CN102463120A - Catalyst containing nickel and manganese and its preparation method and use - Google Patents
Catalyst containing nickel and manganese and its preparation method and use Download PDFInfo
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Abstract
The invention discloses a catalyst containing nickel and manganese and its preparation method and use. The catalyst containing nickel and manganese contains a), nickel oxide, wherein nickel content is in a range of 15 to 55 wt%, and b), manganese oxide, wherein manganese content is in a range of 0.1 to 15 wt%. At least one of alumina, silicon oxide, titanium oxide and zirconia is utilized as a catalyst carrier. The preparation method comprises the following steps of dissolving a nickel salt and a manganese salt in an organic acid solution, dipping the catalyst carrier by the mixed solution obtained by the previous step, drying, and carrying out thermolysis to obtain the catalyst containing nickel and manganese. The organic acid solution is an organic carboxylic acid or a reducing organic acid, wherein a total charge mole ratio of carboxyl to metal ions of the organic carboxylic acid is (0.5 to 3): 1; and a mole ratio of the reducing organic acid to metal ions is (0.2 to 2): 1. The catalyst containing nickel and manganese has good methanation activity, can be utilized for removing a trace amount of oxycarbides in hydrogen-rich process gas, and also can be utilized for a methanation reaction of various synthetic gas having high CO content.
Description
Technical field
The present invention relates to catalyst field, say further, relate to a kind of Catalysts and its preparation method and application of nickeliferous and manganese.
Background technology
Methanation reaction is the simplest Fischer-Tropsch synthesis.Reaction equation is:
Two main application fields of methanation reaction, the one, as the CO hydro-conversion of high concentration, the 2nd, remove oxycarbide in the rich hydrogen raw material.The former effect is with synthesis gas or various CO of being rich in and H
2Raw material to be converted into the unit volume calorific value through methanation higher, and safer stable be the town gas or the substitute natural gas of main component with methane; The latter's effect is to purify the various process gas that are rich in hydrogen, as in ethylene unit and synthetic ammonia installation, using so that qualified hydrogen source to be provided.
At present mostly broad research and the methanation catalyst that uses are with the nickel catalyst of metallic nickel as main active component, commercial catalyst such as G-65, C13-4, and J103, J105 etc.It is methanation catalyst that these catalyst all belong to nickel, and the content of nickel generally adopts Ni/Al between 10%～40%
2O
3Or add other cocatalyst component on this basis and be prepared from.In disclosed patent, a lot of methanation catalysts also are to be active component with nickel, add other auxiliary agent simultaneously to improve activity of such catalysts and stability.As disclosed catalyst among the patent US3933883 be Ni/Co than for the nickel oxide of 1-1.5 and supported by cobalt oxide in containing γ-Al
2O
3The high purity aluminium oxide carrier on, except the Ni metal, also added multiple auxiliary agent in the catalyst, like some alkaline earth oxides and rare earth composition.Other auxiliary agent also comprises some like chromium, potassium, sodium, silicon, zirconium etc., in a lot of documents, relevant report is arranged also.Comprise rare earth metal and magnesium in Chinese patent CN 89105365 its auxiliary agents of disclosed catalyst, its catalyst consist of NiO 20～40%, rare earth oxide 1～20%, MgO1～20%, all the other are Al
2O
3Except adopting lanthanum, magnesium, also introduced sodium or barium in the auxiliary agent of patent CN 88109760 open catalyst, its content is 0.1-1%.Patent CN 200710146033.7 disclosed a kind of methanation catalysts and preparation method thereof, each constituent mass percentage of catalyst consists of: Al
2O
3: 70～86%; NiO:12～20%; La
2O
3: 0.5～5%; MgO:0.5～5%; CeO
2: 0.1～5%; CaO:0.1～3%; Na
2O:0.1～1%; BaO:0.01～2%.
These above-mentioned catalyst, they have methanation activity preferably in specific separately reaction system, mainly be applicable to like CN 89105365 disclosed catalyst to remove a spot of oxycarbide in ammonia factory and the device for producing hydrogen process gas; And CN 200710146033.7 disclosed a kind of methanation catalysts mainly are to be used for reaction raw materials to contain 96% above CH
4System.
Therefore, seek a kind of applied range, the better catalyst of catalytic activity is the present technical issues that need to address.
