CN105013495B - Mg-Al composite oxide is methanation catalyst of carrier and preparation method thereof - Google Patents
Mg-Al composite oxide is methanation catalyst of carrier and preparation method thereof Download PDFInfo
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Abstract
Mg-Al composite oxide is methanation catalyst of carrier and preparation method thereof, is related to methanation catalyst.The Mg-Al composite oxide be the methanation catalyst of carrier using Ni as active component, with La2O3With the composition defined using M as auxiliary agent, with Al2O3, MgO composite oxides be carrier, active component nickel in the form of nickel oxide to be present in catalyst, and M is selected from least one of oxide such as Ca, Ce, Ba, Sm, Mn, Fe, Co.Nickel salt is dissolved in water, acid is added, nickel salt solution is made, gained nickel salt solution is scattered in Alumina gel, and after mix with the M of auxiliary agent lanthana and selection, mixed sols is made, composite surface is formed and modifies adhesive；By composite surface modification adhesive and support powder aluminum oxide, magnesia and the starch kneading in kneading machine, after dough is formed, particle is extruded in banded extruder, is dried, roasting produces the methanation catalyst that Mg-Al composite oxide is carrier.
Description
Technical field
The present invention relates to methanation catalyst, more particularly, to the methanation catalyst that a kind of Mg-Al composite oxide is carrier
Agent and preparation method thereof.
Background technology
China is the country of one typical " rich coal, oil starvation, few gas ", if China's so abundant coal can be made full use of
Charcoal resource, then can to solve coal resources comprehensive utilization, alleviate Chinese postman problem algorithm shortage, safeguard Natural Resources in China side
Play irreplaceable effect in face.CO methanations are simplest Fischer-Tropsch synthesis, and it has high conversion, course of reaction letter
List, low-carbon, it is environmentally safe the advantages of, based on above advantage, CO methanations have become production one of oil substitutes
Important alternative.Therefore, it is worth to develop a kind of effective methanation catalyst, is also eager.
The conventional dipping method such as A of Chinese patent CN 101380581 disclose a kind of be immersed in nickel solution and were calcined
Composite oxide carrier on, then again be calcined be made catalyst.Chinese patent CN101391218B discloses oven gas first
The preparation method of Alkanizing catalyst, using aluminum oxide and magnesia after 1000~1500 DEG C of calcinings of high temperature as magnesium aluminate spinel as
Carrier, dipping active component nickel and other auxiliary agents, then carry out calcining and be made.Chinese patent CN104475119A discloses a kind of height
Warm methanation catalyst, by soluble nickel salt, aluminium salt, lanthanum salt, chromic salts and boehmite or Alpha-alumina or gama-alumina
Add water resulting mixture, moves into after reactor and heats, and adds precipitating reagent, washing of precipitate, filtering, and it is obtained to carry out drying and roasting.
The A of Chinese patent CN 102029161 disclose a kind of preparation method for the full methanation catalyst for being related to hydrothermal chemistry process,
First Hydrothermal Synthesiss presoma, its raw material are nickel, aluminium, zirconium, magnesium, one kind with the carbonate, subcarbonate or nitrate of lanthanum
Or it is several, presoma is filtered, washed, is dried, is calcined, is molded, gained is calcined again.
The content of the invention
It is an object of the invention to provide preparation technology simply and only by once calcining, catalyst has intensity
Greatly, the advantages of active good, methane selectively is high, heat endurance is good, high temperature active is good, suitable for being applied in methanation process
Mg-Al composite oxide for carrier methanation catalyst and preparation method thereof.
The Mg-Al composite oxide be the methanation catalyst of carrier using Ni as active component, with La2O3Defined with M
Composition be auxiliary agent, with Al2O3, MgO composite oxides be carrier, active component nickel is present in catalysis in the form of nickel oxide
In agent, each component content by mass percentage is NiO：10%~50%, MgO：10%~30%, La2O3：1%~10%,
M：1%~5%, surplus is Al2O3；The M is selected from least one of oxides such as Ca, Ce, Ba, Sm, Mn, Fe, Co.
The Mg-Al composite oxide is the preparation method of the methanation catalyst of carrier, is comprised the following steps：
1) nickel salt is dissolved in water, adds acid, nickel salt solution is made, gained nickel salt solution is scattered in Alumina gel,
And after being mixed with the M of auxiliary agent lanthana and selection, mixed sols is made, form composite surface modification adhesive；
2) by step 1) obtained composite surface modification adhesive with support powder aluminum oxide, magnesia and starch in kneading
Kneading in machine, after dough is formed, extrudes particle in banded extruder, dries, roasting, and it is carrier to produce Mg-Al composite oxide
Methanation catalyst.
