CN1186452A - Catalyst and process for preparing ammonia - Google Patents
Catalyst and process for preparing ammonia Download PDFInfo
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- CN1186452A CN1186452A CN96194318A CN96194318A CN1186452A CN 1186452 A CN1186452 A CN 1186452A CN 96194318 A CN96194318 A CN 96194318A CN 96194318 A CN96194318 A CN 96194318A CN 1186452 A CN1186452 A CN 1186452A
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- zeolite
- metal ion
- alkali metal
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012013 faujasite Substances 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- -1 alkali metal alkoxide Chemical class 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 2
- 150000004692 metal hydroxides Chemical class 0.000 claims 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000001455 metallic ions Chemical class 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052707 ruthenium Inorganic materials 0.000 description 14
- 238000005342 ion exchange Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A catalyst for synthesis of ammonia from N2 and H2, containing a basic zeolite support; Group VIII metal clusters supported on the basic zeolite support; and divalent and alkali metal ions incorporated into the zeolite support, and a process for the production of ammonia using such a catalyst.
Description
The research work of this patent obtains the part support of American National science fund appropriation #CTS-9257306, so U.S. government has certain power to this patent.
The patent background
Patent relates to the field
This patent relates to a kind of catalyst of new carrying, and the group VIII transition metal that this catalyst is supported by alkaline molecular sieve is formed, improves synthesizing and Ammonia Process accordingly by nitrogen and ammonia system ammonia.
Background is discussed
Traditional industrial ammonia synthesis technology is for preparing ammonia 400～700 ℃ temperature and above (triply promoted) iron catalyst with triple promotions under the pressure of 300atm.Yet under so high temperature, the balance that nitrogen adds the reaction equation of hydrogen generation ammonia is not satisfactory especially, therefore needs high pressure.
In United States Patent (USP) 3770658, Ozaki etc. have proposed a kind of catalyst based on transition metal, and catalyst is best with ruthenium, comprises alkali metal, being lower than under 400 ℃ the temperature, just can prepare ammonia from nitrogen and hydrogen.
In United States Patent (USP) 4142993, ELofson etc. have also proposed a kind of catalyst that comprises alkali-metal based on the group VIII transition metal element, use this catalyst, under the support of activated carbon, can be under 375 ℃ of temperature or under the higher temperature, pressure is synthetic ammonia under 27～67atm.
This traditional ruthenium-based ammonia synthetic catalyst is made up of ruthenium family element, and exists with the carrier support of carbon, magnesium oxide.In addition, mentioning as Ozaki etc., is the activity that increases ruthenium-based catalyst, often will add alkali metal promoter such as some potassium, caesium.
In United States Patent (USP) 46000571, McCarroll etc. propose a kind of ruthenium-based catalyst of synthetic ammonia, comprise alkali metal and barium in the catalyst, and all the form of supporting with carbon supports.
The paper of delivering recently, resemble Cisneros and Lunsford (" catalyst ", 141 phases, 191～205 pages, 1993) and (" catalyst communication " 25 phases such as Wellenbuscher, the 61-74 page or leaf, 1994) propose to comprise the ruthenium family catalyst of the zeolite of alkali, make that under atmospheric pressure synthetic ammonia becomes possibility from nitrogen and hydrogen.According to the result of Cisneros and Lunsford, synthetic ammonia can be at temperature 650K, under the atmospheric pressure, with 1.7 * 10 under the ruthenium family catalyst action that the X zeolite that has potassium is supported
-5Mol NH
3The speed of/g Ru/sec produces.
Yet existing catalyst still can not have enough activity and reaction rate.This shows, invent a kind of better ammonia synthesis catalyst, is that everybody expects.
Brief summary of the invention
In view of the above, one of purpose of this patent is exactly to propose a kind of improved ammonia synthesis catalyst, and this catalyst can improve the speed of ammonia synthesis under industrial condition.
Two of the purpose of this patent just provides a kind of improved technology, is used for preparing ammonia from nitrogen and hydrogen.
Owing to found ammonia synthesis catalyst by the group VIII transition metal group composition, this catalyst is stated from basic zeolite, form by alkali metal ion and bivalent metal ion furtherly, it has improved the speed that is generated ammonia by nitrogen and hydrogen reaction significantly, has reached these and other purpose of the present invention.
