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CN1086151C - High-activity ommonia decomposition catalyst - Google Patents

High-activity ommonia decomposition catalyst Download PDF

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Publication number
CN1086151C
CN1086151C CN98114265A CN98114265A CN1086151C CN 1086151 C CN1086151 C CN 1086151C CN 98114265 A CN98114265 A CN 98114265A CN 98114265 A CN98114265 A CN 98114265A CN 1086151 C CN1086151 C CN 1086151C
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catalyst
ammonia
nickel
moo
nio
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CN1245737A (en
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魏昭彬
李�灿
辛勤
梁长海
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The present invention relates to a high active catalyst for ammonia decomposition, which is composed of active constituents and carriers, wherein the active constituents comprises molybdenum and nickel, and the carriers are Al2O3 or MgO. The catalyst comprises the following components by weight percentage: 0.5 to 16 of nickel, 3 to 21 of molybdenum and the carriers as the rest. In a method for preparing the catalyst, the salts of the two metals are prepared into a water solution or an ammonia solution and jointly impregnated onto the carriers, wherein the molar ratio of the metallic elements in the impregnation liquid is 0.1 to 1:1; the impregnation liquid is then baked at a temperature of 100 to 140 DEG C and roasted at a temperature of 450 to 600 DEG C, the time of roasting lasts for 2 to 6 hours, and the catalyst is prepared. The present invention can completely decompose ammonia into nitrogen and hydrogen at low temperature, and has the advantage of high catalytic activity.

Description

A kind of high-activity ommonia decomposition catalyst
The present invention relates to catalyst technology, a kind of low-temp reaction catalyst that industry ammonia decomposes that is used for is provided especially.
Be mainly used in two big fields at industrial ammonia decomposition catalyzer: one is aspect the environmental protection, in order to handle oven gas, fuel gas, petroleum refinery's waste gas and NO xThe residual ammonia vapour in the tail gas is handled in reduction, and is not contaminated to preserve the ecological environment.Another is in metallurgical industry, vents one's spleen as the protection gas of steel and non-ferrous metal heat treatment process with the branch of ammonia, is applied to the bright annealing and the soldering of high-alloy steel and magnet steel, the bright quenching of foundry goods and sintered metal product.Therefore, ammonia decomposition catalyzer is an industrial broad-spectrum class catalyst.
At present industrial widely used ammonia decomposition catalyzer is to be that active constituent is carried on Al with one-component such as iron, nickel, zinc, titanium, molybdenum, shackles or many components mixed oxide 2O 3Or on the MgO carrier.
It is an endothermic reaction that ammonia decomposes, Δ H=26 kilocalorie improves the decomposition reaction that operating temperature helps ammonia, and on common Ni base even Ru were catalyst based, its reaction temperature generally was not less than 800 ℃.When catalyst during as the cleaning catalyst of coke-stove gas or general dyestuff coal gas, reaction temperature even will be higher than 1000 ℃ [Fuel, 74 (1995) 1968].Too high reaction temperature has not only increased energy consumption, also can shorten the service life of consersion unit.
U.S.Patent 5,188, and 811 have narrated a kind of catalyst based purification that is used for heating gas of Mo that is prepared by the mixed oxide of Zn, Ti and Mo, and under 700～900 ℃ of reaction temperatures, catalyst is H in removing coal gas 2In the time of S, little ammonia wherein can also be resolved into nitrogen and hydrogen.
The object of the present invention is to provide a kind of catalyst that can at a lower temperature ammonia all be resolved into nitrogen and hydrogen, it has advantages of high catalytic activity.
The invention provides a kind of high-activity ommonia decomposition catalyst, be made up of active constituent and carrier, it is characterized in that: active constituent is molybdenum and nickel, and carrier is Al 2O 3Or MgO; Catalyst consists of (the present invention all is weight percentage) except that special indicating
Nickel 0.5～16
Molybdenum 3～21
The carrier surplus
Nickel is preferably 2～12 among the present invention, and molybdenum is preferably 5～14.
