CN104399485B - A kind of methane vapor low-temperature reformate catalyst and preparation method thereof - Google Patents
A kind of methane vapor low-temperature reformate catalyst and preparation method thereof Download PDFInfo
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Abstract
Embodiments provide a kind of methane vapor low-temperature reformate catalyst and preparation method thereof, belong to methane reforming catalyst field, to improve the catalysis activity of methane vapor low-temperature reformate catalyst.The preparation method of described methane vapor low-temperature reformate catalyst, including: carrier, soluble nickel salt, dispersant, auxiliary agent are put in solvent in mass ratio, stirs, obtain suspension；Control the temperature of described suspension, and in described suspension, drip reducing agent and alkaline solution, regulate the pH value of described suspension；Described suspension is aged, filters, and is dried through inert gas, obtain methane vapor low-temperature reformate catalyst.The present invention can be used in the preparation process of methane vapor low-temperature reformate catalyst.
Description
Technical field
The present invention relates to methane reforming catalyst field, particularly relate to a kind of methane vapor low temperature
Reforming catalyst and preparation method thereof.
Background technology
The approach of reforming of methane on Ni-Ce mainly has three kinds: steam reforming, catalysed partial oxygen
Change and reform and CO 2 reformation.Wherein steam reforming is current industrial methane Transformation Application
Wide method.Methane vapor reforming is the reversible endothermic reaction, has high activity, high-strength
The features such as degree and anti-carbon.It is currently used for the use of the Raney nickel of methane-steam reforming
Typically more than 750 DEG C, there is energy consumption high in temperature, to problems such as equipment requirement are high, therefore, opens
Sending out high activity methane steam low temperature (≤700 DEG C) reforming catalyst is research direction in the future.
The preparation method of current industrial SMR catalyst mainly has infusion process, is total to
The precipitation method, sol-gal process etc., during utilizing said method reduction to obtain Raney nickel,
Not only can cause the reunion of nickel oxide in calcination process and generate the nitrogen oxygen that environment is produced pollution
Compound, also can make the methane-steam reforming technique in later stage due to reducibility gas
Introduce and increasingly complex.
Solution phase chemical reduction is used to prepare the oxidation that Raney nickel can solve to cause due to calcining
Nickel reunion and the problem to environment.But, in existing solution phase chemical reduction system
During Bei, needing first to synthesize nickel hydroxide, then add reducing agent reduction, this is easy to
Agglomeration occur so that nickel element dispersion inequality, reducing agent can not be fully contacted nickel ion,
Ultimately result in reduction insufficient, affect Raney nickel catalysis in methane-steam reforming
Activity.So, the most preferably improve the catalysis of the Raney nickel of methane vapor low-temperature reformate
Activity is the important topic that those skilled in the art are faced.
Summary of the invention
Embodiments provide a kind of methane vapor low-temperature reformate catalyst and preparation side thereof
Method, to improve the catalysis activity of methane vapor low-temperature reformate catalyst.
For reaching above-mentioned purpose, embodiments of the invention adopt the following technical scheme that
A kind of preparation method of methane vapor low-temperature reformate catalyst, including:
Carrier, soluble nickel salt, dispersant, auxiliary agent are put in solvent in mass ratio, stirring
Uniformly, suspension is obtained；
Control the temperature of described suspension, and dropping reducing agent and alkalescence are molten in described suspension
Liquid, regulates the pH value of described suspension；
Described suspension is aged, filters, and is dried through inert gas, obtain methane water
Steam low-temperature reformate catalyst.
Optionally, described carrier, soluble nickel salt, dispersant, the mass ratio of auxiliary agent are 10:
0.5～2.5:0.5～3:0.05～1.
Optionally, the temperature of described suspension is controlled in the range of 40-80 DEG C.
Optionally, described suspension is alkalescence.
Further, the pH value of described suspension is 9-12.
Optionally, described reducing agent and the alkaline solution of dripping in described suspension includes:
In described suspension, first drip reducing agent, instill alkaline solution the most again；Or
In described suspension, drip reducing agent and alkaline solution simultaneously.
Preferably, in described suspension, dripping reducing agent, treating that suspension is become black by green
After look, then instill alkaline solution.
Further, after dripping reducing agent in described suspension, described suspension is carried out
Dispersion processes.