Detailed Description Of The Invention
This patent relates to group VIII transition metal/basic zeolite catalyst, is used for from nitrogen and hydrogen synthetic ammonia.This catalyst is made up of the group VIII transition metal that is stated from basic zeolite.Group VIII transition metal bunch preferably is made up of iron, ruthenium, osmium, is best with ruthenium wherein.Group VIII transition metal can prepare (seeing " catalyst manufacturing " second edition, A.B.Stiles, T.A.Koch, Marcel Dekker, New York, 1995) by traditional method.For example, ruthenium family can resemble Ru (NH by various ruthenium compounds
3)
6Cl
3Form.Particularly, the group VIII metallic compound is with ion-exchange, or the immersion method is attached on the zeolite, and the material of gained just is reduced subsequently, for example, by hydrogenization, has just obtained the compound of the corresponding metal (as Ru °) that exists with oxide form.
Be used to the zeolite (or faujasite) of supporting the zeolite of group VIII transition metal to be preferably the Faujasite type in this patent, as X zeolite, zeolite Y, EMT, ZSM-3, ZSM-20, trbasic zinc phosphate X or SAPO-37.Zeolite is the alumina silicate of microporous crystalline preferably, and preferred silicon is 1: 1 to 6: 1 with the ratio of aluminium, more preferably 1: 1 to 2.5: 1.
The catalyst that this patent proposes also contains alkali-metal cation of first family and divalent metal.Divalent metal can be alkaline-earth metal ions or divalent transition metal ion.Preferably using alkaline-earth metal ions, is best with barium ions.Bivalent metal ion can be used traditional handicraft, is incorporated into group VIII transition metal/zeolite catalyst as ion-exchange or immersion method.
The zeolite that is purchased contains alkali metal ion usually, as sodium.For example X zeolite contains sodium ion, generally is called the NaX zeolite.When but these zeolite former states are used, or at first to carry out processing such as ion-exchange or immersion, use other alkali metal, replace sodium, preferably replace with potassium, rubidium, caesium as potassium.Comprise alkali-metal zeolite, then will be, as use alkaline-earth metal ions through the processing of bivalent cation, combine by ion-exchange or ion-exchange and immersion and to carry out.
Forward and backward in the bivalent cation processing, the group VIII metal enters in the zeolite, forms metal cluster and prepares group VIII/M by traditional technological means
+ 2/ basic zeolite catalyst.Above-mentioned processing procedure can be used to prepare catalyst of the present invention, the preparation process order can be any, to carry out the combination of bivalent metal ion and group VIII transition metal, produce the described catalyst of this patent, this catalyst has activity in the reaction of preparation ammonia from nitrogen and hydrogen.
The catalyst based on the group VIII metal that this patent proposes promptly uses seldom group VIII metal adding basic zeolite, and the improvement of reaction rate is also benefited.Yet based on the weight of zeolite, the scope that supports preferably is 0.1～10%, is preferably 1～5%.If the group VIII metal is very expensive, best interpolation scope is 0.1～2.0%.
Seldom bivalent metal ion joins in the catalyst, just can improve its performance.The concentration ratio of bivalent metal ion and alkali metal ion preferably can be preferably 10～100 0.01～100.
In case divalent ion and group VIII metal join in the zeolite, it is very important investing zeolite alkalescence.Preferably composition is immersed alkali compounds, resemble bivalent metal ion or alkali metal hydride, alkaline alkoxide, basic anhydride, alkali metal wait and carry out.
The catalyst of using in this patent, when contacting with hydrogen with nitrogen, N
2With H
2Mol ratio should be 10: 1～1: 10, be preferably 1: 3～1: 6.Under the high enough temperature and pressures of the output that can make the ammonia that reacts the unit interval that produces, react.Temperature suitable during ammonia synthesis is 200～600 ℃, and pressure is atmospheric pressure to 400 atmospheric pressure.These parameters can be adjusted, and so that optimum reaction rate to be provided, depend primarily on the accessible condition of reactor in the reaction.Time of contact, weight (hourly) space velocity (WHSV) (g charging/g catalyst/hour), all be adjustable parameter, to obtain satisfied hydrazine yield (promptly extending contact time to obtain more ammonia, and vice versa).Furtherly, course of reaction not only can be interruption but also can be continuous.
