CN106311250A - Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming - Google Patents
Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming Download PDFInfo
- Publication number
- CN106311250A CN106311250A CN201510346603.1A CN201510346603A CN106311250A CN 106311250 A CN106311250 A CN 106311250A CN 201510346603 A CN201510346603 A CN 201510346603A CN 106311250 A CN106311250 A CN 106311250A
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- cerium
- base catalyst
- based catalyst
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a nickel-based catalyst, a preparation method of the nickel-based catalyst, a reduction state nickel-based catalyst and a method for preparing a synthesis gas through methane auto-thermal reforming. The preparation method of the nickel-based catalyst comprises the following steps: (1) under ultrasonic and stirring conditions, enabling a precipitant, hydrogen peroxide, a cerium salt and a zirconium salt to be in contact in a water phase, performing aging, separating an aged product, and performing first drying and first roasting, so as to obtain a cerium-zirconium solid solution; and (2) introducing a nickel precursor into the cerium-zirconium solid solution obtained in the step (1), and performing second drying and second roasting, thereby obtaining the nickel-based catalyst. By adopting the preparation method disclosed by the invention, the nickel-based catalyst which is large in specific surface area and uniform in nickel material dispersion can be prepared, and the reduction state nickel-based catalyst is good in catalytic performance when being used in a reaction for preparing the synthesis gas through methanol auto-thermal reforming.
Description
Technical field
The present invention relates to the preparation method of a kind of nickel-base catalyst, nickel-base catalyst prepared by the method, also
Ortho states nickel-base catalyst and use this reduction-state nickel-base catalyst carry out methane autothermal reforming reaction system close
The method becoming gas.
Background technology
Reforming of methane on Ni-Ce is the main path of gas industry application.Wherein, methane self-heating recapitalization
React the steam reforming reaction and the partial oxidation reaction of heat release having coupled heat absorption because of it and receive much attention.
By regulation proportioning raw materials, methane autothermal reforming reaction can obtain the different synthesis gas of proportion of products with suitable
For the production of multiclass downstream product, realize the part of system from heat supply simultaneously.Therefore, from saving the energy
For the angle of regulation product proportioning, methane self-heating recapitalization preparing synthetic gas be can yet be regarded as a kind of efficient, cheap
Natural gas conversion technology.
In addition to Os, VIII transition metal is respectively provided with catalysis activity, wherein your gold to methane reforming reaction
The catalysis activity belonging to (such as Pt, Pd, Rh, Ir etc.) is higher, and anti-carbon deposition ability is relatively strong, and stability is preferable,
But the synthesis of noble metal catalyst is relatively costly.In order to reduce catalyst cost, research worker is to inexpensively
Transition-metal catalyst has done numerous studies, mainly includes the metallic catalysts such as Ni, Co, Fe, wherein
The performance of Ni base catalyst is best.Compared with noble metal catalyst, transition-metal catalyst metal state holds
Easily change in course of reaction, and then cause catalyst stability poor and be prone to carbon distribution.Carrier
Structure and properties, the interaction of carrier and metal component and the caltalyst caused therefrom are tied mutually
Structure, composition, granular size, dispersion change to the reduction act of active component and reactivity worth and
Coking resistivity etc. all have a certain impact.In order to improve transition-metal catalyst catalytic methane reforming reaction
Performance, people have carried out careful screening to catalyst carrier.
Because methane reforming reaction temperature higher (more than 700 DEG C), typically can select that there is good heat steady
Material is as carrier qualitatively, mainly includes SiO2、TiO2、A12O3, MgO, CaO, carborundum,
Rare earth oxide and some metal composite oxide and molecular sieve etc. (CN100388975C,
CN101402041B、CN1994561A、CN102416328A、CN102974353A、
CN102698789A、CN102974353A、CN101450310A、CN101462058A).These
Carrier should be provided simultaneously with interaction suitable between suitable specific surface area and pore structure and metal,
The features such as stable crystalline phase composition, higher fusing point.
It was discovered by researchers that not only the physical arrangement of carrier can produce impact, carrier to the performance of catalyst
The redox property on surface also can affect the reactivity worth of catalyst to a certain extent.Such as: Zr4+
Enter CeO2Lattice produces distortion of lattice, forms CeO_2-ZrO_2 solid solution, and this solid solution has good storage oxygen
Ability.The research group of Tsing-Hua University Xu Baiqing professor has carried out CO with cerium zirconium sosoloid for catalyst2
Reformation CH4Reaction.Result shows, the Ce that redox property is the strongest0.75Zr0.25O2Catalyst shows
The highest catalysis activity, anti-carbon deposition ability and stability (catalysis journal, 2006,27 (2): 151-156).
But, only using cerium zirconium sosoloid as catalyst carry out methane reforming reaction time, catalyst activity is relatively low,
Under the conditions of the reaction temperature of 850 DEG C, the conversion ratio of methane is only about 20%.But conventional preparation side
The cerium zirconium sosoloid specific surface area that method obtains is less, and metal component degree of scatter on carrier surface is not
Height, the metallic catalyst prepared using cerium zirconium sosoloid as carrier merely catalysis in methane reforming reaction
Performance still can not be fully up to expectations.
