CN110026197A - Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application - Google Patents
Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 87
- 239000002243 precursor Substances 0.000 claims abstract description 50
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 239000002671 adjuvant Substances 0.000 claims abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 57
- 239000007789 gas Substances 0.000 claims description 37
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 22
- 235000019257 ammonium acetate Nutrition 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 230000002269 spontaneous effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000005695 Ammonium acetate Substances 0.000 claims description 14
- 229940043376 ammonium acetate Drugs 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 74
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- 230000004913 activation Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 25
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000000227 grinding Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005049 combustion synthesis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NWUTVFAUXDEIQS-UHFFFAOYSA-N [Ni].CC Chemical compound [Ni].CC NWUTVFAUXDEIQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alkyl biphenyl Chemical compound 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/394—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
Abstract
The invention discloses a kind of Ni-based methanation catalyst and its controllable type solution combustion the preparation method and applications, belong to catalyst technical field.A kind of Ni-based methanation catalyst, by mass percentage, consisting of: 10 ~ 60wt% of Ni；Al2O340~90wt%；The granularity of the catalyst is 60 ~ 220 mesh, and specific surface area is 180 ~ 400 m2/ g, Ni metal dispersity are 3.3 ~ 8.0%.The controllable type solution combustion the preparation method of the Ni-based methanation catalyst is combustion adjuvant to be added in nitrate and urea mixed solution precursor solution is made, and make precursor solution carry out burning under reducing atmosphere and be made.Catalyst of the present invention has better nickel species dispersion degree, is not necessarily to sequential reduction activation step, and catalytic activity is high, performance is stablized.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of Ni-based methanation catalyst and its controllable type solution
Combustion process for preparing and application.
Background technique
Due to growing energy demand and severe Environmental Protection Situation, the clean conversion of coal resources and efficient utilize are
The hot issue and huge challenge of China Today.Natural gas (main component is methane) is a kind of clean type fossil energy, can be made
For effective substituted or supplemented product of coal.Natural gas from coal technology is the main way realizing coal in technique and converting to natural gas
Diameter, the core process of this technology first is that the methanation reaction of synthesis gas, i.e. CO catalytic hydrogenation synthesize CH4And H2O。
Existing industrial production generallys use nickel-base catalyst and carries out catalysis reaction, mostly by skills such as dipping, precipitating, collosol and gels
Art preparation gained, these conventional methods need complicated, interminable rate-determining steps during the preparation process, such as control the soda acid of solution
Degree, aging or temperature of roasting etc., and particle size of the catalyst in active component, metal dispersity can not be avoided completely mostly
And the defect in the crucial governing factor such as specific surface area, thus directly affect the activity and stability of catalyst.
Solution combustion synthesis is a kind of fast and efficiently material preparation method, which there is synthetic material to form more
Uniformly, the features such as metal dispersity is preferably, partial size is smaller.Patent CN103801306B discloses a kind of synthesis of solution combustion,
The method of nickel-base catalyst suitable for slurry phasd methanation reaction.But while solution combustion synthesis has all the advantages, but
The technology also has following defect, and combustion process is mostly explosive vigorous reaction and abrupt release amount of heat, be easy to cause crystalline substance
The growth of grain is reunited；Burning non-uniform feature be easy to cause the part of material to reunite；Liquid combustion product is metal oxide shape
State, thus the method is that metal simple-substance nickel just has catalysis work applied to further reduction activation is needed when synthesizing nickel-base catalyst
Property；These upper factors are unfavorable for the industrialization promotion of this method.
In order to solve drawbacks described above of the existing technology, the present invention have developed a kind of Ni-based methanation catalyst and its
Controllable type solution combustion the preparation method and application.
Summary of the invention
The object of the present invention is to provide a kind of Ni-based methanation catalyst and its controllable type solution combustion the preparation method and answer
With.
The present invention is achieved by the following technical solutions:
A kind of Ni-based methanation catalyst, by mass percentage, consisting of: 10 ~ 60wt% of Ni；Al2O340~90wt%；
The granularity of the catalyst is 60 ~ 220 mesh, and specific surface area is 180 ~ 400 m2/ g, Ni metal dispersity are 3.3 ~ 8.0%.
The controllable type solution combustion the preparation method of the Ni-based methanation catalyst, is in nitrate and urea mixed solution
Combustion adjuvant is added, precursor solution is made, and so that precursor solution is carried out burning under reducing atmosphere and be made.