Summary of the invention
For solving the problem that exists in the prior art; The invention provides a kind of Catalysts and its preparation method and application of nickeliferous and manganese; The system dip loading oxide carrier that adopts metal active constituent and organic carboxyl acid to dissolve each other; The catalyst that generates has better methanation activity, both can be used as the trace amounts of oxycarbide that removes in the rich hydrogen process gas and has used, and can in the methanation reaction of the higher synthesis gas of various CO content, use again.
One of the object of the invention provides a kind of catalyst of nickeliferous and manganese.
With the total restatement of catalyst, comprise following component:
A) nickel oxide, wherein nickel content is 15～55 weight %, preferred 15～45 weight %, more preferably 15～40 weight %
B) manganese oxide, wherein manganese content is 0.1～15 weight %, preferred 0.5～10 weight %, more preferably 0.5～5 weight %,
Said catalyst carrier is at least a in aluminium oxide, silica, titanium oxide, the zirconia;
Said catalyst is the method preparation through may further comprise the steps:
Nickel salt and manganese salt and organic acid soln dissolve each other, and are impregnated on the said carrier, after oven dry, thermal decomposition, make;
Said organic acid is organic carboxyl acid or organic acid with reproducibility, optimization citric acid, tartaric acid, at least a in butanedioic acid, the ascorbic acid (being vitamin C);
Wherein the carboxyl in the organic carboxyl acid is (0.5～3) with the ratio of metal ion total electrical charge molal quantity: 1, preferred (0.5～2): 1;
The preferred nickel nitrate of nickel salt, the preferred manganese nitrate of manganese salt.
Two of the object of the invention provides a kind of Preparation of catalysts method of nickeliferous and manganese, comprises:
Nickel salt and manganese salt and organic acid soln dissolve each other, and are impregnated on the said carrier, after oven dry, thermal decomposition, make;
Said organic acid is organic carboxyl acid or organic acid with reproducibility, optimization citric acid, tartaric acid, at least a in butanedioic acid, the ascorbic acid (being vitamin C);
Wherein the carboxyl in the organic carboxyl acid is (0.5～3) with the ratio of metal ion total electrical charge molal quantity: 1, preferred (0.5～2): 1; Said organic acid with reproducibility is (0.2～2) with the ratio of metal ion molal quantity: 1;
The preferred nickel nitrate of nickel salt, the preferred manganese nitrate of manganese salt.
In the concrete preparation process of catalyst of the present invention; Described active component a), b) can the substep or be impregnated into simultaneously on the described carrier; That is to say; Described active component nickel component a) can be prior to or subsequent to described active component b) manganese be impregnated on the carrier, also can with described active component b) manganese be impregnated on the carrier simultaneously.
Catalyst through oven dry after, again under 300 ℃～600 ℃ through 2～12 hours thermal decomposition process.
Three of the object of the invention provides a kind of application of catalyst in methanation reaction and purified hydrogen of nickeliferous and manganese.
Catalyst of the present invention is applicable to that oxycarbide (comprises CO, CO
2) carry out being particularly useful for the purification process of process gas in synthetic ammonia installation or the ethylene unit in the technology of methanation reaction with hydrogen, and the process of synthesis gas system substitute natural gas or high heating value gas.
Catalyst of the present invention has following characteristics:
1,, makes that the methanation activity of catalyst of the present invention is high because the present invention has introduced manganese as auxiliary agent.
2,, make that auxiliary agent manganese is better to the modifying function of active component nickel in the catalyst of the present invention owing to adopt the organic acid soln impregnated carrier of metallic compound in the catalyst preparation process of the present invention.
3, catalyst of the present invention has adaptability widely, promptly under very wide reaction condition, all has high reactivity to embody, and is not only applicable to remove the oxycarbide in the hydrogen-rich gas, also is applicable to the methanation reaction of the synthesis gas of various CO content.
The specific embodiment
Below in conjunction with embodiment, further specify the present invention.
The titania support that uses in the embodiment of the invention is commodity titanium white powder (the big titanium white powder of the friend of Jinzhou City Manufacturing Co., Ltd, nanoscale TiO
2); Activated alumina (Dongchang, Zibo industry aluminium oxide Co., Ltd, high purity aluminium oxide, γ-Al
2O
3Content is not less than 99.995%) carrier and the alumina support that mixes titanium dioxide (press TiO
2Percentage by weight is that 1%-10% takes by weighing titanium dioxide and alumina support powder; The weight of titanium dioxide accounts for 1%-10% in the mixed carrier; All the other are aluminium oxide, the mixed oxide carrier that obtains through roasting, moulding after mechanical mixture is even), the about 0.4g/cm of their bulk density
3, the about 170m of specific area
2/ g; Other reagent is commercially available chemical reagent, is the solution that contains 50% manganese nitrate when wherein manganese nitrate reagent is buied.