Solution of the prior art has two classes: (1) in addition to cerium oxide and zirconia components, methane weight
The carrier of whole catalyst is also added into other components such as MgO, CaO, Al2O3Deng, form composite oxygen
Compound carrier (CN101049566A, CN102112227A, CN102133532B)；Or (2)
Noble metal component (CN101224427A) is added in the active metal component of catalyst.But above-mentioned respectively
The method of kind there is problems in that (a) catalyst component is more complicated, and preparation technology is more loaded down with trivial details, is difficult to
Repeat；(b) interpolation noble metal component can directly result in catalyst preparation cost to be increased, and manufacturing cycle
Extend.
Therefore, commercial Application for convenience, need exploitation a kind of more convenient and can obtain to have more preferably to urge
The preparation method of the nickel-base catalyst of agent performance.
Summary of the invention
The invention aims to acquisition and there is more preferable methane self-heating recapitalization preparing synthetic gas catalysis activity
Catalyst, it is provided that nickel-base catalyst and preparation method thereof, reduction-state nickel-base catalyst and methane from
The method of thermal reforming preparing synthetic gas.
The present inventor finds when carrying out nickel-base catalyst preparation research, and customary preparation methods obtains
Cerium zirconium sosoloid specific surface area less, metal component degree of scatter on carrier surface is the highest, seriously
Affect catalyst performance, be prone to carbon distribution, less stable when catalytic methane reforming reaction.
If use ultrasonic assistant means and oxidation and co-precipitation during preparing cerium zirconium sosoloid simultaneously
Shallow lake method, promotes Ce4+And Zr4+Dispersed, it is favorably improved the degree of scatter of metallic nickel species, i.e.
Can not increasing operating procedure and difficulty, without noble metal on the premise of obtain reduction-state nickel catalyst
Agent, this catalyst has more preferable catalytic performance in methane self-heating recapitalization preparing synthetic gas reacts.
To achieve these goals, the present invention provides a kind of method preparing nickel-base catalyst, the method bag
Include: precipitant, hydrogen peroxide, cerium salt and zirconates with under stirring condition, are connect in aqueous phase by (1) ultrasonic
Touch, and carry out aging, carry out the product after aging separating, first be dried and the first roasting, obtain cerium
Zirconium solid solution；(2) cerium zirconium sosoloid obtained in step (1) introduces the presoma of nickel, and carries out
Second is dried and the second roasting, obtains nickel-base catalyst.
Present invention also offers the nickel-base catalyst that a kind of method provided by the present invention prepares.
Present invention also offers the reduction that a kind of nickel-base catalyst provided by the present invention obtains through reduction
State nickel-base catalyst, wherein, described reduction includes reducing nickel-base catalyst under hydrogen atmosphere, institute
The temperature stating reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, in described hydrogen atmosphere
Hydrogen content is 10-60 volume %.
A kind of method that present invention also offers methane self-heating recapitalization preparing synthetic gas, the method includes: by first
Alkane, oxygen and water react in the presence of a catalyst, wherein, and the nickel that described catalyst provides for the present invention
Base catalyst.
Employing the method have the advantages that:
(1) can use common facile inorganic salt is raw material, uses the letter of ultrasonic method preparation manipulation
Single, it is simultaneously introduced hydrogen peroxide and can prepare the reduction-state nickel catalyst that specific surface area cost pore volume is bigger
Agent, this catalyst has good activity and stability in course of reaction, is difficult to because metallic is reunited
And inactivate, expensive noble metal can be used, reduce the preparation cost of nickel-base catalyst；
(2) the preparation method step operation of the present invention is simple, and condition is easily controllable, good repetitiveness；
(3) the reduction-state nickel-base catalyst that the present invention provides is used for the anti-of methane self-heating recapitalization preparing synthetic gas
At once, show more preferable catalytic performance, have higher methane conversion, carbon monoxide selective, hydrogen
Selectivity, and H2/ CO ratio can regulate within the specific limits along with the change of reaction condition.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is CeO2And the X of the nickel-base catalyst in embodiment 1, comparative example 1 and comparative example 2
X ray diffration pattern x.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method preparing nickel-base catalyst, the method includes: (1) ultrasonic and
Under stirring condition, precipitant, hydrogen peroxide, cerium salt are contacted with zirconates in aqueous phase, and carry out aging,
Carry out the product after aging separating, first be dried and the first roasting, obtain cerium zirconium sosoloid；(2) to
The cerium zirconium sosoloid obtained in step (1) introduces the presoma of nickel, and carries out second dry and the second roasting
Burn, obtain nickel-base catalyst.
One preferred implementation of the present invention, in step (1) by precipitant, hydrogen peroxide with containing cerium salt
Contact with the aqueous solution of zirconates, and carry out after regulating the pH ＞ 7 of product obtained aging；Preferably,
PH=9-11.
According to the present invention, step (1) can use cheap and easily-available, and can be configured to aqueous solution
Cerium salt., under preferable case, described cerium salt is Inorganic Cerium salt, and the most described cerium salt is cerous nitrate, trichlorine
Change at least one in cerium and cerous sulfate.
