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
- Publication number
- CN110026197A CN110026197A CN201910153453.0A CN201910153453A CN110026197A CN 110026197 A CN110026197 A CN 110026197A CN 201910153453 A CN201910153453 A CN 201910153453A CN 110026197 A CN110026197 A CN 110026197A
- Authority
- CN
- China
- Prior art keywords
- combustion
- preparation
- solution
- catalyst
- controllable type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910153453.0A CN110026197A (en) | 2019-02-28 | 2019-02-28 | Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910153453.0A CN110026197A (en) | 2019-02-28 | 2019-02-28 | Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110026197A true CN110026197A (en) | 2019-07-19 |
Family
ID=67235037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910153453.0A Withdrawn CN110026197A (en) | 2019-02-28 | 2019-02-28 | Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110026197A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731422A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Preparation method of slurry bed methane synthesis catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120063963A1 (en) * | 2009-04-24 | 2012-03-15 | University Of Yamanashi | Selective co methanation catalyst, method of producing the same, and apparatus using the same |
| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
| CN103801304A (en) * | 2014-02-27 | 2014-05-21 | 太原理工大学 | Reduction-free methanation catalyst for slurry reactor as well as preparation method and application thereof |
| CN103816895A (en) * | 2014-02-27 | 2014-05-28 | 赛鼎工程有限公司 | Supported precious metal methanation catalyst, and preparation method and application thereof |
-
2019
- 2019-02-28 CN CN201910153453.0A patent/CN110026197A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120063963A1 (en) * | 2009-04-24 | 2012-03-15 | University Of Yamanashi | Selective co methanation catalyst, method of producing the same, and apparatus using the same |
| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
| CN103801304A (en) * | 2014-02-27 | 2014-05-21 | 太原理工大学 | Reduction-free methanation catalyst for slurry reactor as well as preparation method and application thereof |
| CN103816895A (en) * | 2014-02-27 | 2014-05-28 | 赛鼎工程有限公司 | Supported precious metal methanation catalyst, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| YUAN GAO ET AL.: "Influence of fuel additives in the urea nitrates solution combustion Synthesis of Ni-Al2O3 Catalyst for slurry phase CO methanation", 《APPLIED CATALYSIS A：GENERAL》 * |
| 吉可明等: "溶液燃烧法制备的Ni基催化剂及其浆态床甲烷化催化性能", 《无机化学学报》 * |
| 高源: "溶液燃烧合成Ni基催化剂结构调控及催化甲烷化性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731422A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Preparation method of slurry bed methane synthesis catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105618061B (en) | A kind of slurry bed system carbon dioxide methanation bimetallic catalyst and its preparation method and application | |
| CN105562014B (en) | A kind of preparation method of Ni-based methanation catalyst | |
| CN105107515B (en) | Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane | |
| CN109126845A (en) | Supported transition metal carbide catalyst and its one-step synthesis method method | |
| CN109908946A (en) | Catalyst for preparing biological aviation fuel component from jatropha oil and preparation method thereof | |
| CN110075888B (en) | Preparation method of MoC @ C catalyst and application of MoC @ C catalyst in CO2Application of hydrogenation methanol synthesis reaction | |
| CN109806874B (en) | A kind of preparation method and application of carbon dioxide methanation nickel-based polymetallic catalyst | |
| CN107376936B (en) | Platinum-cobalt/attapulgite catalyst and preparation method and application thereof | |
| CN103801304B (en) | A kind of exempt to reduce slurry bed system methanation catalyst and method for making and application | |
| CN110026197A (en) | Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application | |
| CN116393158A (en) | Preparation method and application of catalyst for preparing synthesis gas by dry reforming of methane | |
| CN103331165A (en) | Preparation method of high-purity metal Cu/ZnO catalyst | |
| CN103801290B (en) | Noble metal methanation catalyst prepared by solution combustion method and method for making and application | |
| CN108114743A (en) | A kind of solid phase synthesis process of hydroisomerization catalyst | |
| CN116586068B (en) | Preparation method and application of single-atom Fe/CeO2 catalyst | |
| CN103586029B (en) | Catalyst for hydrogen production by water-phase reforming of biomass depolymerization product and preparation method thereof | |
| CN113652698A (en) | Tungsten-doped nickel phosphide bifunctional catalytic material with cross nanosheet structure | |
| CN106111134A (en) | The preparation of a kind of hydrocarbon fuel catalyst for cracking, coat and apply | |
| CN104148077B (en) | The preparation method of a kind of nickel cobalt/montmorillonite catalyst | |
| CN101264450A (en) | Preparation method of sulfur-resistant molybdenum-based catalyst by all-microwave method | |
| CN115920948B (en) | A preparation method and application of Ni-based catalyst enhanced by radio frequency plasma | |
| CN102389832A (en) | Catalyst for producing C5 and C6 alkanes by aqueous phase hydrogenation of high activity sorbitol and preparation method thereof | |
| CN106391020A (en) | Methane carbon dioxide reforming catalyst and preparation method and using method thereof | |
| CN116565238A (en) | A kind of biomass carbon-based nitrogen quantum dot alloy catalyst and preparation method thereof | |
| CN109833875A (en) | High-dispersion nano nickel-base catalyst and its salt help combustion process for preparing and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190719 |