Optionally, described reducing agent is selected from sodium borohydride or ethylene glycol, 1,2 propane diols and a contracting
At least one in diethylene glycol.
Optionally, during described soluble nickel salt is selected from nickel acetate, nickel chloride and nickel sulfate at least
A kind of.
A kind of preparation side of the methane vapor low-temperature reformate catalyst provided by technique scheme
The methane vapor low-temperature reformate catalyst that method prepares.
Optionally, including carrier, soluble nickel salt and auxiliary agent, and described carrier, soluble nickel
The mass ratio of salt and auxiliary agent is 10:0.5～2.5:0.05～1.
Embodiments provide a kind of methane vapor low-temperature reformate catalyst and preparation side thereof
Method, in the method, by using first load reduction regulate pH value again or complete load simultaneously
Reduction and the technological means of pH value regulation, can make nickel ion fully be reduced and effectively prevention
Grain is reunited, thus improves the catalysis activity of nickel.
Accompanying drawing explanation
The preparation side of the methane vapor low-temperature reformate catalyst that Fig. 1 provides for the embodiment of the present invention
The flow chart of method.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, to the technical side in the embodiment of the present invention
Case is clearly and completely described, it is clear that described embodiment is only the present invention one
Divide embodiment rather than whole embodiments.Based on the embodiment in the present invention, this area is general
The every other embodiment that logical technical staff is obtained under not making creative work premise,
Broadly fall into the scope of protection of the invention.
The methane vapor low-temperature reformate the catalyst below in conjunction with the accompanying drawings embodiment of the present invention provided
And preparation method thereof be described in detail.
The preparation side of the methane vapor low-temperature reformate catalyst that Fig. 1 provides for the embodiment of the present invention
The flow chart of method.As it is shown in figure 1, embodiments provide a kind of methane vapor low temperature
The preparation method of reforming catalyst, including:
S1: carrier, soluble nickel salt, dispersant, auxiliary agent are put in solvent in mass ratio,
Stir, obtain suspension.
In this step, carrier can be nanometer Al2O3, cordierite nano-powder, Nano-meter SiO_22；
Dispersant can be one or more in polysorbate85, PEG 2000, F127, P123；Auxiliary agent
Can be one or more in zirconium oxide, magnesia, cerium oxide, lanthana, manganese oxide；Molten
Agent can be water, ethanol.Wherein, dispersant is conducive to improving the dispersiveness of the nickel particles generated,
Prevent nickel particles from reuniting, thus improve the catalysis activity of Raney nickel；Auxiliary agent is conducive to subtracting
Carbon distribution during little use, increases the life-span of catalyst.Above-mentioned raw materials is put in mass ratio
In solvent, stir, to obtain finely dispersed suspension.
S2: control the temperature of described suspension, and drip reducing agent and alkali in described suspension
Property solution, regulates the pH value of described suspension.
In this step, the purpose dripping reducing agent in described suspension is to make soluble nickel
Salt reacts with reducing agent, is supported on carrier so that nickel ion is reduced to nickel particle.
Owing to some acidic materials also can be generated while reacting with reducing agent in soluble nickel salt,
And the nickel particle generated can be played dissolution by these acidic materials, so and then to suspension
Middle dropping alkaline solution, neutralizes acidic materials, the pH value of regulation suspension.In this step one
In preferred embodiment, described alkaline solution can be sodium hydroxide solution.It is understood that
It can be not only that NaOH is molten that suspension carries out the alkaline solution that pH value regulation used
Liquid, it is also possible to be other suitable alkaline solution, such as potassium hydroxide, calcium hydroxide, ammoniacal liquor etc.,
But owing to these alkaline solutions can introduce impurity, at subsequent wash dedoping step in reaction system
In be difficult to be washed away, or have penetrating odor, so final choice hydrogen-oxygen in the present embodiment
Change sodium and neutralize the acidic materials that reaction generates, to reach to regulate the mesh of the pH value of reaction system
's.Wherein, naoh concentration can be 0.1mol/L-1mol/L, and those skilled in the art can basis
Actual conditions select the NaOH of variable concentrations to be adjusted.
S3: described suspension is aged, filters, and is dried through inert gas, obtain first
Alkane steam low-temperature reformate catalyst.