According to the present invention, as long as the amount of the cerium salt contained in described aqueous solution meets prepares nickel-base catalyst
Consumption, under preferable case, Ce in described aqueous solution3+Concentration be 0.1-0.3mol/L.
According to the present invention, step (1) can use cheap and easily-available, and can be configured to aqueous solution
Zirconates.Under preferable case, described zirconates is inorganic zirconium salts, and the most described zirconates is zirconium nitrate, Nitric Acid Oxidation
At least one in zirconium, zirconium oxychloride and Disulfatozirconic acid..
According to the present invention, as long as the amount of the zirconates contained in described aqueous solution meets prepares nickel-base catalyst
Consumption, under preferable case, in described aqueous solution, zirconium ion can be 0.5-2 with the mol ratio of cerium ion:
1.When in aqueous solution, zirconium ion and cerium ion ratio are less than 0.5:1, the cerium zirconium sosoloid pattern of formation is more
Close to pure zirconia cerium, sample specific surface area is less, pore volume is less, the dispersion journey of nickel species on catalyst
Spend catalytic performance relatively low, reduction-state nickel-base catalyst poor；When zirconium ion and cerium ion ratio are higher than 2:1
Time, sample is the mixed phase of pure zirconia and cerium zirconium sosoloid, and the specific surface area of this sample is less, hole body
On long-pending less, catalyst, the degree of scatter of nickel species is relatively low, the catalytic performance of reduction-state nickel-base catalyst relatively
Difference.
In the case of according to the invention it is preferred to, the concentration of described hydrogen peroxide is 1-5mol/L.In the present invention,
Step (1) adds hydrogen peroxide and can aid in the cerium zirconium sosoloid obtaining structure evenly.
In the case of according to the invention it is preferred to, Ce in described aqueous solution3+It is 1 with the mol ratio of hydrogen peroxide:
0.5-1。
In the present invention, described precipitant can be in ammonia, sodium bicarbonate, sodium hydroxide and potassium hydroxide
At least one, the most described precipitant is ammonia.Preferably, the concentration of described ammonia can be
2-8mol/L。
In the present invention, it may be preferred to hydrogen peroxide is added described water-soluble with the rate of addition of 0.5-1ml/min
In liquid, it is simultaneously introduced the pH ＞ 7 of the product that ammonia obtains with the described contact of holding.
In the step (1) of the present invention, take at the same time ultrasonic and stirring under conditions of carry out precipitant,
Hydrogen peroxide contacts with the aqueous solution containing cerium salt and zirconates, can by supersonic generator provide ultrasonic
Condition promotes conventional stirring, is conducive to improving the described effect contacted in terms of microcosmic with macroscopic view two.
Such as can ultrasonic cleaner (as Kunshan Ultrasonic Instruments Co., Ltd. produce model be
KQ-300GTDV ultrasonic cleaner) in add ammonia, hydrogen peroxide with containing cerium salt and the water of zirconates
Solution, carries out described contact.Under preferable case, described ultrasound condition may include that ultrasonic temperature is
20-60 DEG C, ultrasonic power is 150-250W.The cerium in aqueous solution is can aid under ul-trasonic irradiation
Ion and zirconium ion dispersed.
In the present invention, there is no particular limitation for the stirring condition in step (1), and preferably stir speed (S.S.) can
Think 500-1500rpm.Coordinate with ultrasound condition and realize described contact process is effectively disperseed.
According to the present invention, carrying out aging condition in step (1) does not has particular/special requirement, can include old
The temperature changed is 20-40 DEG C, and the aging time is 2-16h.Product contact obtained can be specially enter
Row stands.
In the present invention, first in step (1) is dried and the first roasting does not has particular/special requirement, concrete
Implementation condition can determine according to the condition that this area is conventional, and such as, the first condition being dried may include that
The temperature being dried is 100-150 DEG C, preferably 110-130 DEG C；The time being dried is 1-20h, is preferably
2-5h.The condition of the first roasting may include that the temperature of roasting is 450-700 DEG C, preferably 500-600
℃；The time of roasting is 2-15h, preferably 3-10h.Under first roasting condition, obtain cerium zirconium sosoloid.
According to the present invention, step (2) is for introducing cerium zirconium sosoloid by metallic nickel.The forerunner of described nickel
Body is the material that can be changed into nickel oxide under the second roasting condition, under preferable case, before described nickel
Driving body is at least one in nickel nitrate, nickel acetate, nickelous carbonate and nickel sulfate.
In the case of according to the invention it is preferred to, the nickel in the presoma of described nickel and the quality of cerium zirconium sosoloid
Ratio is 1:4-20, preferably 1:5-15.
In the case of according to the invention it is preferred to, the method for the presoma introducing nickel is dipping or precipitation.Described
Dipping can be the solution with the presoma of nickel or suspension impregnation cerium zirconium sosoloid, then removes solvent；
Described precipitation can be solution or the suspension of the presoma of nickel to be mixed with cerium zirconium sosoloid, is subsequently adding
The presoma of nickel is deposited on cerium zirconium sosoloid by ammonia.It is preferably dipping, is specifically as follows before nickel
Drive the aqueous impregnation cerium zirconium sosoloid of body, then carry out except water.