With the catalyst of this patent, compare with previous catalyst, can make the speed of ammonia synthesis that surprising improvement is arranged.Because the improvement of speed makes to have better economic and security by the service condition milder in industrialization.
Can further set forth the purposes of this patent invention by some specific examples below, be confined to following several usage unless stated otherwise and not only.
Example
Catalyst synthesizes example
Example 1.Ru/NaX
(elementary analysis: Si-20.48%, Al-16.55% Na-12.6%), in 300 milliliters of distillation deionized waters, restrain Ru (NH with 0.936 to NaX zeolite (15 gram) for Union Carbide Corporation produces
3)
6Cl
3Carry out ion-exchange, then the solid with gained filter, drying, and under the temperature of 723K, use H
2Reduction contains ruthenium 1.85% weight in the final solid.
Example 2.Ru/KX
At first, (elementary analysis: Si-20.48%, Al-16.55% Na-12.67%), use 1molL to the NaX zeolite of Union Carbide Corporation
-1(1 mol) KNO
3The aqueous solution carries out ion-exchange three times (each consumption be 75,230,350ml), and dry back generates the KX zeolite.15 gram KX zeolites restrain Ru (NH with 0.936 in 1.2 premium on currency
3)
6Cl
3Carry out ion-exchange.The solid of gained after filtration, drying, and under the 723K temperature with the H that flows
2Reduction, the solid after the reduction immerses in the KOH aqueous solution that 310ml concentration is 0.2molal again, dry then the processing.Elementary analysis is: Ru-2.04%, Si-19.7%, Al-13.03%, Na-0.58%, K-16.08%.
Example 3.Ru/CsX
Get the gram of 1.24 in the example 2 sample (before immersing KOH), use 1mol L
-1The cesium acetate aqueous solution carry out ion-exchange three times (consumption is respectively 12.5,12.5,30 milliliters), after filtration and dry the processing, be Cs (OH) aqueous solution of 0.2molal with immersing concentration in the solid then.Elementary analysis is: Ru-2.01%, Si.13.88%, Al-7.9%%, Na-0.93%, K-2.5%, Cs-24.53%.
Example 4.Ru/BaX
Get 1.22 in the example 2 gram sample (before immersing KOH), carry out ion-exchange secondary (consumption be respectively 10 and 15ml) with the barium acetate aqueous solution of concentration 1 mol, filter and dry, the solid immersion 50ml concentration of generation is the Ba (OH) of 0.2molal
2In the aqueous solution.Elementary analysis: Ru.2.05%, Si-13.12%, Al-9.48%, K-1.32%, Ba-24.4%.
Example 5.Ru/BaX (2)
At first, (elementary analysis: Si-20.48%.Al-16.55% Na-12.67%), uses 1molL to the NaX zeolite of Union Carbide Corporation
-1KNO
3The aqueous solution carries out ion-exchange three times, and dry back generates the KX zeolite.17.68 gram KX zeolite restrains Ru (NH with 1.1048 in water
3)
6Cl
3Carry out ion-exchange.The solid of gained after filtration, dry and under the temperature of 723K with the hydrogen reducing that flows.Get 3.285 these solids of gram, carry out ion-exchange secondary (consumption is respectively 10 and 10 milliliters), filter and drying with the barium acetate aqueous solution of 1mol/L concentration.The solid that generates immerses the Ba that 30ml concentration is 0.2moal (OH) again
2The aqueous solution.Elementary analysis: Ru-2.10%, Si-14.38%, Al-9.004%, K-1.47%, Ba-21.6%.