The controllable type solution combustion the preparation method of the Ni-based methanation catalyst, step are as follows:
1) mixed solution for configuring urea and metal nitrate, is placed in 60 DEG C of water-baths, and combustion adjuvant is added under agitation and obtains
Precursor solution；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 10 ~ 80 mL/
Then the reducibility gas of min starts microwave heating equipment, carries out spontaneous combustion after precursor solution heating, collect powder, grind
Mill, be granulated to get.
Metal nitrate described in step 1) is Ni (NO3)2•6H2O and Al (NO3)3•9H2The mixture of O, wherein Ni2++
Al3+/ urea mol ratio is 1:0.15 ~ 0.85.
Combustion adjuvant described in step 1) is one of ammonium acetate, ammonium nitrate or glucose or a variety of.
Ni described in step 1)2++Al3+/ combustion adjuvant molar ratio is 1:0.5 ~ 2.0, to prepare 10 g Ni/Al2O3Catalyst
For, the quality that accurately weighs of nitrate is 5.20 ~ 19.50 g Ni (NO3)2•6H2O and 44.50 ~ 65.80 g Al (NO3)3•
9H2O, then urea requirement takes 2.20 ~ 9.50 g, and above-mentioned solution is placed under 60 DEG C of water-baths and is stirred continuously, and is added in the process preparatory
The combustion adjuvant of weighing obtains precursor solution.
The microwave frequency of microwave heating equipment described in step 2 is 2450 MHz, and output power is 400 ~ 1100 w.
The reducibility gas being continually fed into during spontaneous combustion described in step 2,
The reducibility gas is made of hydrogen, nitrogen or argon gas, and volume group becomes 0.3 ~ 5.5% H2With 94.5~99.7%
N2Or Ar.
Application the invention further relates to above-mentioned catalyst in paste state bed reactor synthesis gas methanation, reaction condition are as follows: with
The substance that the thermal coefficients such as paraffin hydrocarbon, alkyl biphenyl type conduction oil or methyl-silicone oil are big, thermal capacitance is big, boiling point is high is as inertia liquid phase
Component, 240 ~ 310 DEG C of reaction temperature；0.1 ~ 3.0 MPa of reaction pressure；1500 ~ 4500 mL/(g h of air speed)；Slurry bed system catalysis
Agent concentration 0.011 ~ 0.055 g/mL, unstripped gas H2/ CO volume ratio is 2.6 ~ 3.8.
Reduced nickel methylmethane catalyst is exempted from controllable type solution combustion preparation of the present invention, is that combustion adjuvant is added to solution combustion
Reaction is burnt, plays the role of controlling key factor in combustion process, reduces flame temperature in combustion and to fire
It is more mild, uniform to burn reaction, to prevent the reunion of active component nickel crystallite, improves the dispersibility of nickel, catalyst first
Alkanisation performance is improved；Using the high efficiency of microwave heating, body phasic property, precursor solution has more on fire when lighting
Point can quickly spread to whole system, therefore ensure that the homogeneity of combustion product；Precursor solution is one in reproducibility atmosphere
The problems such as walking conbustion synthesis metalNicatalyst, avoiding the sintering of nickel crystallite caused by subsequent high temperature reduction activation link, reunite,
And the preparation time period has been saved, reduce material consumption and energy consumption.
In conclusion combustion adjuvant is added in the present invention in combustion system, heat release, the burning of control solution combustion reaction are realized
Intensity and uniformity coefficient, further adjusting the ratio of oxide and fuel in precursor solution is reproducibility composition, and makes forerunner
Combustion reaction occurs under reducing atmosphere protection for liquid solution, and obtained catalyst has better nickel species dispersion degree, nothing
Sequential reduction activation step is needed, and catalytic activity is high, performance is stablized.
Specific embodiment
The present invention is further detailed combined with specific embodiments below, it is to be understood that these embodiments are only used
In illustrating the present invention rather than limit the scope of the invention.Those skilled in the art on the basis of the present invention make the present invention
Various changes or modification, should all equally fall within protection scope of the present invention.