In the present invention, introducing the mode except water after the presoma of nickel can go in the way of being known in the art
Remove, for example with Rotary Evaporators, except water under the conditions of uniform temperature and certain pressure.
In the present invention, second in step (2) is dried and the second roasting does not has particular/special requirement, concrete
Implementation condition can determine according to the condition that this area is conventional, and such as, the second condition being dried may include that
The temperature being dried is 100-150 DEG C, preferably 110-130 DEG C；The time being dried is 1-20h, is preferably
2-5h.The condition of the second roasting may include that the temperature of roasting is 450-700 DEG C, preferably 500-600
℃；The time of roasting is 2-15h, preferably 3-10h.Under second roasting condition, obtain catalyst precarsor,
Wherein contain cerium zirconium sosoloid and nickel nitrate is changed into the oxide of nickel.
Present invention also offers the nickel-base catalyst that a kind of method provided by the present invention prepares.
Present invention also offers the reduction that a kind of nickel-base catalyst provided by the present invention obtains through reduction
State nickel-base catalyst, wherein, described reduction includes reducing nickel-base catalyst under hydrogen atmosphere, institute
The temperature stating reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, in described hydrogen atmosphere
Hydrogen content is 10-60 volume %.
In the present invention, the nickel oxide in nickel-base catalyst is changed into metal simple-substance by described being also originally intended to, institute
Nickel oxide in described nickel-base catalyst is only changed into metal simple-substance by the condition stating reduction, and other are golden
Belong to, as cerium zirconium sosoloid will not change.
In the present invention, described reduction can be carried out after prepared nickel-base catalyst immediately, it is also possible to is using
Before (i.e. for methane self-heating recapitalization preparing synthetic gas) carry out.Owing to nickel easily aoxidizes, and nickel-base catalyst
In nickel exist in the form of an oxide, therefore for ease of transport, preferably by nickel-base catalyst reduction carrying out
Carry out before methane self-heating recapitalization preparing synthetic gas.Base in the described reduction-state nickel-base catalyst being reduced to make to obtain
The nickel of reduction-state is there is in basis.
In the case of according to the invention it is preferred to, on the basis of the gross weight of this catalyst, containing 6.2-16.7
The nickel of weight %, the cerium zirconium sosoloid of 83.3-93.8 weight %.
In the present invention, the method for step (1) prepares cerium zirconium sosoloid, can be by prepared catalysis
The structural analysis of agent reflects this solid solution.The easily oxidation when carrying out structural analysis of reduction-state nickel-base catalyst,
And nickel-base catalyst cerium zirconium sosoloid in reduction process will not change, it is also possible to the nickel catalyst to preparation
Agent carries out X-ray diffraction analysis (XRD).From the XRD spectra obtained, such as Fig. 1 it will be seen that
First Emission in Cubic CeO2XRD spectra in, be positioned at diffraction maximum at 2 θ=28.4 ° corresponding to (111)
Crystal face, the diffraction maximum at 2 θ=33.1 ° corresponds to (200) crystal face, and the diffraction maximum at 2 θ=47.3 ° is corresponding
In (220) crystal face, the diffraction maximum at 2 θ=56.1 ° corresponds to (311) crystal face, at 2 θ=58.9 °
Diffraction maximum corresponds to (222) crystal face, and the diffraction maximum at 2 θ=69.3 ° corresponds to (400) crystal face.And cerium
After zirconium forms solid solution, CeO2The diffraction maximum of (111), (200), (220) and (311) crystal face send out
Raw widthization and displacement, the diffraction maximum of (222) and (400) crystal face disappears or displacement, concrete different ceriums
In the XRD spectra of the cerium zirconium sosoloid of zirconium mol ratio such as Fig. 1 shown in (a), (b) and (c).So
Cerium zirconium sosoloid can be that the reduction-state nickel-base catalyst that obtains further provides more preferable methane self-heating
The catalysis activity of preparing synthetic gas by reforming.Preferably, this catalyst elements cerium is 0.5-2 with the mol ratio of zirconium:
1。
In the present invention, the more preferably specific surface area of this catalyst is 130-150m2/ g, pore volume is 1.2-1.4
cm3/g；Nickel can be present in the surface of cerium zirconium sosoloid with the state of high degree of dispersion.
A kind of method that present invention also offers methane self-heating recapitalization preparing synthetic gas, the method includes: by first
Alkane, oxygen and water react in the presence of a catalyst, and wherein, described catalyst is going back that the present invention provides
Ortho states nickel-base catalyst.
In the case of according to the invention it is preferred to, the mol ratio of described methane, oxygen and water is 1:0.1-0.5:
0.5-2, the condition of described contact includes: temperature is 750-850 DEG C, and pressure is 0.1-0.2MPa, methane
Air speed be 4000-40000ml/gcat h.
Hereinafter will be described the present invention by embodiment.