In step 1) in, the nickel salt may be selected from one kind in nickel nitrate, nickel acetate etc.；The acid may be selected from sulfuric acid, nitre
At least one of acid, acetic acid, citric acid etc.；4~14h is preferably placed after the mixing.
In step 2) in, the big I of the particle is Φ 5mm × 5mm；The condition of the drying can be at 100~120 DEG C
8~12h of lower drying；The condition of the roasting can move to dried catalyst in Muffle furnace, be heated up with 5~10 DEG C/min fast
Rate is warming up to 600~900 DEG C, is calcined 4~8h.
When Mg-Al composite oxide is used for the catalyst of synthesis gas methanation for the methanation catalyst of carrier, methanation
The reaction condition of reaction system is：Reaction temperature be 350~700 DEG C, reaction pressure be 0.5~4.0MPa, air speed be 2000~
10000ml/ (gh), unstripped gas H2/ CO volume ratios are 2~12.5.
Compared with prior art, the technical advantages of the present invention are that
(1) auxiliary agent La is added in catalyst prepared by the present invention2O3, can effectively suppress the generation of nickel aluminate, together
When promote active component nickel be evenly distributed on carrier, improve the activity and selectivity of catalyst.
(2) catalyst of the invention has preferable pyroreaction activity, in wider reaction temperature interval (350~700
DEG C) interior with high conversion ratio.
(3) catalyst preparation process is simple, and easy control of reaction conditions, raw material is cheap and easy to get, and catalyst is reproducible, tool
There is the good prospect of commercial Application.
Brief description of the drawings
Fig. 1 is that the activity rating in methanation reaction is varied with temperature.
Fig. 2 is that the activity rating in methanation reaction is changed over time.
Embodiment
The present invention is further illustrated with embodiment below.
Embodiment 1
(1) formation of adhesive：Accurately weigh 389.2g Ni (NO3)2·6H2O, is dissolved in 75ml H2In O, 75ml is added
Concentrated nitric acid, it is to be mixed it is uniform after, add 15g La2O3, 15gCaO, stirring, and be allowed to be sufficiently mixed, then add 115.38g and intend
Boehmite is stirred as peptizing agent with stainless steel bar, allows mixture to be sufficiently mixed, and is made after colloidal sol and is stood 4h, forms compound
Surface modification adhesive；
(2) extrusion shapes：By composite surface modification adhesive obtained by step (1) and 300g alumina powders, 75g magnesia
Kneading fully, when dough is formed, is extruded into the type bar of diameter of phi 5, and cut in banded extruder inside kneading machine with 10g starch
It is cut into the particle of Φ 5mm × 5mm sizes；
(3) dry：In the drying box of 120 DEG C of the catalyst precursor formed in step (2) after the completion of extrusion, in air
12h is dried under atmosphere；
(4) it is calcined：Step (3) dried catalyst is being warming up to 600 DEG C with 5 DEG C/min heating rates, and big
Under gas atmosphere, after 600 DEG C are calcined 4h, crush, screen the catalyst sample of 40~60 mesh granular sizes.
Activity rating uses fixed bed reactors, and loaded catalyst is 0.5ml, and 10%H is used at 450 DEG C2/N2Reduction
4h, unstripped gas proportioning is H2∶CO∶N2=73: 2: 25, reactor air speed is 5000h-1, operating pressure is 2MPa, reaction temperature point
Wei not be 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, CO conversion ratios and CH4Selectivity reaches
100%.
The result that activity rating of the catalyst manufactured in the present embodiment in methanation reaction is varied with temperature is shown in Fig. 1.
Embodiment 2
(1) formation of adhesive：Accurately weigh 389.2g Ni (NO3)2·6H2O, is dissolved in 75ml H2In O, 75ml is added
Concentrated nitric acid, it is to be mixed it is uniform after, add 15g La2O3, 10g BaO, stirring, and be allowed to be sufficiently mixed, then add 115.38g
Boehmite is stirred as peptizing agent with stainless steel bar, allows mixture to be sufficiently mixed, and is made after colloidal sol and is stood 14h, forms multiple
Close surface modification adhesive；
(2) extrusion：By composite surface modification adhesive obtained by step (1) and 285g alumina powders, 100g magnesia with
10g starch kneading in kneading machine fully, when dough is formed, is extruded into the type strip of diameter of phi 5, and cut into Φ in banded extruder
The particle of 5mm × 5mm sizes；
(3) dry：The catalyst precursor formed in step (2) after the completion of extrusion is put into 100 DEG C of drying box,
8h is dried under air atmosphere；
(4) it is calcined：Step (3) dried catalyst is being warming up to 600 DEG C with 5~10 DEG C/min heating rates, and
Under air atmosphere after 600 DEG C are calcined 4h, crush, screen the catalyst sample of 40~60 mesh granular sizes.