The present invention also provides the preparation method of above-mentioned high-activity ommonia decomposition catalyst, it is characterized in that: the salt of two kinds of metals is made the aqueous solution or ammonia solution is immersed on the carrier jointly, the mol ratio Ni of metallic element: Mo is 0.1～1: 1 in the maceration extract; Carry out 100～140 ℃ of temperature oven dry again, 450～600 ℃ of temperature roastings, roasting time 2～6 hours makes catalyst.
In the said method, maceration extract is preferably ammonia solution.Nickel salt is selected from a kind of of nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickelous sulfate, and molybdenum salt is selected from a kind of of ammonium molybdate, sodium molybdate.
Ni of the present invention and Mo composite oxide catalysts are in the ammonia decomposable process, and its phase structure will be by composite oxides NiMoO 4Be transformed into a kind of stable complex nitride, its structural formula is Ni 3Mo 3N; Partly with MoO 3The oxide that crystalline phase exists will be transformed into Mo 2The N nitride.Ni 3Mo 3N and Mo 2Has excellent ammonia decomposition catalytic activity on nitride.
Therefore, before use, catalyst of the present invention preferably carries out pre-nitrogen treatment, and programming rate is not more than 10 ℃/minute, and final nitriding temperature is 650～750 ℃, and the ammonia air speed is not less than 400h -1, nitridation time is not less than 1 hour.This catalyst can be widely used in the decomposition reaction of various ammonia, is specially adapted to be decomposed by ammonia the gaseous mixture of preparation nitrogen and hydrogen, as the protection gas of various heat treatment processes in the metallurgical industry.
The volume space velocity of reaction temperature and ammonia has appreciable impact to the decomposition efficiency of ammonia.Among the present invention, to loading on Al 2O 3Or the Ni on the MgO carrier and/or Mo ammonia decomposition catalyzer be 600～750 ℃ of temperature ranges, and the volume space velocity of ammonia is at 600～3600h -1Scope is investigated.At 900h -1Under the volume space velocity, reaction temperature is not higher than 650 ℃, unreacted NH in the product tail gas 3Can be lower than 0.07%.When the volume space velocity of ammonia is brought up to 1800h -1, when reaction temperature is 700 ℃, unreacted NH 3Be lower than 0.06%.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 NiO/Al 2O 3Prepare with NiO/MgO
Nickel nitrate is dissolved in is mixed with maceration extract in the ammoniacal liquor, add α-Al 2O 3Or the MgO carrier flooded 4 hours.α-Al 2O 3The specific area of carrier is 1.8m 2/ g, the specific area of MgO carrier is 43m 2/ g.Stir down and boil off solution, dried 12 hours for 120 ℃, 500 ℃ of roastings 4～5 hours.Make NiO/Al respectively 2O 3With the NiO/MgO catalyst.
Embodiment 2 MoO 3/ Al 2O 3And MoO 3/ MgO preparation
Ammonium molybdate is dissolved in ammoniacal liquor is mixed with in the maceration extract, add the α-Al described in the example 1 2O 3Or MgO carrier dipping 4 hours, stir down and boil off solution, dried 12 hours 500 ℃ of roastings 4～5 hours for 120 ℃.Make MoO respectively 3/ Al 2O 3And MoO 3/ MgO catalyst.
Embodiment 3 NiO-MoO 3/ Al 2O 3And NiO-MoO 3/ MgO preparation
Two component NiO-MoO 3Loaded catalyst can be used the graded impregnation method, soaks twice dipping preparation of nickel order after soaking molybdenum earlier; Also can promptly earlier ammonium molybdate and nickel nitrate be mixed with dipping solution with soaking method altogether, immerse carrier again, single-steeping supports NiO and MoO simultaneously 3Component.The present invention adopts and soaks the preparation of method single-steeping altogether.Earlier ammonium molybdate and nickel nitrate are dissolved in altogether and are mixed with maceration extract in the ammoniacal liquor, add α-Al 2O 3Or MgO carrier dipping 4 hours, stir down and boil off solution, dried 10 hours 500 ℃ of roastings 4～5 hours for 120 ℃.Thereby make NiO-MoO 3/ Al 2O 3And NiO-MoO 3/ MgO catalyst.
Change the addition of ammonium molybdate and nickel nitrate, can make and have different Ni/the two component NiO-MoO of series of Ni+Mo atomic ratio 3Catalyst.