In following example, used reagent is commercially available analytical reagent；
Ultrasonic cleaner is that Kunshan Ultrasonic Instruments Co., Ltd. produces, model KQ-300GTDV；
Rotary Evaporators is that IKA company of Germany produces, and model is RV10 digital；
Drying baker is that Shanghai Yiheng Scientific Instruments Co., Ltd produces, model DHG-9030A；
Muffle furnace is that CARBOLITE company produces, model C WF1100.
In following example and comparative example, the X ' that the XRD test of sample produces in Philips company of Holland
Carry out on Pert MPD type x-ray powder diffraction instrument；
The N of sample2Adsorption-desorption experiment produces in Micromeritics company of the U.S.
Carrying out on ASAP2020-M+C type adsorption instrument, the specific surface area of sample calculates and uses BET method.
In the reduction-state nickel-base catalyst of preparation, the content of each component feeds intake calculating really by raw material during preparation
Fixed.
Embodiment 1
The present embodiment is for illustrating that what the present invention provided prepares nickel-base catalyst and reduction-state nickel-base catalyst
Method.
(1) by the Ce (NO of 0.2mol3)3·6H2ZrO (the NO of O and 0.2mol3)2·2H2O is configured to
The mixed aqueous solution of 1000ml, and be transferred in there-necked flask.
Being put into by there-necked flask in ultrasonic cleaner, regulation ultrasonic power is 200W, and ultrasonic temperature is 40
℃.Under conditions of opening ultrasonic and continuous stirring 1000rpm, with the speed of 0.5ml/min to three mouthfuls
Drip the hydrogen peroxide 50ml of 3.0mol/L in Ping, in there-necked flask, drip the ammonia of 5mol/L to protect simultaneously
Hold the pH=10 of system.After whole dropping process, continue ultrasonic and stir 2 hours；Then room
Gentle and quiet put aging 10 hours, sucking filtration, obtain solid product.
Cleaning solid product 3 times with the distilled water of 2000ml, then solid product is placed in temperature is 120
DEG C drying baker in be dried 3 hours, then 550 DEG C of roastings 6 hours in Muffle furnace, obtain cerium zirconium solid solution
Body.
(2) by the Ni (NO of 3.94g3)2·6H2O is dissolved in 100ml distilled water, prepares with above-mentioned
The cerium zirconium sosoloid mixing of 10.0g, continuous stirring is reacted 5 hours at ambient temperature.Use rotary evaporation
Instrument boils off the water in system, obtains solid product.
Solid product is placed in the drying baker that temperature is 120 DEG C, is dried 3 hours.Then at Muffle furnace
In, temperature is 550 DEG C of roastings 6 hours, obtains nickel-base catalyst-1.
(3) by nickel-base catalyst-1 reductase 12 h at 425 DEG C in hydrogen atmosphere, reduction-state is obtained Ni-based
Catalyst A.
The composition of this catalyst A contains: the nickel of 7.4 weight %, the cerium zirconium sosoloid of 92.6 weight %；
Cerium is 1:1 with the mol ratio of zirconium.The specific surface area of catalyst A is 146m2/ g, pore volume is 0.69cm3/g。
Nickel-base catalyst-1 is carried out X-ray diffraction, and spectrogram is as shown in the spectral line (a) in Fig. 1.Can
To find out that nickel-base catalyst-1 has and CeO2Similar Emission in Cubic structure, (111), (200), (220)
(311) diffraction maximum of crystal face there occurs widthization and displacement.(111) crystallographic plane diffraction peak is moved to 2 θ=29.0
At °, (200) crystallographic plane diffraction peak is moved at 2 θ=33.6 °, and (220) crystallographic plane diffraction peak is moved to
At 2 θ=48.7 °, (311) crystallographic plane diffraction peak is moved at 2 θ=58.2 °；Simultaneously (222) and (400)
The diffraction maximum of crystal face disappears.Spectrogram (a) does not occur corresponding to ZrO2The diffraction maximum of crystalline phase, explanation
Zr4+Dissolve in CeO2Lattice defines cerium zirconium sosoloid structure.With simple Emission in Cubic CeO2Compare, nickel
The diffraction peak intensity of base catalyst-1 is relatively low, and the angle of diffraction is bigger than normal, and significantly broadened.This is due to following
Two aspect reasons cause: the cerium zirconium sosoloid crystal grain diameter that (1) uses the inventive method to prepare is less,
Therefore diffraction peaks broadening is caused；(2)Zr4+Ionic radius is less than Ce4+Ionic radius, forms solid solution
After, Zr4+Embed CeO2Lattice, causes distortion of lattice, causes lattice paprmeter to diminish, and the angle of diffraction becomes big.
It addition, there is no that in the XRD spectra of nickel-base catalyst-1 diffracted signal corresponding to nickel oxide occurs.
This explanation, the crystallite dimension that nickel species are formed on cerium zirconium sosoloid carrier surface is less than X-ray diffraction
Detectable limit.Thus may certify that, use the nickel-base catalyst-1 prepared of the inventive method and reduced state nickel
In base catalyst A, nickel is the surface being present in cerium zirconium sosoloid carrier with homodisperse state.
Embodiment 2
The present embodiment is for illustrating that what the present invention provided prepares nickel-base catalyst and reduction-state nickel-base catalyst
Method.