In this step, to after above-mentioned reaction and regulate the suspension of pH value and be aged, old
The time changed is about 2 hours, so that nickel particle and builder granule fully load on carrier, so
Afterwards system filtered, wash, to wash away dispersant and foreign ion, such as NaOH
In sodium ion, and it is dried through inert gas, to finally give methane vapor low temperature weight
Whole catalyst fines.It is understood that the inert gas used in the present embodiment can be
Nitrogen, argon gas etc., the present embodiment is also not specifically limited.
Embodiments provide the preparation side of a kind of methane vapor low-temperature reformate catalyst
Method, in the method, by using first load reduction regulate pH value again or complete load simultaneously
Reduction and the technological means of pH value regulation, can make nickel ion fully be reduced and effectively prevention
Grain is reunited, thus improves the catalysis activity of nickel.
In one embodiment of this invention, described carrier, soluble nickel salt, dispersant, auxiliary agent
Mass ratio be 10:0.5～2.5:0.5～3:0.05～1.The present embodiment is with the quality of carrier as base
Other each component is defined by standard.Under this proportion, dispersant can be by above-mentioned raw materials
Formed in suspension and preferably play peptizaiton, so that soluble nickel salt is in the assistance of auxiliary agent
Under be supported on the most uniformly on carrier.Preferably, described carrier, soluble nickel salt, dispersion
Agent, the mass ratio of auxiliary agent are 10:1:3:1.Under this ratio, the suspension of formation more bonus point
Dissipate uniformly, and then obtain catalysis activity higher methane steam low-temperature reformate reaction catalyst particles
Grain.
In one embodiment of this invention, the temperature of described suspension is controlled the model at 40-80 DEG C
In enclosing.In the present embodiment, control the temperature of suspension to be mainly in the range of 40-80 DEG C
Because the temperature controlling suspension can control to generate size and the speed of nickel particle.Such as, when
When temperature is less than 40 DEG C, the reaction of reaction system is relatively slow, and the nickel particle of generation is less, the most easily
It is attached on carrier, is the most easily attached on the wall of reaction vessel, thus cause waste；Work as temperature
When degree is higher than 80 DEG C, reducing agent activity is high, and the reaction of reaction system is more violent, the nickel of generation
Particle is relatively big, thus affects catalyst activity.Optionally, the temperature of described suspension controls
50℃、60℃、70℃。
In one embodiment of this invention, described suspension is alkalescence.Described suspension is alkalescence,
Can effectively neutralize the acidic materials that reaction generates, so that it is guaranteed that the nickel particle of the generation of reaction is not
Can again be dissolved.In the preferred embodiment of the present invention, the pH value of described suspension is
9-12.The pH value of described suspension is maintained at 9-12, not only can effectively neutralize reaction and generate
Acidic materials, also can avoid affecting produced by reaction system because alkalescence is too strong.
In one embodiment of this invention, described dropping reducing agent and alkalescence in described suspension
Solution includes: first drips reducing agent in described suspension, instills alkaline solution the most again；Or
In described suspension, drip reducing agent and alkaline solution simultaneously.In the present embodiment, alkalescence is molten
Liquid, preferably sodium hydroxide solution must instill suspension after reducing agent drips or while dropping
In, generate nickel hydroxide precipitate to avoid first dripping NaOH, cause nickel element to disperse not
Uniformly, the problem that reducing agent can not be fully contacted nickel ion.In a preferred embodiment of the present invention
In, first can drip reducing agent in described suspension, instill alkaline solution the most again.
In another embodiment of the present invention, in described suspension, dripping reducing agent, wait to hang
After turbid liquid is become black by green, then instill alkaline solution, so that it is guaranteed that reducing agent with can solution
Nickel salt reaction is completely.In another embodiment of the present invention, in order to ensure to described suspension
After middle dropping reducing agent, reducing agent with can be fully contacted and react completely by solution nickel salt, also
Described suspension can be carried out dispersion process.It is understood that in order to make reducing agent with
Can be fully contacted and react completely by solution nickel salt, it can be ultrasonically treated that described dispersion processes,
But in addition to which, it is also possible to make otherwise to process, the present embodiment does not do to be had
Body limits.