Embodiment 1
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 15.29 g ammonium nitrate are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium nitrate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 15 mL/min,
Volume group becomes 3.0%H2/97.0%N2Mixed gas, start microwave heating equipment after a period of time, heating power is 500 W,
Spontaneous combustion is carried out after driving liquid solution heating, collects powder, is granulated after grinding and is urged to 160 ~ 200 mesh to get to methanation is Ni-based
Agent, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Catalyst activity
The specific steps of evaluation: the above-mentioned catalyst of certain mass and 120 mL inert liquid mediums are injected into 250 mL slurry reactor kettles
In, at room temperature, use N2It is pressurized to reaction pressure to system, with 5oC/min is warming up to reaction temperature, then to reaction kettle
In be passed through 25 mL/min CO and a certain amount of H2, start to react under 750 r/min stirring, react sampling point after a period of time
Analysis.
Embodiment 2
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 50 mL/min,
Volume group becomes 5.0%H2The mixed gas of/95.0%Ar starts microwave heating equipment, heating power 700 after a period of time
W carries out spontaneous combustion after driving liquid solution heating, collects powder, is granulated after grinding and urges to 80 ~ 120 mesh to get to methanation is Ni-based
Agent, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 3
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 34.41 g glucose are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/glucose molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 25 mL/min,
Volume group becomes 2.5%H2The mixed gas of/97.5%Ar starts microwave heating equipment, heating power 800 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 120 ~ 160 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 4
(1) 4.96 g Ni (NO of precise3)2•6H2O、66.23 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 35 mL/min,
Volume group becomes 1.5%H2/98.5%N2Mixed gas, start microwave heating equipment after a period of time, heating power is 900 W,
Spontaneous combustion is carried out after precursor solution heating, collects powder, is granulated after grinding and is urged to 80 ~ 120 mesh to get to methanation is Ni-based
Agent, catalyst composition are as follows: Ni 10wt.%, Al2O3 90wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 5
(1) 18.83 g Ni (NO of precise3)2•6H2O、45.62 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 50 mL/min,
Volume group becomes 1.0%H2The mixed gas of/99.0%Ar starts microwave heating equipment, heating power 700 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 120 ~ 160 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 38wt.%, Al2O3 62wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 6
(1) 29.23 g Ni (NO of precise3)2•6H2O、30.17 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 50 mL/min,
Volume group becomes 4.0%H2/96.0%N2Mixed gas, start microwave heating equipment after a period of time, heating power is 800 W,
Spontaneous combustion is carried out after precursor solution heating, collects powder, is granulated after grinding to 160 ~ 200 mesh to get Ni-based to methanation
Catalyst, catalyst composition are as follows: Ni 59wt.%, Al2O3 41wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 7
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 8.83 g ammonium acetates are added in the process and obtain precursor solution,
In (Ni2++Al3+)/ammonium acetate molar ratio is 1:0.6；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 75 mL/min,
Volume group becomes 3.5%H2The mixed gas of/96.5%Ar starts microwave heating equipment, heating power 700 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 100 ~ 140 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 8
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 26.50 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1.8；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 40 mL/min,
Volume group becomes 2.5%H2/97.5%N2Mixed gas, start microwave heating equipment, heating power 1000 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 100 ~ 140 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 9
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 2.32 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 30 mL/min,
Volume group becomes 0.5%H2The mixed gas of/99.5%Ar starts microwave heating equipment, heating power 800 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 160 ~ 200 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 10
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 9.26 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 14.72 g ammonium acetates are added in the process and obtain precursor solution,
Wherein (Ni2++Al3+)/ammonium acetate molar ratio is 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 25 mL/min,
Volume group becomes 2.0%H2/98.0%N2Mixed gas, start microwave heating equipment after a period of time, heating power is 500 W,
Spontaneous combustion is carried out after precursor solution heating, collects powder, is granulated after grinding and is urged to 80 ~ 120 mesh to get to methanation is Ni-based
Agent, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 11
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 7.64g ammonium nitrate is added in the process and 7.36g ammonium acetate obtains
Precursor solution, wherein (Ni2++Al3+)/(ammonium nitrate+ammonium acetate) molar ratio be 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 50 mL/min,
Volume group becomes 3.5%H2/96.5%N2Mixed gas, start microwave heating equipment after a period of time, heating power is 600 W,
Spontaneous combustion is carried out after precursor solution heating, collects powder, is granulated after grinding to 120 ~ 160 mesh to get Ni-based to methanation
Catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Embodiment 12
(1) 9.91 g Ni (NO of precise3)2•6H2O、58.87 g Al(NO3)3•9H2O and 5.79 g urea prepare mixing
Mixed solution is placed under 60 DEG C of water-baths and is stirred continuously by solution, and 7.36g ammonium acetate is added in the process and 17.21g glucose obtains
Precursor solution, wherein (Ni2++Al3+)/(ammonium acetate+glucose) molar ratio be 1:1；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 65 mL/min,
Volume group becomes 4.5%H2The mixed gas of/95.5%Ar starts microwave heating equipment, heating power 700 after a period of time
W, carries out spontaneous combustion after precursor solution heating, collects powder, is granulated after grinding to 100 ~ 140 mesh to get methanation nickel is arrived
Base catalyst, catalyst composition are as follows: Ni 20wt.%, Al2O3 80wt.%。
Activity rating actual conditions and result of the catalyst in preparing methane by synthetic gas reaction see attached list 1.Specific steps are such as
Shown in embodiment 1.