(1) by the CeCl of 0.3mol3ZrOCl with 0.15mol2·8H2O is configured to the mixed of 1000ml
Heshui solution, and be transferred in there-necked flask.
Being put into by there-necked flask in ultrasonic cleaner, regulation ultrasonic power is 150W, and ultrasonic temperature is 60
℃.Under conditions of opening ultrasonic and continuous stirring 500rpm, with the speed of 0.5ml/min to three mouthfuls
Drip the hydrogen peroxide 30ml of 5.0mol/L in Ping, in there-necked flask, drip the ammonia of 2mol/L to protect simultaneously
Hold the pH=9 of system.After whole dropping process, continue ultrasonic and stir 2 hours, then room temperature
Stand aging 10 hours, sucking filtration, obtain solid product.
Cleaning solid product 3 times with the distilled water of 2000ml, then solid product is placed in temperature is 130
DEG C drying baker in be dried 2 hours, then 600 DEG C of roastings 3 hours in Muffle furnace, obtain cerium zirconium solid solution
Body.
(2) by the Ni (NO of 9.85g3)2·6H2O is dissolved in 100ml distilled water, prepares with above-mentioned
The cerium zirconium sosoloid mixing of 10.0g, continuous stirring is reacted 5 hours at ambient temperature.Use rotary evaporation
Instrument boils off the water in system, obtains solid product.
Solid product is placed in the drying baker that temperature is 130 DEG C, is dried 2 hours.Then at Muffle furnace
In, temperature is 600 DEG C of roastings 3 hours, obtains nickel-base catalyst-2.
(3) by nickel-base catalyst-2 reductase 12 h at 425 DEG C in hydrogen atmosphere, reduction-state is obtained Ni-based
Catalyst B.
The composition of this catalyst B contains: the nickel of 16.7 weight %, the cerium zirconium sosoloid of 83.3 weight %；
Cerium is 2:1 with the mol ratio of zirconium.The specific surface area of catalyst B is 134m2/ g, pore volume is 0.65cm3/g。
The X-ray diffraction spectrogram of nickel-base catalyst-2 is similar to Fig. 1 (a), illustrates that nickel is uniformly to divide
The state dissipated is present in the surface of cerium zirconium sosoloid carrier.
Embodiment 3
The present embodiment is for illustrating that what the present invention provided prepares nickel-base catalyst and reduction-state nickel-base catalyst
Method.
(1) by the Ce of 0.1mol2(SO4)3·8H2Zr (the SO of O and 0.2mol4)2·4H2O is configured to
The mixed aqueous solution of 1000ml, and be transferred in there-necked flask.
Being put into by there-necked flask in ultrasonic cleaner, regulation ultrasonic power is 250W, and ultrasonic temperature is 20
℃.Under conditions of opening ultrasonic and continuous stirring 1500rpm, with the speed of 1.0ml/min to three mouthfuls
Drip the hydrogen peroxide 200ml of 1.0mol/L in Ping, drip in there-necked flask simultaneously the ammonia of 8mol/L with
The pH=11 of holding system.After whole dropping process, continue ultrasonic and stir 2 hours, then
Room temperature stands aging 10 hours, and sucking filtration obtains solid product.
Cleaning solid product 3 times with the distilled water of 2000ml, then solid product is placed in temperature is 110
DEG C drying baker in be dried 5 hours, then 500 DEG C of roastings 10 hours in Muffle furnace, obtain cerium zirconium solid solution
Body.
(2) by the Ni (NO of 3.28g3)2·6H2O is dissolved in 100ml distilled water, prepares with above-mentioned
The cerium zirconium sosoloid mixing of 10.0g, continuous stirring is reacted 5 hours at ambient temperature.Use rotary evaporation
Instrument boils off the water in system, obtains solid product.
Solid product is placed in the drying baker that temperature is 110 DEG C, is dried 5 hours.Then at Muffle furnace
In, temperature is 500 DEG C of roastings 10 hours, obtains nickel-base catalyst-3.
(3) by nickel-base catalyst-3 reductase 12 h at 425 DEG C in hydrogen atmosphere, reduction-state is obtained Ni-based
Catalyst C.
The composition of this catalyst C contains: the nickel of 6.2 weight %, the cerium zirconium sosoloid of 93.8 weight %；
Cerium is 1:1 with the mol ratio of zirconium.The specific surface area of catalyst C is 141m2/ g, pore volume is 0.67cm3/g。
The X-ray diffraction spectrogram of nickel-base catalyst-3 is similar to Fig. 1 (a), illustrates that nickel is uniformly to divide
The state dissipated is present in the surface of cerium zirconium sosoloid carrier.
Comparative example 1
According to the method for embodiment 1, except for the difference that, step (1) do not has ultrasound condition.
Obtain nickel-base catalyst-4.
Nickel-base catalyst-4 is reduced, obtains reduction-state nickel-base catalyst D1.