NiO-MoO 3/ Al 2O 3And NiO-MoO 3/ MgO catalyst series is formed as table 1.
Table 1 support type NiO-MoO 3The composition sample title carrier NiO wt% MoO of catalyst series 3Wt% Ni/Ni+Mo bulk density g/ml Ni-Al α-Al 2O 36.0 0 1.174 Mo-Al α-Al 2O 30 10.0 0.719NiMo-Al (1) α-Al 2O 33.0 10.0 0.325: 1 1.223NiMo-Al (2) α-Al 2O 36.0 10.0 0.5: 1 0.705NiMo-Al (3) α-Al 2O 39.0 10.0 0.625: 1 0.749NiMo-Al (4) α-Al 2O 312.0 10.0 0.85: 1 0.852 Mo-Mg MgO 0 10.0 0.481NiMo-Mg (1) MgO 3.0 10.0 0.325: 1 0.604
The nitrogen treatment of embodiment 4 catalyst
To NiMo/Al 2O 3Also carry out pre-nitrogen treatment, make the activity of such catalysts component become the nitrogen state.The pre-nitrogen treatment of sample is to carry out in crystal reaction tube, with NH 3Be nitrogenize gas, its volume space velocity is 10000h -1, the nitrogenize final temperature is 700 ℃, keeps 2 hours.Be mainly Ni after the nitrogenize on the sample 3Mo 3The N phase also has a small amount of γ-Mo 2N exists mutually.
Embodiment 5
Example 5 narration MoO 3/ Al 2O 3And NiO-MoO 3/ Al 2O 3The ammonia decomposability of catalyst.The evaluation of ammonia decomposability is carried out in crystal reaction tube.Catalyst amount 1 gram, granularity 20～40 orders, steel cylinder ammonia are reaction gas.
Because ammonia decomposition reaction is an endothermic reaction, improve reaction temperature and will help the carrying out of ammonia decomposition reaction, the ammonia concentration that reaction is in other words flowed out in the tail gas reduces.Catalyst NiO/Al to example 1,2 and 3 preparations 2O 3, MoO 3/ Al 2O 3And NiO-MoO 3/ Al 2O 3The ammonia decomposition reaction performance estimate, with NH 3Volume space velocity be fixed as 1800h -1, it the results are shown in table 2.
Comparative example 1 catalyst performance compares 1
Under the reaction condition identical with example 5 an industrial ammonia decomposition catalyzer AD-946 is carried out the test of ammonia decomposability, it the results are shown in table 2.
NH in table 2 reaction end gas 3Concentration (%) catalyst reaction temperatures/℃
600 650 700 750 Ni-Al 1.42 Mo-Al 14.2 0.63 0.14NiMo-Al(2) 11.80 0.16 0.06 AD-946 17.9 6.61 0.72 0.06
The result shows, of the present invention couple of component NiO-MoO 3/ Al 2O 3The ammonia degrading activity of catalyst compares NiO/Al 2O 3And MoO 3/ Al 2O 3Catalyst is much higher, and higher than industrial AD-946 activity of such catalysts.Ammonia concentration in tail gas is similarly at 0.06% o'clock, the two component NiO-MoO of the present invention 3/ Al 2O 3The reaction temperature of catalyst is than low 50 ℃ of industrial catalyst.
Embodiment 6
To NiO (6wt%)-MoO 3(10wt%)/Al 2O 3Catalyst is also at NH 3Volume space velocity is 3600h -1Under the condition, investigated the influence of reaction temperature to the ammonia degrading activity, the result is as shown in table 3.
NiO (6wt%)-MoO under the table 3 differential responses temperature 3(10wt%)/
Al 2O 3NH on the catalyst 3The conversion ratio reaction temperature (℃) 600 650 700 750NH 3NH in conversion ratio (%) 78.90 90.36 99.88＞99.90 tail gas 3Concentration (%) 11.79 5.06 0.06＜0.05
Can find out by table 3 result, for NiO (6wt%)-MoO 3(10wt%)/Al 2O 3Catalyst is at NH 3Air speed is 3600h -1The time, when reaction temperature is higher than 750 ℃, the NH in the reaction end gas 3Concentration is less than 0.05%.