In one embodiment of this invention, described reducing agent selected from sodium borohydride or ethylene glycol,
At least one in 1,2 propane diols and diglycol.Reducing agent selected in the present embodiment
Be chosen as during utilizing reducing agent and soluble nickel salt to react not to reaction system
Other element impurity of middle introducing, even if or introducing other element, also for be prone in follow-up washing
During be prone to the element that washes away.It is understood that those skilled in the art can be according to reality
Situation selects rational reducing agent.Wherein, the amount of reducing agent can be 50～100mL, and consumption is
Depending on whole visual response is required.
In one embodiment of this invention, described soluble nickel salt selected from nickel acetate, nickel chloride and
At least one in nickel sulfate.In the present embodiment, it is emphasized that, present stage, made
Soluble nickel salt mostly be nitrate, but the most unusable, this is because
Nickel nitrate and reducing agent react generated product in an acidic solution (the most not yet to
Suspension adds before NaOH) moment is i.e. dissolved, thus unsuitable in the present embodiment
Select nickel nitrate, but select any one or it in nickel acetate, nickel chloride and nickel sulfate
Combination.
A kind of preparation method of the methane vapor low-temperature reformate catalyst provided by above-described embodiment
The methane vapor low-temperature reformate catalyst prepared.The methane prepared by said method
Steam low-temperature reformate catalyst, owing to effectively preventing reaction particles to send out in course of reaction
Raw reunion, nickel ion has obtained abundant reduction so that the Raney nickel catalysis activity finally given
Higher.
In one embodiment of this invention, including carrier, soluble nickel salt and auxiliary agent and described
The mass ratio of carrier, soluble nickel salt and auxiliary agent is 10:0.5～2.5:0.05～1.In this enforcement
In example, owing to dispersant is washed away in final washing process, so the nickel finally given is urged
Agent does not contains dispersant, wherein, the mass ratio of described carrier, soluble nickel salt and auxiliary agent
For 10:0.5～2.5:0.05～1, it is preferred that the matter of described carrier, soluble nickel salt and auxiliary agent
Amount ratio is 10:1:1.
In order to methane vapor low-temperature reformate catalysis that the embodiment of the present invention provided is better described
Agent and preparation method thereof, is specifically described below in conjunction with embodiment.
Embodiment 1
Nanometer cordierite, nickel acetate, F127, auxiliary agent (magnesia: lanthana=2:1) are pressed
Mass ratio 10:1:3:1 puts in 200mL water, stirs 20min, makes suspension be uniformly dispersed；
Control described suspension temperature, at 40 DEG C, drip 80mL 1,2 propane diols, make at ultrasonic wave
With lower reaction 40min, then dropping concentration is that 0.5mol/L NaOH regulates reaction system
PH value is to 11, then reacts 30min, is aged 2h, filters, washing, and dry through nitrogen protection
Dry obtain catalyst powder；By the catalyst fines compressing tablet obtained and be crushed to 40～60 mesh particles,
Obtain methane vapor low-temperature reformate reaction catalyst granules 1.
Embodiment 2-6
It is anti-that embodiment 2-6 uses method same as in Example 1 to prepare methane vapor low-temperature reformate
Applications catalyst particle, the design parameter in each embodiment sees table 1, finally gives methane water and steams
Catalyst granules 2-6 is used in the reaction of gas low-temperature reformate.
Design parameter in table 1 embodiment 2-6
Comparative example
Nanometer cordierite, nickel acetate, F127, auxiliary agent (magnesia: lanthana=2:1) are pressed
Mass ratio 10:1:3:1 puts in 200mL water, stirs 20min, makes suspension be uniformly dispersed；
Controlling described suspension temperature, dripping concentration at 40 DEG C is that the regulation of 0.5mol/L NaOH is anti-
Answer the pH value of system to 11, then drip 80mL 1,2 propane diols, then react 30min,
Ageing 2h, filters, washing, and nitrogen protection is dried to obtain catalyst powder；The catalysis that will obtain
Agent pressed powder is also crushed to 40～60 mesh particles, obtains the reaction of methane vapor low-temperature reformate and uses
Catalyst granules 7.
Catalysis active testing
The catalyst granules 1 that respectively 5g prepared by embodiment 1 and being prepared into by comparative example
To catalyst granules 7 be filled in methane vapor low-temperature reformate reactor, be passed through mol ratio
For methane and the steam of 1:2.5, react at 500 DEG C, carry out being catalyzed active testing, specifically
Active testing the results are shown in Table 2.