Activity rating uses fixed bed reactors, and loaded catalyst is 0.5ml, and catalyst uses 10%H at 450 DEG C2/
N24h is reduced, unstripped gas proportioning is H2∶CO∶N2∶CO2=44: 4: 32: 20, reactor air speed is 5000h-1, operating pressure is
2MPa, reaction temperature is 500 DEG C.CO conversion ratios reach 100%.
Embodiment 3
(1) formation of adhesive：Accurately weigh 291.9g Ni (NO3)2·6H2O, is dissolved in 75ml H2In O, 35ml is added
Concentrated nitric acid, 20ml acetic acid, 20g citric acids are to be mixed uniform into after solution, add 10g La2O3, 10g Fe2O3, 7.5gSm2O3,
Stirring, and be allowed to be sufficiently mixed, 115.38g boehmites are then added as peptizing agent, and 10g starch is used as expanding agent
Stainless steel bar is stirred, and allows mixture to be sufficiently mixed, and is made after colloidal sol and is stood 12h, forms composite surface modification adhesive；
(2) extrusion shapes：By composite surface modification adhesive obtained by step (1) and 310g alumina powders, 100g oxidations
Magnesium kneading inside kneading machine fully, when dough is formed, is extruded into the type bar of diameter of phi 5, and cut into Φ in banded extruder
The particle of 5mm × 5mm sizes；
(3) dry：The catalyst precursor formed in step (2) after the completion of extrusion is put into 120 DEG C of drying box,
12h is dried under air atmosphere；
(4) it is calcined：Step (3) dried catalyst is being warming up to 650 DEG C with 5~10 DEG C/min heating rates, and
Under air atmosphere, after 650 DEG C are calcined 4h, crush, screen the catalyst sample of 40~60 mesh granular sizes.
Activity rating uses fixed bed reactors, and loaded catalyst is 0.5ml, and 10%H is used at 450 DEG C2/N2Reduction
3h, unstripped gas proportioning is H2∶CO∶N2=73: 2: 25, reactor air speed is 5000h-1, operating pressure is 2MPa, and reaction temperature is
700℃.250h is reacted, CO conversion ratios can be stablized 100%.
The result that activity rating of the catalyst manufactured in the present embodiment in methanation reaction is changed over time is shown in Fig. 2.
Embodiment 4
(1) formation of adhesive：Accurately weigh 291.9g Ni (NO3)2·6H2O, is dissolved in 75ml H2In O, 35ml is added
Concentrated nitric acid, 20ml acetic acid, 20g citric acids are to be mixed uniform into after solution, add 10g La2O3, 5gCaO, 5g MnO2, 5g
CoO, stirring, and be allowed to be sufficiently mixed, 115.38g boehmites are then added as peptizing agent, and 10g starch is used as reaming
Agent, is stirred with stainless steel bar, allows mixture to be sufficiently mixed, and is made after colloidal sol and is stood 12h, forms composite surface modification adhesive；
(2) extrusion shapes：By composite surface modification adhesive obtained by step (1) and 310g alumina powders, 50g magnesia
Kneading fully, when dough is formed, is extruded into the type strip of diameter of phi 5 in banded extruder inside kneading machine, and cut into Φ 5mm ×
The particle of 5mm sizes；
(3) dry：The catalyst precursor formed in step (2) after the completion of extrusion is put into 100 DEG C of drying box,
12h is dried under air atmosphere；
(4) it is calcined：Step (3) dried catalyst is being warming up to 650 DEG C with 5~10 DEG C/min heating rates, and
Under air atmosphere, after 650 DEG C are calcined 4h, essence, the catalyst sample of screening Φ 5mm × 5mm granular sizes are broken.
Activity rating uses fixed bed reactors, and loaded catalyst is 0.5ml, and 10%H is used at 450 DEG C2/N2Reduction
3h, unstripped gas proportioning is H2∶CO∶N2=73: 2: 25, reactor air speed is 5000h-1, operating pressure is 2MPa, and reaction temperature is