Embodiment 7
NH under certain reaction temperature 3The ammonia decomposability of volume space velocity appreciable impact catalyst.Reaction temperature is fixed as 650 ℃, changes NH 3Air speed, MoO 3/ Al 2O 3And NiO-MoO 3/ Al 2O 3The ammonia decomposability is as shown in table 4 on the catalyst.
Comparative example 2 NH 3Air speed influences catalyst performance
With example 7 the same terms under, industrial AD-946 catalyst is carried out relevant NH 3Air speed influence test, gained the results are shown in table 4.
NH in table 4 reaction end gas 3Concentration (%) reaction temperature: 650 ℃ of catalyst n H 3Air speed/h -1
900 1800 2700 3600 Ni-Al 1.42 Mo-Al 0.30 0.63 0.79 1.38NiMo-Al(2) 0.07 0.33 0.75 0.98 AD-946 1.42 6.61 12.2
The result shows, at various NH 3Under the air speed, NiO-MoO 3/ Al 2O 3The ammonia degrading activity of catalyst all is higher than one-component NiO/Al 2O 3Or MoO 3/ Al 2O 3Catalyst is more higher than industrial AD-946 catalyst performance.
Embodiment 8
Under identical reaction condition, reaction temperature is 650 ℃, NH 3Air speed is 1800h -1, investigate NiO-MoO with different Ni/Ni+Mo atomic ratio 3/ Al 2O 3The ammonia decomposability of catalyst, its result is as shown in table 6.
Table 5 Ni/Ni+Mo atomic ratio is to NiO-MoO 3/ Al 2O 3The ammonia decomposability of catalyst influence Ni/Ni+Mo 0 0.325 0.5 0.625 0.85 1.0NH 3NH in conversion ratio (%) 98.75 99.34 99.64 99.79 99.68 97.20 tail gas 3Concentration (%) 0.63 0.33 0.16 0.10 0.16 1.42
Table 5 is clear to show two component NiO-MoO 3/ Al 2O 3The ammonia decomposability of catalyst is higher than NiO/Al 2O 3And MoO 3/ Al 2O 3Catalyst, and under suitable Ni/Ni+Mo atom proportioning, the ammonia decomposability of catalyst can reach optimum.
Embodiment 9
Carrier α-the Al of different catalyst is adopted in this example narration 2O 3And MgO, prepared NiO, MoO 3And NiO-MoO 3Ammonia decomposability Deng catalyst also obviously has difference, result such as table 6.
The different carriers of table 6 are to catalyst ammonia decomposability influence (NH 3Conversion ratio %) catalyst base NiO (6wt%) MoO 3(10wt%) NiO (6wt%)-
MoO 3(10wt％) MgO 98.49 96.54α-Al 2O 3 97.20 98.75 99.64
Table 6 data are that ammonia is 650 ℃ in reaction temperature, NH 3Air speed is 1800h -1The time conversion ratio.Obviously, α-Al 2O 3NiO on the carrier, MoO 3And NiO-MoO 3Ammonia decomposability Deng catalyst is all good than catalyst on the corresponding M gO carrier.For the MgO carrier, single-activity component MoO 3Than two component NiO-MoO 3, its ammonia degrading activity is higher, and the ammonia degrading activity of NiO/MgO is very different.Because α-Al 2O 3Different with the surface nature of MgO carrier, the active constituent of the same content of load, its catalyst performance has shown notable difference.
Embodiment 10
The narration of this example is carried on α-Al 2O 3With the MoO on the MgO carrier 3And NiO-MoO 3The ammonia degrading activity of catalyst the results are shown in table 7 with the variation in reaction time.
Table 7 NH 3Degrading activity and reaction time concern NH 3Conversion ratio (%)
650 ℃ of reaction temperatures, NH 3Air speed 1800h -1Reaction time (h) Mo-Al NiMo-Al (2) Mo-Mg NiMo-Mg0.5 72.58 76.21 88.49 68.593.5 97.29 97.47 97.78 92.616.5 99.23 99.64 98.29 95.830.5 99.21 99.62 98.49 96.54
Table 7 is the result show, is carried on α-Al 2O 3With the MoO on the MgO carrier 3And NiO-MoO 3When catalyst had just begun in reaction, the degrading activity of its ammonia was all lower, but along with the carrying out that reacts, ammonia dissociation rate progressively improves, and surpassed 6.5 hours when the reaction time, and its catalyst activity is basicly stable.
