum-based catalyst obtained by the present invention is preferably in the range of 0.025 to 0.150cm 3 g-1, preferably 0.050-0.120cm 3 g-1, more preferably 0.065-0.100cm 3 g-1, more preferably 0.085-0.095cm 3 g-1. The catalyst in the preferable range of the pore volume has optimal activity when ammonia is converted into hydrogen, and has the highest ammonia conversion rate during the catalytic reaction.
The metal salt used in the invention is Fe salt, ni salt and Mo salt.
The Fe salt is selected from FeCO 3 ，Fe(NO 3 ) 2 、FeCl 3 、FeCl 2 One or more of (a).
The Ni salt is selected from NiNO 3 、NiSO 4 One or more of them.
Mo salt is selected from Mo 2 (O 2 CCF 3 ) 4 、Mo 2 (OAc) 4 、Mo(CO) 6 、H 8 MoN 2 O 4 、Na 2 MoO 4 、 (NH 4 ) 6 Mo 7 O 24 ·4H 2 One or more of O.
The present invention is preferably a Mo salt.
The preparation method scheme of the catalyst for preparing hydrogen by decomposing molybdenum amino in the embodiment of the invention is explained below.
Example 1
A preparation method of a catalyst for preparing hydrogen by decomposing molybdenum-based ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) Metal Mo salt Mo2 (O2 CCF 3) 4 and citric acid are mixed according to a molar ratio of 1:0.5 are respectively dissolved in deionized water and stirred until the materials are completely dissolved;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-5 into the solution, and carrying out ion exchange at 60 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 120 ℃ for 4 hours;
(5) The dried product is roasted for 5 hours at 500 ℃ to obtain the catalyst for decomposing molybdenum amino to prepare hydrogen.
Example 2
A preparation method of a catalyst for preparing hydrogen by decomposing molybdenum base ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) And (2) mixing a metal Mo salt Na2MoO4 and citric acid according to a molar ratio of 1:1.2 respectively dissolving in deionized water, and stirring until the materials are completely dissolved;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-5 into the solution, and carrying out ion exchange at 70 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 100 ℃ and the drying time is 4 hours;
(5) The dried product is roasted for 5 hours at 650 ℃ to obtain the catalyst for decomposing molybdenum amino to prepare hydrogen.
Example 3
A preparation method of a catalyst for preparing hydrogen by decomposing molybdenum-based ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) Metal Mo salt Mo2 (OAc) 4 and citric acid are mixed according to a molar ratio of 1:1, respectively dissolving in deionized water, and stirring until the materials are completely dissolved;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-11 into the solution, and carrying out ion exchange at 55 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 100 ℃ and the drying time is 4h;
(5) And roasting the dried product at 550 ℃ for 8 hours to obtain the catalyst for preparing hydrogen by decomposing molybdenum base ammonia.
Example 4
A preparation method of a catalyst for preparing hydrogen by decomposing molybdenum base ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) Metal Mo salt (NH 4) 6Mo7O 24.4H 2O and citric acid are mixed according to a molar ratio of 1:1.5 respectively dissolving in deionized water, and stirring until the materials are completely dissolved;
(2) Under the condition of stirring, putting a hydrogen type molecular sieve into the ZSM-5 solution, and carrying out ion exchange at 60 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 100 ℃ and the drying time is 4 hours;
(5) The dried product is roasted for 5 hours at the temperature of 600 ℃ to obtain the catalyst for decomposing molybdenum amino to prepare hydrogen.
Example 5
A preparation method of a catalyst for preparing hydrogen by decomposing molybdenum-based ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) Metal Mo salt Mo (CO) 6 and citric acid are mixed according to a molar ratio of 1:0.3 are respectively dissolved in deionized water and stirred until the materials are completely dissolved;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-11 into the solution, and carrying out ion exchange at 60 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 120 ℃ for 4 hours;
(5) The dried product is roasted for 5 hours at 500 ℃ to obtain the catalyst for decomposing molybdenum amino to prepare hydrogen.
Example 6
A preparation method of an iron-based catalyst for hydrogen production by ammonia decomposition is characterized by comprising the following steps: the method comprises the following steps:
(1) The metal Fe salt FeCO 3 And citric acid in a molar ratio of 1:0.5 respectively dissolving in deionized water, stirring toCompletely dissolving;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-5 into the solution, and carrying out ion exchange at 60 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 120 ℃ for 4 hours;
(5) The dried product is roasted for 5 hours at 500 ℃ to obtain the catalyst for preparing hydrogen by decomposing molybdenum amino.
Example 7
A preparation method of a nickel-based ammonia decomposition hydrogen production catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Metal Ni salt NiSO 4 And citric acid in a molar ratio of 1:0.5 are respectively dissolved in deionized water and stirred until the materials are completely dissolved;
(2) Under the condition of stirring, putting hydrogen type molecular sieve ZSM-5 into the solution, and carrying out ion exchange at 60 ℃;
(3) Filter-pressing the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and filter-pressing the molybdenum-containing molecular sieve with deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing, wherein the drying temperature is controlled at 120 ℃ and the drying time is 4h;
(5) The dried product is roasted for 5 hours at 500 ℃ to obtain the catalyst for decomposing molybdenum amino to prepare hydrogen.