700 DEG C, CO conversion ratios can be stablized 100%.
Embodiment 5
(1) formation of adhesive：Accurately weigh 389.2g Ni (NO3)2·6H2O, is dissolved in 75ml H2In O, 75ml is added
Concentrated nitric acid, it is to be mixed uniform into after solution, add 10g La2O3, 5g CaO, 5g Ce2O3, stirring, and be allowed to be sufficiently mixed, so
115.38g boehmites are added afterwards as peptizing agent, and 10g starch is stirred as expanding agent with stainless steel bar, allows mixture to fill
Divide mixing, be made after colloidal sol and stand 8h, form composite surface modification adhesive；
(2) extrusion shapes：By composite surface modification adhesive obtained by step (1) and 285g alumina powders, 100g oxidations
Magnesium kneading inside kneading machine fully, when dough is formed, is extruded into the type strip of diameter of phi 5, and cut into Φ 5mm in banded extruder
The particle of × 5mm sizes；
(3) dry：The catalyst precursor formed in step (2) after the completion of extrusion is put into 100 DEG C of drying box,
12h is dried under air atmosphere；
(4) it is calcined：Step (3) dried catalyst is being warming up to 900 DEG C with 5~10 DEG C/min heating rates, and
Under air atmosphere, after 900 DEG C are calcined 8h, crush, screen the catalyst sample of 40~60 mesh granular sizes.
Activity rating uses fixed bed reactors, and loaded catalyst is 0.5ml, and 10%H is used at 450 DEG C2/N2Reduction
3h, unstripped gas proportioning is H2∶CO∶N2=73: 2: 25, reactor air speed is 10000h-1, operating pressure is 2MPa, reaction temperature
For 500 DEG C, CO conversion ratios can be stablized 100%.
The present invention is provided using Mg-Al composite oxide as carrier, using Ni as the methanation catalyst of active component and its preparation
Method.The catalyst also contains La2O3With other accelerator；The catalyst can be applied to the methanation of natural gas from coal
Cheng Zhong, the preparation process of catalyst is：Nickel salt solution, auxiliary agent and Alumina gel are sufficiently mixed obtained composite surface and modify gluing first
Agent, then with Al2O3, MgO, accelerator, pore creating material carry out kneading it is uniform after extrusion, through drying, roasting, obtain of the present invention urge
Agent.The catalyst made of the method for the present invention has that good catalytic activity, high mechanical strength, heat endurance be good, anti-carbon energy
The features such as power is strong.Preparation process is easy, and cost is low, is preferable high temperature resistant methanation catalyst.
Claims (7)
1. Mg-Al composite oxide is the preparation method of the methanation catalyst of carrier, it is characterised in that the Mg-Al composite oxidation
Thing is the methanation catalyst of carrier, using Ni as active component, with La2O3With the composition defined using M as auxiliary agent, with Al2O3、MgO
Composite oxides be carrier, active component nickel in the form of nickel oxide to be present in catalyst, each group by mass percentage
It is NiO to divide content：10%~50%, MgO：10%~30%, La2O3：1%~10%, M：1%~5%, surplus is Al2O3；
The M is selected from least one of Ca, Ce, Ba, Sm, Fe, Co oxide；
The preparation method comprises the following steps：
1) nickel salt is dissolved in water, adds acid, nickel salt solution is made, gained nickel salt solution is scattered in Alumina gel, and with
After auxiliary agent lanthana and the M of selection mixing, mixed sols is made, composite surface modification adhesive is formed；
2) by step 1) obtained composite surface modification adhesive with support powder aluminum oxide, magnesia and starch in kneading machine
Kneading, after dough is formed, extrudes particle in banded extruder, dries, roasting, produces the methane that Mg-Al composite oxide is carrier
Change catalyst.
2. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 1) in, the one kind of the nickel salt in nickel nitrate, nickel acetate.
3. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 1) in, the acid is selected from least one of sulfuric acid, nitric acid, acetic acid, citric acid.
4. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 1) in, 4~14h is placed after the mixing.
5. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 2) in, the size of the particle is Φ 5mm × 5mm.
6. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 2) in, the condition of the drying is that 8~12h is dried at 100~120 DEG C.
7. Mg-Al composite oxide as claimed in claim 1 is the preparation method of the methanation catalyst of carrier, it is characterised in that
In step 2) in, the condition of the roasting is to move to dried catalyst in Muffle furnace, with 5~10 DEG C/min heating rates
600~900 DEG C are warming up to, 4~8h is calcined.
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| CN109225241A (en) * | 2018-10-11 | 2019-01-18 | 刘博男 | A kind of methanation catalyst and preparation method thereof |
| CN111001403A (en) * | 2019-11-29 | 2020-04-14 | 华南理工大学 | Ozone catalytic oxidation catalyst and application thereof in removing VOCs under wet and cold conditions |
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| CN103706373B (en) * | 2013-12-26 | 2015-08-12 | 西南化工研究设计院有限公司 | A kind of Low-temperature high-activity methanation catalyst and preparation method thereof |
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