Embodiment 1
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
124.6 gram nickel nitrate [Ni (NO
3)
26H
2O] and 4.1 grams, 50% manganese nitrate [Mn (NO
3)
2] and 30.8 gram citric acid [C
6H
8O
7H
2O] dissolve each other, carboxyl is 0.5 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 50 gram dissolvings, is impregnated on the A.110 ℃ were dried by the fire 5 hours, and obtained B1.
B1 in air atmosphere, was respectively decomposed 2 hours under 300 ℃ and 450 ℃, obtain nickeliferous weight 20%, the catalyst of manganese weight 0.5%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 1.5ppm.
Embodiment 2
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
190.5 gram nickel nitrate [Ni (NO
3)
26H
2O] and 100.2 grams, 50% manganese nitrate [Mn (NO
3)
2] and 280.7 gram tartaric acid [C
4H
6O
6] dissolve each other, the ratio 3 of carboxyl and metal ion electric charge total mole number in the organic carboxyl acid after deionized water 10 gram dissolvings, is impregnated on the A.110 ℃ were dried by the fire 7 hours, and obtained B2.
B2 in air atmosphere, was respectively decomposed 2 hours under 350 ℃ and 450 ℃, obtain nickeliferous weight 25%, the catalyst of manganese weight 10%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 4000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration less than 1.1ppm.
Embodiment 3
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
228.6 gram nickel nitrate [Ni (NO
3)
26H
2O] and 50.2 grams, 50% manganese nitrate [Mn (NO
3)
2] and 26.0 gram citric acid [C
6H
8O
7H
2O] dissolve each other, carboxyl is 0.2 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 20 gram dissolvings, is impregnated on the A.110 ℃ were dried by the fire 5 hours, and obtained B3.
B3 in air atmosphere, was respectively decomposed 4 hours under 350 ℃ and 400 ℃, obtain nickeliferous weight 30%, the catalyst of manganese weight 5%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 8000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 1ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 360 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 97%, CH in the reaction end gas
4Concentration 83 volume %.
Embodiment 4
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
270.9 gram nickel nitrate [Ni (NO
3)
26H
2O] and 10.2 grams, 50% manganese nitrate [Mn (NO
3)
2] and 67.2 gram citric acid [C
6H
8O
7H
2O] dissolve each other, carboxyl is 0.5 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 70 gram dissolvings, is impregnated on the A.110 ℃ were dried by the fire 5 hours, and obtained B4.
B4 in air atmosphere, was respectively decomposed 3 hours under 350 ℃ and 450 ℃, obtain nickeliferous weight 35%, the catalyst of manganese weight 1%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 180 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 1ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 360 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 98%, CH in the reaction end gas
4Concentration 84 volume %.
Embodiment 5
Take by weighing the titanium dioxide (TiO of 500 ℃ of roastings after 4 hours
2) carrier 100 grams, note is made A1.
125.4 gram nickel nitrate [Ni (NO
3)
26H
2O] and 8.2 grams, 50% manganese nitrate [Mn (NO
3)
2] and 95.4 gram citric acid [C
6H
8O
7H
2O] dissolve each other, carboxyl is 1.5 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 25 gram dissolvings, is impregnated on the A1.110 ℃ were dried by the fire 5 hours, and obtained B5.
B5 in air atmosphere, was respectively decomposed 2 hours under 300 ℃ and 450 ℃, obtain nickeliferous weight 20%, the catalyst of manganese weight 1%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 4000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 0.2ppm.
Embodiment 6
Take by weighing 500 ℃ of roastings and be mixed with 5% weight titanium dioxide (TiO after 4 hours
2) aluminium oxide (γ-Al
2O
3) carrier 100 grams, note is made A2.
228.6 gram nickel nitrate [Ni (NO
3)
26H
2O] and 100.2 grams, 50% manganese nitrate [Mn (NO
3)
2] and 74.7 gram citric acid [C
6H
8O
7H
2O] dissolve each other, carboxyl is 1.5 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 45 gram dissolvings, is impregnated on the A2.110 ℃ were dried by the fire 5 hours, and obtained B6.