Catalyst D1 specific surface area is 97m2/ g, pore volume is 0.53cm3/g。
Obviously, compared with catalyst A, specific surface area and the pore volume of catalyst D1 are the least.Ni-based
Shown in X-ray diffraction spectrogram such as Fig. 1 (b) of catalyst-4, although (111) crystallographic plane diffraction peak displacement
To 2 θ=29.0 °, (200) crystallographic plane diffraction peak is moved at 2 θ=33.5 °, (220) crystallographic plane diffraction peak
Being moved at 2 θ=48.3 °, (311) crystallographic plane diffraction peak is moved at 2 θ=57.0 °, and (222) crystal face spreads out
Penetrating peak position and move at 2 θ=59.1 °, (400) crystallographic plane diffraction peak is moved at 2 θ=69.8 °, but also exists
The diffracted signal corresponding to NiO is occurred in that at 2 θ=37.1 °, at 2 θ=43.1 ° and at 2 θ=62.8 °.
This explanation, the crystallite dimension that on nickel-base catalyst-4, nickel oxide species are formed is apparently higher than X-ray diffraction
Detection limit.It can be seen that preparation nickel-base catalyst-4 and reduction-state nickel-base catalyst D1 in, nickel
It not the surface being present in cerium zirconium sosoloid carrier with homodisperse state, there are nickel species and reunite existing
As, cause crystallite dimension excessive, XRD spectra produces diffracted signal.
Thus, it is indicated, that the preparation method using the present invention to provide, specific surface area and hole body can be obtained
Long-pending bigger, the more uniform reduction-state nickel-base catalyst of Ni species dispersion.Relatively, at ultrasound condition
The reduction-state nickel-base catalyst of lower preparation, on carrier, the dispersion of nickel is low.
Comparative example 2
According to the method for embodiment 1, except for the difference that, step does not has ultrasound condition in (1), is not added with yet
Enter hydrogen peroxide.
Obtain nickel-base catalyst-5.
Nickel-base catalyst-5 is reduced, obtains reduction-state nickel-base catalyst D2.
Catalyst D2 specific surface area is 31m2/ g, pore volume is 0.40cm3/g。
Specific surface area and the pore volume of catalyst D2 are less.The X-ray diffraction spectrogram of nickel-base catalyst-5
As shown in Fig. 1 (c).Although (111) crystallographic plane diffraction peak is moved at 2 θ=29.0 °, (200) crystal face
Diffraction peak moves at 2 θ=33.6 °, and (220) crystallographic plane diffraction peak is moved at 2 θ=48.1 °, (311)
Crystallographic plane diffraction peak is moved at 2 θ=57.1 °, and (222) crystallographic plane diffraction peak is moved at 2 θ=59.1 °,
(400) crystallographic plane diffraction peak is moved at 2 θ=70.0 °.But at 2 θ=37.2 °, at 2 θ=43.2 °
Higher with the diffracted signal of the corresponding NiO occurred at 2 θ=62.9 °.Illustrate, with nickel-base catalyst-4 and
Reduction-state nickel-base catalyst D1 compares, nickel thing on nickel-base catalyst-5 and reduction-state nickel-base catalyst D2
The dispersion planted is lower.
Thus, it is indicated, that it is permissible to use the method for present invention offer to prepare reduction-state nickel-base catalyst simultaneously
Having bigger specific surface area and pore volume, less crystallite dimension, the nickel species dispersion of load is higher.
Test case 1-8
The method of the methane self-heating recapitalization preparing synthetic gas that the present embodiment provides for the present invention is described.
Being loaded by the catalyst A of 0.5g in fixed-bed quartz reactor, the temperature controlling reaction is 700
DEG C, the pressure of reaction is 0.1MPa, and other conditions are reacted as listed in table 1.Product is through cold
Solidifying except being analyzed with Agilent 6890N gas chromatograph after water.Reaction result is shown in Table 1.
Table 1
As it can be seen from table 1 use catalyst A prepared by the inventive method for methane self-heating recapitalization system
During standby synthesis gas reaction, all can show good catalytic performance under the conditions of differential responses, methane turns
Rate is higher than 86%, and CO selectivity is higher than 87%, H2Selectivity maintains 100% always.It addition, with
The change of reaction temperature, proportioning raw materials and feed space velocity, it is provided that product in H2The ratio of/CO is permissible
Change between 2.6-5.0.It is anti-that such products distribution goes for the most different synthesis gas downstreams
Should, catalyst provided by the present invention can be that Downstream processing provides the wider array of raw material of the scope of application.
Test case 9
Being loaded by the catalyst A of 0.5g in fixed-bed quartz reactor, the temperature controlling reaction is 850
DEG C, the pressure of reaction is 0.1MPa, CH4:O2:H2The mol ratio of O is 1:0.2:1.0, the air speed of methane
For 18000ml/gcat h.Reaction result is shown in Table 2.