Table 1 is evaluation result of the catalyst in synthesis gas methanation reaction of each embodiment preparation.
Subordinate list 1
Table 2 is that the specific surface area of the catalyst of each embodiment preparation and Ni metal dispersity measurement result compare.
Subordinate list 2
| Embodiment/comparative example | Specific surface area of catalyst/m2/g | Ni metal dispersity/% |
| Embodiment 1 | 268 | 5.1 |
| Embodiment 2 | 388 | 7.8 |
| Embodiment 3 | 189 | 3.5 |
| Embodiment 4 | 379 | 7.9 |
| Embodiment 5 | 343 | 6.9 |
| Embodiment 6 | 325 | 6.7 |
| Embodiment 7 | 311 | 6.4 |
| Embodiment 8 | 356 | 7.2 |
| Embodiment 9 | 310 | 6.3 |
| Embodiment 10 | 276 | 5.3 |
| Embodiment 11 | 340 | 6.7 |
| Embodiment 12 | 202 | 3.7 |
Claims (10)
1. a kind of Ni-based methanation catalyst, which is characterized in that by mass percentage, consisting of: 10 ~ 60wt% of Ni；
Al2O340~90wt%；The granularity of the catalyst is 60 ~ 220 mesh, and specific surface area is 180 ~ 400 m2/ g, Ni metal dispersity
It is 3.3 ~ 8.0%.
2. the controllable type solution combustion the preparation method of Ni-based methanation catalyst described in claim 1, which is characterized in that be in nitre
Combustion adjuvant is added in hydrochlorate and urea mixed solution, precursor solution is made, and fires precursor solution under reducing atmosphere
It fires.
3. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 2, which is characterized in that step
Suddenly are as follows:
1) mixed solution for configuring urea and metal nitrate, is placed in 60 DEG C of water-baths, and combustion adjuvant is added under agitation and obtains
Precursor solution；
(2) precursor solution is placed in the atmosphere protection cover in microwave heating equipment, being continually fed into flow is 10 ~ 80 mL/
Then the reducibility gas of min starts microwave heating equipment, carries out spontaneous combustion after precursor solution heating, collect powder, grind
Mill, be granulated to get.
4. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 3, which is characterized in that step
It is rapid 1) described in metal nitrate be Ni (NO3)2•6H2O and Al (NO3)3•9H2The mixture of O, wherein Ni2++Al3+/ urea rubs
You are than being 1:0.15 ~ 0.85.
5. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 3, which is characterized in that step
It is rapid 1) described in combustion adjuvant be one of ammonium acetate, ammonium nitrate or glucose or a variety of.
6. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 3, which is characterized in that step
It is rapid 1) described in Ni2++Al3+/ combustion adjuvant molar ratio is 1:0.5 ~ 2.0.
7. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 3, which is characterized in that step
It is rapid 2) described in microwave heating equipment microwave frequency be 2450 MHz, output power be 400 ~ 1100 w.
8. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 3, which is characterized in that step
The reducibility gas being continually fed into during rapid 2) the described spontaneous combustion.
9. the controllable type solution combustion the preparation method of Ni-based methanation catalyst according to claim 8, which is characterized in that institute
The reducibility gas stated is made of hydrogen, nitrogen or argon gas, and volume group becomes 0.3 ~ 5.5% H2With 94.5~99.7% N2Or
Ar。
10. catalyst made from method as claimed in any of claims 2 to 9 is closed in paste state bed reactor
At the application in gas methanation.
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