B6 in air atmosphere, was respectively decomposed 2 hours under 300 ℃ and 450 ℃, obtain nickeliferous weight 30%, the catalyst of manganese weight 5%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 180 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 0.2ppm.
Embodiment 7
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
106.2 gram nickel nitrate [Ni (NO
3)
26H
2O] and 139.6 grams, 50% manganese nitrate [Mn (NO
3)
2] and 264 gram ascorbic acid [vitamin C, C
6H
8O
6] dissolve each other, ascorbic acid is 2 with the ratio of metal ion total mole number, after deionized water 40 gram dissolvings, is impregnated on the A2.110 ℃ were dried by the fire 5 hours, and obtained B7.
B7 in air atmosphere, was respectively decomposed 2 hours under 300 ℃ and 450 ℃, obtain nickeliferous weight 15%, the catalyst of manganese weight 15%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 180 ℃, 3.0MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 1.15ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 460 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 97%, CH in the reaction end gas
4Concentration 81 volume %.
Embodiment 8
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
606.7 gram nickel nitrate [Ni (NO
3)
26H
2O] and 1.45 grams, 50% manganese nitrate [Mn (NO
3)
2] and 123.4 gram butanedioic acid [succinic acid, C
4H
6O
4] dissolve each other, carboxyl is 0.5 with the ratio of metal ion electric charge total mole number in the organic carboxyl acid, after deionized water 208 gram dissolvings, is impregnated on the A2.110 ℃ were dried by the fire 5 hours, and obtained B8.
B8 in air atmosphere, was respectively decomposed 2 hours under 350 ℃ and 450 ℃, obtain nickeliferous weight 55%, the catalyst of manganese weight 0.1%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 170 ℃, 3.0MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration 0.2ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 440 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 99%, CH in the reaction end gas
4Concentration 84 volume %.
Comparative example 1
Take by weighing the aluminium oxide (γ-Al of 600 ℃ of roastings after 4 hours
2O
3) carrier 100 grams, note is made A.
124.6 gram nickel nitrate [Ni (NO
3)
26H
2O], 4.1 grams, 50% manganese nitrate [Mn (NO
3)
2], after deionized water 35 gram dissolvings, be impregnated on the A.110 ℃ were dried by the fire 5 hours, and obtained B9.
B9 in air atmosphere, was respectively decomposed 2 hours under 300 ℃ and 450 ℃, obtain nickeliferous weight 20%, the catalyst of manganese weight 0.5%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration be 105ppm.
Comparative example 2
NiO-La according to the preparation of Chinese patent CN 89105365 disclosed methods
2O
3-MgO-Al
2O
3Catalyst, wherein, in metal oxide weight, the content of active component is NiO 20 weight %, MgO weight 5%, La
2O
3Weight 5%.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration be 32ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 360 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 78%, CH in the reaction end gas
4Concentration 64 volume %.
Comparative example 3
Form according to disclosed method preparation among the Chinese patent CN 200710146033.7: NiO content 18%, MgO content 1%, La
2O
3Content 0.5%, CeO
2Content 0.5%, CaO/Na
2O/BaO content is all 0.1%, and all the other are the catalyst of alumina support.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to the rich hydrogen raw material that contains 0.5%CO, at 200 ℃, 2.8MPa, gas space velocity 6000h
-1Reaction condition under, through after the reactor of above-mentioned catalyst is housed, chromatogram detects total oxycarbide (CO+CO in the gas
2) concentration be 312ppm.
Above-mentioned catalyst sieve is got 20-40 purpose particle 2ml, through 400 ℃ of following H
2After the reduction, switch to H
2/ CO is 3 synthesis gas, and reaction temperature is 360 ℃, reaction pressure 2.2MPa, gas space velocity 4000h
-1, reaction result CO conversion ratio 62%, CH in the reaction end gas
4Concentration 53 volume %.
The catalytic effect of embodiment and comparative example is seen table 1
Table 1
Data from table 1 can see, it is active to have good purification during the CO of catalyst trace in removing H2 of the present invention's preparation, and purification temperature is below 200 ℃, through purge outlet CO+CO
2Concentration is lower than 2ppm; Simultaneously, in the synthesis gas methanation reaction of high concentration CO content, the present invention also embodies excellent activity.