Reactive example
All samples divides before reaction and is sieved to 170 orders (96 μ m).Before the reaction, catalyst is put into the constant recirculation reactor of volume, under the 723K temperature, carry out in-situ reducing.Under an atmospheric pressure, mol ratio is 3: 1 H
2, N
2Mixture is sent in the system.The ammonia of producing concentrates in the liquid nitrogen gatherer, hinders reaction to prevent product.The speed that ammonia produces by always falling calculating as the pressure in the system of the function of time, and is expressed as the molal quantity that every gram ruthenium in the unit interval produces ammonia.Be exposed to the ruthenium (dispersion) on top layer, measure by the hydrogenation absorption measuring instrument of standard, this result is used for calculating the specific speed that each top layer nail atom produces.Use the ammonia synthesis reaction result of ruthenium catalyst
| Routine number | Sample | The share of the Ru that exposes | Temperature/K (± 5K) | Reaction speed/10 -6molNH 3， (gRu) -1s -1 | Specific speed/10 -4g -1 |
| 1 | Ru/NaX | 0.57 | 650 | 4.48 | 7.94 |
| 2a 2b 3a 3b 4a 4b 5a 5b | Ru/KX Ru/KX Ru/CsX Ru/CsX Ru/BaX Ru/BaX Ru/BaX(2) Ru/BaX(2) | 0.93 0.93 0.72 0.72 0.92 0.92 0.79 0.79 | 650 700 650 700 650 700 650 700 | 2.84 14.2 7.62 25.9 34.5 105 33.6 127 | 3.09 15.4 10.7 36.4 37.9 115 43.0 163 |
To under the fixed temperature, the Ru catalyst that contains Ba is used for ammonia synthesis has higher activity than the catalyst that alkali metal containing ion (Na, K, Cs) does not contain Ba.
Obviously, it is possible by the instruction of above-mentioned example this patent being carried out various modifications and variations.But what state is that in the scope of additional right and requirement, this patent can be implemented outside the special narration of this paper.
Claims (31)
1. one kind is used for by N
2And H
2Catalyst of synthetic ammonia comprises:
The basic zeolite carrier;
Be stated from the group VIII transition metal bunch of basic zeolite;
Be incorporated into divalence and monovalent metallic ion in the Zeolite support;
2. the catalyst in the claim 1, Zeolite support is a kind of alumina silicate.
3. the catalyst in the claim 2, the ratio of silicon and aluminium is 1: 1 to 6: 1 in the zeolite.
4. the catalyst in the claim 2, the ratio of silicon and aluminium is 1: 1 to 2: 1 in the zeolite.
5. the catalyst in the claim 3, zeolite is the zeolite of faujasite type.
6. the catalyst in the claim 5, faujasite are from by X zeolite, zeolite Y, and EMT, ZSM-3, ZSM-20 selects in the group that SAPO-37 and trbasic zinc phosphate X form.
7. the catalyst in the claim 1, group VIII transition metal bunch are meant the ruthenium metal cluster.
8. the catalyst in the claim 1, wherein bivalent metal ion is meant alkaline-earth metal ions.
9. the catalyst in the claim 1, wherein bivalent metal ion is meant transition metal ions.
10. the catalyst in the claim 1, wherein bivalent metal ion is Ba
+ 2
11. the catalyst in the claim 1 further comprises the alkali metal ion that is stated from described zeolite.
12. the catalyst in the claim 11 is wherein selected in the group that alkali metal ion is made up of potassium, rubidium and caesium.
13. the catalyst in the claim 1, group VIII transition metal bunch wherein, its content is the 0.1-10% of zeolite weight.
14. the catalyst in the claim 1, the mol ratio of bivalent metal ion and alkali metal ion are 0.1 to 100.
15. the catalyst in the claim 14, the mol ratio of bivalent metal ion and alkali metal ion are 10 to 100.
16. the catalyst in the claim 1, this catalyst pass through to immerse from divalent metal hydroxide, alkali metal hydroxide, and alkali metal alkoxide, the solution of the alkali compounds of selecting in alkali metal oxide and the alkali metal, thus present alkalescence.
17. the catalyst in the claim 16, divalent metal hydroxide are the hydroxide of the divalent metal identical with the bivalent metal ion that exists in the catalyst.
18. a method of producing ammonia comprises:
With catalyst and N
2And H
2Mist contact, catalyst comprises: (i) basic zeolite carrier, (ii) the 8th group 4 transition metal of being supported by basic zeolite bunch (iii) is attached to the bivalent metal ion in the Zeolite support, (iv) is attached to the alkali metal ion in the Zeolite support.
Under enough temperature and pressures, N
2And H
2Reaction generates NH
3
19. the method for claim 18, Zeolite support are a kind of alumina silicate.
20. the method for claim 19, the ratio of Si and Al was from 1: 1 to 6: 1 in the Zeolite support.
21. the method for claim 19, the ratio of Si and Al was from 1: 1 to 2: 1 in the Zeolite support.
22. the method in the claim 18, Zeolite support is meant faujasite.