Embodiment 11
To NiO-MoO in the example 5 3/ Al 2O 3Nitrogenize attitude catalyst n iMoNx/Al behind pre-nitrogen treatment 2O 3Be used for ammonia decomposition reaction, and compare, investigate NH in the reaction end gas with oxidized catalyst 3The relation in concentration and reaction time the results are shown in table 8.
NH in table 8 reaction end gas 3Concentration and time relationship
Reaction temperature: 650 ℃, NH 3Air speed: 1800h -1Reaction time 0.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5NiO-MoO 3/ Al 2O 310.8 0.71 0.31 0.21 0.12 0.09 0.10 0.10NiMoNx/Al 2O 32.17 0.62 0.21 0.15 0.09 0.07 0.06 0.06
Table 8 presentation of results is worked as NiO-MoO 3/ Al 2O 3Behind pre-nitrogen treatment, its catalytic activity obviously improves, and shows that not only ammonia concentration in the product tail gas had only 1/5 of oxidized catalyst when reaction was initial, and reaches when stablizing NH in the tail gas when ammonia decomposition reaction 3Concentration is also much lower.Certainly, oxidation state NiO-MoO 3/ Al 2O 3This also is transformed into the nitrogenize attitude gradually catalyst in the cracked ammonium reaction.The XRD data show that nitrogenize attitude catalyst and oxidized catalyst are behind ammonia decomposition reaction, and its diffraction spectrogram much at one.We think, Ni 3Mo 3N and γ-Mo 2N is the active phase of catalyst in ammonia decomposition reaction mutually.

Claims (6)

1. a high-activity ommonia decomposition catalyst is made up of active constituent and carrier, it is characterized in that: active constituent is molybdenum and nickel, and carrier is Al 2O 3Or MgO; Catalyst weight percentage consists of
Nickel 0.5～16
Molybdenum 3～21
The carrier surplus.
2. according to the described high-activity ommonia decomposition catalyst of claim 1, it is characterized in that:
Nickel 2～12
Molybdenum 5～14.
3. the preparation method of the described high-activity ommonia decomposition catalyst of claim 1 is characterized in that: the salt of two kinds of metals is made the aqueous solution or ammonia solution is immersed on the carrier jointly, the mol ratio Ni of metallic element: Mo is 0.1～1: 1 in the maceration extract; Carry out 100～140 ℃ of temperature oven dry again, 450～600 ℃ of temperature roastings, roasting time 2～6 hours makes catalyst.
4. according to the preparation method of the described high-activity ommonia decomposition catalyst of claim 3, it is characterized in that: maceration extract is an ammonia solution.
5. according to the preparation method of the described high-activity ommonia decomposition catalyst of claim 3, it is characterized in that: nickel salt is selected from a kind of of nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickelous sulfate, and molybdenum salt is selected from a kind of of ammonium molybdate, sodium molybdate.
6. according to the preparation method of the described high-activity ommonia decomposition catalyst of claim 3, it is characterized in that: catalyst carries out pre-nitrogen treatment, and final nitriding temperature is 650～750 ℃, ammonia air speed 400h -1～3600h -1, nitridation time 1～2 hour.
CN98114265A 1998-08-26 1998-08-26 High-activity ommonia decomposition catalyst Expired - Fee Related CN1086151C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105293591A (en) * 2015-11-10 2016-02-03 沈阳化工大学 Method for preparing magnesium-nickel metal compound oxide with active magnesium oxide as raw material
CN108031474A (en) * 2017-12-14 2018-05-15 西安元创化工科技股份有限公司 A kind of coke-stove gas ammonia decomposition catalyzer and preparation method thereof
CN108486391A (en) * 2018-03-23 2018-09-04 宁夏大学 A kind of preparation method of elemental Germanium
CN114100661A (en) * 2021-11-30 2022-03-01 福州大学 Catalyst for preparing hydrogen by decomposing molybdenum-based ammonia and preparation method thereof
CN115555015A (en) 2022-09-16 2023-01-03 福州大学 Supported Ru and/or Ni catalyst and preparation method thereof

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