Comparative example 1 only is with the difference of embodiment 1; In the catalyst preparation process, use be the solution impregnating carrier of slaine, rather than like the citric acid solution of the salt that uses among the embodiment 1; Reaction result shows that the catalyst of comparative example 1 is inferior to embodiment 1 on the trace amounts of CO clean-up effect.
The result of comparative example 2-3 explains that then the result of catalyst in trace amounts of CO purification and high CO content synthesis gas methanation conversion reaction who adopts correlation technique to obtain can not compare and adopt the catalyst sample of the present invention's preparation.
Claims (9)
1. the catalyst of nickeliferous and manganese with the total restatement of catalyst, comprises following component:
A) nickel oxide, wherein nickel content is 15～55 weight %;
B) manganese oxide, wherein manganese content is 0.1～15 weight %;
Said catalyst carrier is at least a in aluminium oxide, silica, titanium oxide, the zirconia;
Said catalyst is the method preparation through may further comprise the steps:
Nickel salt and manganese salt and organic acid soln dissolve each other, and are impregnated on the said carrier, after oven dry, thermal decomposition, make;
Said organic acid is organic carboxyl acid or organic acid with reproducibility;
Wherein the carboxyl in the organic carboxyl acid is (0.5～3) with the ratio of metal ion total electrical charge molal quantity: 1;
Said organic acid with reproducibility is (0.2～2) with the ratio of metal ion molal quantity: 1.
2. the catalyst of a kind of nickeliferous and manganese as claimed in claim 1 is characterized in that:
Said nickel content is 15～45 weight %;
Said manganese content is 0.5～10 weight %.
3. the catalyst of a kind of nickeliferous and manganese as claimed in claim 2 is characterized in that:
Said nickel content is 15～40 weight %;
Said manganese content is 0.5～5 weight %.
4. the catalyst of a kind of nickeliferous and manganese as claimed in claim 1 is characterized in that:
Said organic acid is citric acid, tartaric acid, at least a in butanedioic acid, the ascorbic acid.
5. the catalyst of a kind of nickeliferous and manganese as claimed in claim 1 is characterized in that:
Said nickel salt is a nickel nitrate, and said manganese salt is manganese nitrate.
6. the catalyst of a kind of nickeliferous and manganese as claimed in claim 1 is characterized in that:
Carboxyl in the said organic carboxyl acid is (0.5～2) with the ratio of metal ion total electrical charge molal quantity: 1.
7. method for preparing like the catalyst of one of claim 1～6 described a kind of nickeliferous and manganese comprises:
Nickel salt and manganese salt and organic acid soln dissolve each other, and are impregnated on the said carrier, after oven dry, thermal decomposition, make;
Said organic acid is organic carboxyl acid or organic acid with reproducibility;
Wherein the carboxyl in the organic carboxyl acid is (0.5～3) with the ratio of metal ion total electrical charge molal quantity: 1;
Said organic acid with reproducibility is (0.2～2) with the ratio of metal ion molal quantity: 1.
8. method as claimed in claim 7 is characterized in that:
300 ℃～600 ℃ of the temperature ranges of said thermal decomposition, 2～8 hours time.
9. like the application of catalyst in methanation reaction and purified hydrogen of described a kind of nickeliferous and manganese of one of claim 1～6.
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| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
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| CN110201678A (en) * | 2019-07-16 | 2019-09-06 | 云南电网有限责任公司电力科学研究院 | A kind of catalyst and preparation method thereof |
| CN115532279A (en) * | 2022-11-28 | 2022-12-30 | 淄博蓝景膜环保科技有限公司 | Honeycomb integral catalytic wet oxidation catalyst and preparation method and application thereof |
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| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| US10888846B2 (en) | 2017-01-31 | 2021-01-12 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| CN109569559A (en) * | 2019-01-15 | 2019-04-05 | 宁波石墨烯创新中心有限公司 | A kind of preparation method of photochemical catalyst |
| CN110201678A (en) * | 2019-07-16 | 2019-09-06 | 云南电网有限责任公司电力科学研究院 | A kind of catalyst and preparation method thereof |
| CN115532279A (en) * | 2022-11-28 | 2022-12-30 | 淄博蓝景膜环保科技有限公司 | Honeycomb integral catalytic wet oxidation catalyst and preparation method and application thereof |
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