The active testing result of the catalyst granules that table 2 is prepared by embodiment 1 and comparative example
From data in above-mentioned table, by the first of the preparation-obtained catalyst granules of embodiment 1
Alkane average conversion is 33.14%, and by the methane of the preparation-obtained catalyst granules of comparative example
Average conversion is only 20.94%.It follows that the methane water provided by the embodiment of the present invention
The catalysis of the preparation-obtained Raney nickel of preparation method of steam low-temperature reformate catalyst is active to be obtained
Arrive significant raising.
Obviously, above-described embodiment is only for clearly demonstrating example, and not to reality
Execute the restriction of mode.For those of ordinary skill in the field, at the base of described above
Can also make other changes in different forms on plinth.Here without also cannot be to all
Embodiment give exhaustive.And the obvious change thus extended out or variation are still located
Protection domain in the invention.
Claims (10)
1. the preparation method of a methane vapor low-temperature reformate catalyst, it is characterised in that bag
Include:
Carrier, soluble nickel salt, dispersant, auxiliary agent are put in solvent in mass ratio, stirring
Uniformly, obtaining suspension, wherein, described soluble nickel salt is selected from nickel acetate, nickel chloride and sulphur
At least one in acid nickel；
Control the temperature of described suspension, and dropping reducing agent and alkalescence are molten in described suspension
Liquid, regulates the pH value of described suspension, wherein, drips reducing agent and alkali in described suspension
Property solution include: in described suspension, first drip reducing agent, instill alkaline solution the most again；
Or in described suspension, drip reducing agent and alkaline solution simultaneously；
Described suspension is aged, filters, and is dried through inert gas, obtain methane water
Steam low-temperature reformate catalyst.
Preparation method the most according to claim 1, it is characterised in that described carrier, can
Insoluble nickel salt, dispersant, the mass ratio of auxiliary agent are 10:0.5～2.5:0.5～3:0.05～1.
Preparation method the most according to claim 1, it is characterised in that by described suspension
Temperature control in the range of 40-80 DEG C.
Preparation method the most according to claim 1, it is characterised in that described suspension is
Alkalescence.
Preparation method the most according to claim 4, it is characterised in that described suspension pH
Value is 9-12.
Preparation method the most according to claim 5, it is characterised in that to described suspended
Liquid drips reducing agent, after suspension is become black by green, then instills alkaline solution.
Preparation method the most according to claim 6, it is characterised in that to described suspended
After liquid drips reducing agent, described suspension is carried out dispersion process.
Preparation method the most according to claim 1, it is characterised in that described reducing agent selects
At least one in sodium borohydride or ethylene glycol, 1,2 propane diols and diglycol.
9. the methane vapor low-temperature reformate catalyst as described in any one of claim 1-8
The methane vapor low-temperature reformate catalyst for preparing of preparation method.
Methane vapor low-temperature reformate catalyst the most according to claim 9, its feature
It is, including carrier, soluble nickel salt and auxiliary agent, and described carrier, soluble nickel salt and help
The mass ratio of agent is 10:0.5～2.5:0.05～1.
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| JP6828877B2 (en) * | 2016-08-29 | 2021-02-10 | 国立大学法人九州大学 | Paper-like catalyst and its production method, paper-like catalyst array and hydrocarbon reforming method |
| CN109529855A (en) * | 2018-12-26 | 2019-03-29 | 济南大学 | A kind of efficient low carrying capacity acetic acid reformation hydrogen production nickel-base catalyst and preparation method thereof that KOH is modified |
| CN112844476B (en) * | 2021-01-18 | 2023-09-26 | 武汉科技大学 | Biomass-based carbon material loaded nano nickel catalyst and preparation method and application thereof |
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| ATE385441T1 (en) * | 2001-03-29 | 2008-02-15 | Idemitsu Kosan Co | CATALYTIC PROCESS FOR REFORMING HYDROCARBON USING CATALYST |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
| CN101829577A (en) * | 2010-04-23 | 2010-09-15 | 浙江大学 | Composite catalyst, preparation and application thereof |
| CN102489311B (en) * | 2011-11-23 | 2013-07-17 | 重庆大学 | Catalyst for hydrogen production through catalytic cracking of methane and its preparation method |
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| CN103752319B (en) * | 2013-12-31 | 2016-08-17 | 南昌大学 | Anti-carbon Ni methylmethane vapor reforming hydrogen production catalyst and preparation method thereof |
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