23. the method in the claim 22, faujasite are from by X zeolite, zeolite Y, and EMT, ZSM-3, ZSM-20 selects in the group that SAPO-37 and trbasic zinc phosphate are formed.
24. the method in the claim 18, group VIII transition metal bunch is the ruthenium metal cluster.
25. the method in the claim 18, bivalent metal ion are alkaline-earth metal ions.
26. the method in the claim 18, bivalent metal ion are transition metal ions.
27. the method in the claim 18, bivalent metal ion are Ba
+ 2
28. the method in the claim 18 further is included in the alkali metal ion in the Zeolite support.
29. select in the group that the method in the claim 28, alkali metal ion are made up of potassium, rubidium and caesium.
30. the method in the claim 18, temperature range are 200～600 ℃.
31. the method in the claim 18, pressure limit are 1 atmospheric pressure～400 atmospheric pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44388595A | 1995-05-31 | 1995-05-31 | |
| US08/443,885 | 1995-05-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1186452A true CN1186452A (en) | 1998-07-01 |
Family
ID=23762565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194318A Pending CN1186452A (en) | 1995-05-31 | 1996-05-31 | Catalyst and process for preparing ammonia |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0840646A1 (en) |
| CN (1) | CN1186452A (en) |
| AU (1) | AU5950396A (en) |
| BR (1) | BR9608749A (en) |
| CA (1) | CA2222806A1 (en) |
| WO (1) | WO1996038222A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK173814B1 (en) | 1999-03-15 | 2001-11-12 | Topsoe Haldor As | Process for the preparation of ammonia and catalyst for the synthesis of ammonia |
| EP1170255B1 (en) | 2000-07-06 | 2006-12-13 | Haldor Topsoe A/S | Recovery of ammonia synthesis catalyst |
| EP2650047B1 (en) | 2010-12-07 | 2018-01-31 | Tokyo Institute of Technology | Ammonia synthesis catalyst and ammonia synthesis method |
| JP6344052B2 (en) * | 2014-05-20 | 2018-06-20 | 株式会社Ihi | Ammonia synthesis catalyst and ammonia synthesis method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3253887A (en) * | 1962-08-03 | 1966-05-31 | Exxon Research Engineering Co | Ammonia synthesis catalyst and process |
| CA965766A (en) * | 1970-06-22 | 1975-04-08 | Akio Furuta | Ammonia synthesis catalyst and process |
| US4142993A (en) * | 1977-12-07 | 1979-03-06 | The Research Council Of Alberta | Transition metal catalyst |
| SE415173B (en) * | 1977-12-19 | 1980-09-15 | Atomenergi Ab | PROCEDURE FOR THE MANUFACTURING OF AMMONIA BY CATALYZED REACTION BETWEEN WHEAT AND NITROGEN |
| US4348370A (en) * | 1980-01-08 | 1982-09-07 | Phillips Petroleum Company | Ammonia synthesis with catalyst derived by heating on a support a salt selected from alkali metal, alkaline earth metal, iron and cobalt hexacyanocobaltates and hexacyanoruthenates |
| GB8307612D0 (en) * | 1983-03-18 | 1983-04-27 | British Petroleum Co Plc | Ammonia production and catalysts |
| FR2660578B1 (en) * | 1990-04-09 | 1994-09-23 | Elf Aquitaine | CATALYST BASED ON HIGH SYNTHESIS SI: AL FAUJASITE AND ITS APPLICATION TO ACID CATALYSIS REACTIONS CARRIED OUT ON HYDROCARBONIC LOADS. |
-
1996
- 1996-05-31 CA CA002222806A patent/CA2222806A1/en not_active Abandoned
- 1996-05-31 AU AU59503/96A patent/AU5950396A/en not_active Abandoned
- 1996-05-31 WO PCT/US1996/007948 patent/WO1996038222A1/en not_active Application Discontinuation
- 1996-05-31 CN CN96194318A patent/CN1186452A/en active Pending
- 1996-05-31 BR BR9608749-8A patent/BR9608749A/en unknown
- 1996-05-31 EP EP96916741A patent/EP0840646A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9608749A (en) | 1999-12-07 |
| EP0840646A1 (en) | 1998-05-13 |
| AU5950396A (en) | 1996-12-18 |
| WO1996038222A1 (en) | 1996-12-05 |
| CA2222806A1 (en) | 1996-12-05 |
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