Comparative example 1
Using example 1 as reference, a comparative catalyst was obtained with the same process parameters and procedures except that SAPO-34 was selected as the hydrogen-type molecular sieve.
Comparative example 2
Using example 1 as reference, a comparative catalyst was obtained with the same process parameters and flow scheme except that ZSM-4 was selected as the hydrogen form of the molecular sieve.
Comparative example 3
Using example 1 as reference, the same materials and processes were used to obtain a gel by a sol-gel method, which was then dried, calcined, nitrided, and oxidized to obtain a comparative catalyst.
Evaluation of catalytic Properties
The catalysts obtained in examples 1 to 5 and comparative examples 1 to 3 were evaluated for their catalytic activity. Taking an appropriate amount of catalyst (Mo content: 7%) and placing in a quartz reactor, at 30% H 2 Heating to 500 ℃ at the temperature of 5 ℃/min in an Ar atmosphere (80 ml/min), activating for 2h at the temperature, and then introducing high-purity ammonia gas to react at the temperature of 500 ℃, wherein the flow rate of the ammonia gas is 100ml/min. The results of the catalytic reaction evaluations are shown in table 1.
TABLE 1
| Sample (I) | Conversion of Ammonia% | Duration of time |
| Example 1 | 99.4 | >6h |
| Example 2 | 99.5 | >6h |
| Example 3 | 98.9 | >6h |
| Example 4 | 98.4 | >6h |
| Example 5 | 98.5 | >6h |
| Example 6 | 94.2 | >5h |
| Example 7 | 90.9 | >4h |
| Comparative example 1 | 70.2 | <2h |
| Comparative example 2 | 68.7 | <2h |
| Comparative example 3 | 64.5 | <2h |
As can be seen from the above table, the molybdenum-based catalyst is obtained by the ion exchange method, the prepared ammonia decomposition catalyst has a nearly equilibrium conversion rate when the ammonia conversion reaction is carried out at 500 ℃, the high-temperature reaction time lasts for 4 hours, and the high catalytic activity can be maintained.
Table 2 shows the properties of a set of catalyst samples of different pore volumes obtained by controlling the calcination temperature and time according to the procedure of example 1.
TABLE 2
| Sample (I) | Pore volume cm 3 g -1 | Percent conversion% |
| A1 | 0.100 | 99.4％ |
| A2 | 0.300 | 98.5 |
| A3 | 0.150 | 98.1％ |
| A4 | 0.085 | 99.7％ |
| A5 | 0.250 | 84.3％ |
| A6 | 0.015 | 88.4％ |
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Those skilled in the art may make modifications and variations to the embodiments disclosed herein without departing from the scope and spirit of the invention.
Claims (10)
1. A preparation method of a catalyst for preparing hydrogen by decomposing ammonia is characterized by comprising the following steps: the method comprises the following steps:
(1) Respectively dissolving metal salt and citric acid in deionized water, and stirring until the metal salt and the citric acid are completely dissolved;
(2) Under the condition of stirring, putting a hydrogen type molecular sieve into the solution, and carrying out ion exchange at a certain temperature;
(3) Carrying out filter pressing on the mixture to obtain a molybdenum-containing molecular sieve, and repeatedly washing and carrying out filter pressing by using deionized water for multiple times;
(4) Drying the molecular sieve obtained after filter pressing;
(5) And roasting the dried product to obtain the catalyst.
2. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the metal salt in the step (1) is Fe salt, ni salt or Mo salt.
3. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the Fe salt in the step (1) is selected from FeCO 3 ，Fe(NO 3 ) 2 、FeCl 3 、FeCl 2 One or more of (a); the Ni salt is selected from NiNO 3 、NiSO 4 One or more of the above; mo salt is selected from Mo 2 (O 2 CCF 3 ) 4 、Mo 2 (OAc) 4 、Mo(CO) 6 、H 8 MoN 2 O 4 、Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 ·4H 2 And one or more of O.
4. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: in the step (1), the molar ratio of the Mo salt to the citric acid is 1.
5. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the ion exchange temperature in the step (2) is 50-100 ℃.
6. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the drying temperature in the step (4) is 100-160 ℃, and the drying time is 3-10h.
7. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the roasting temperature in the step (5) is 300-800 ℃, and the roasting time is 2-26h.
8. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: the pore volume distribution of the ammonia decomposition hydrogen production catalyst is 0.025-0.150cm 3 g-1, preferably 0.050-0.120cm 3 g-1, more preferably 0.065-0.100cm 3 g-1, more preferably 0.085-0.095cm 3 g-1。
9. The method for producing a catalyst for ammonia decomposition hydrogen production according to claim 1, characterized in that: in the step 2), the hydrogen type molecular sieve is a ZSM-5, SAPO-34, ZSM-11, ZSM-4, beta, MOR, ERI or ZK-5 hydrogen type molecular sieve.
10. Use of a molybdenum-based catalyst prepared according to the method of any one of claims 1 to 8 in a hydrogen production reaction by ammonia decomposition.
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