Test case 10-13
According to the method for test case 9, except for the difference that, respectively with catalyst B, C, catalyst D1 and
Catalyst D2 alternative catalysts A, carries out the reaction of methane self-heating recapitalization preparing synthetic gas.Reaction result is shown in Table
2。
Table 2
| Numbering | Catalyst | Methane conversion (%) | CO selectivity (%) | H2Selectivity (%) | H2/CO |
| Test case 9 | A | 95.3 | 96.7 | 100.0 | 2.83 |
| Test case 10 | B | 95.0 | 97.0 | 100.0 | 2.81 |
| Test case 11 | C | 95.5 | 96.3 | 100.0 | 2.84 |
| Test case 12 | D1 | 86.6 | 88.0 | 98.3 | 3.10 |
| Test case 13 | D2 | 63.2 | 70.1 | 93.2 | 3.62 |
From table 2 it can be seen that use catalyst A prepared by the inventive method for methane self-heating recapitalization system
During standby synthesis gas reaction, its catalytic performance is substantially better than the catalyst D1 being provided without ultrasonic technique synthesis,
Methane conversion, carbon monoxide selective and hydrogen selectivity are all significantly improved.
By comparing the experimental result of test case 9 and test case 13 it is found that use ultrasonic skill simultaneously
Art and oxidation and coprecipitation method prepare cerium zirconium sosoloid, for the nickel-base catalyst obtained further and reduction-state
Nickel-base catalyst can provide more preferable catalyst pore structure (bigger serface and pore volume), also promotes
Nickel species spread more evenly across with less crystal grain on cerium zirconium sosoloid, and catalyst A is than using routine
Catalyst D2 prepared by method shows more preferable catalytic performance, and methane conversion improves 32.1%, one
Carbonoxide selectivity improves 26.6%, and hydrogen selectivity improves 6.8%.
Claims (12)
1. the method preparing nickel-base catalyst, the method includes:
(1) under ultrasonic and stirring condition, by precipitant, hydrogen peroxide, cerium salt and zirconates in aqueous phase
Contact, and carries out aging, carries out the product after aging separating, first is dried and the first roasting, obtains
Cerium zirconium sosoloid；
(2) cerium zirconium sosoloid obtained in step (1) introduces the presoma of nickel, and it is dry to carry out second
Dry and the second roasting, obtains nickel-base catalyst.
Method the most according to claim 1, wherein, by precipitant, hydrogen peroxide in step (1)
Contact with the aqueous solution containing cerium salt and zirconates, and carry out after regulating the pH ＞ 7 of product obtained aging；
Preferably, pH=9-11.
Method the most according to claim 2, wherein, described cerium salt is Inorganic Cerium salt, preferably institute
Stating cerium salt is at least one in cerous nitrate, cerous chloride and cerous sulfate；Ce in described aqueous solution3+Dense
Degree is 0.1-0.3mol/L.
Method the most according to claim 2, wherein, described zirconates is inorganic zirconium salts, preferably institute
Stating zirconates is at least one in zirconium nitrate, zirconyl nitrate, zirconium oxychloride and Disulfatozirconic acid.；Described aqueous solution
Middle zirconium ion is 0.5-2:1 with the mol ratio of cerium ion.
Method the most according to claim 2, wherein, the concentration of described hydrogen peroxide is 1-5mol/L；
Preferably, Ce in described aqueous solution3+It is 1:0.5-1 with the mol ratio of hydrogen peroxide.
Method the most according to claim 1, wherein, the presoma of described nickel is nickel nitrate, vinegar
At least one in acid nickel, nickelous carbonate and nickel sulfate；Preferably, the nickel in the presoma of described nickel and cerium
The mass ratio of zirconium solid solution is 1:4-20, preferably 1:5-15；It is highly preferred that introduce the presoma of nickel
Method for dipping or precipitation.
7. according to the method described in any one in claim 1-6, wherein, described ultrasound condition bag
Including: ultrasonic temperature is 20-60 DEG C, ultrasonic power is 150-250W.
8. the nickel-base catalyst that in claim 1-7, method described in any one prepares.
9. the reduction-state nickel-base catalyst obtained through reduction by the nickel-base catalyst described in claim 8,
Wherein, described reduction includes reducing nickel-base catalyst under hydrogen atmosphere, and the temperature of described reduction is
300-600 DEG C, the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60
Volume %.
Reduction-state nickel-base catalyst the most according to claim 9, wherein, total with this catalyst
On the basis of weight, containing the nickel of 6.2-16.7 weight %, the cerium zirconium sosoloid of 83.3-93.8 weight %；Excellent
Selection of land, in this catalyst, elemental cerium is 0.5-2:1 with the mol ratio of zirconium；It is highly preferred that this catalyst
Specific surface area is 260-310m2/ g, pore volume is 1.2-1.4cm3/g。
The method of 11. 1 kinds of methane self-heating recapitalization preparing synthetic gas, the method includes: by methane, oxygen and
Water haptoreaction in the presence of a catalyst, it is characterised in that described catalyst is claim 9 or 10
Described reduction-state nickel-base catalyst.
12. methods according to claim 11, wherein, described methane, oxygen and water mole
Ratio is 1:0.1-0.5:0.5-2, and the condition of described contact includes: temperature is 750-850 DEG C, and pressure is
0.1MPa, the air speed of methane is 4000-40000ml/gcat h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510346603.1A CN106311250A (en) | 2015-06-19 | 2015-06-19 | Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510346603.1A CN106311250A (en) | 2015-06-19 | 2015-06-19 | Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106311250A true CN106311250A (en) | 2017-01-11 |
Family
ID=57728915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510346603.1A Pending CN106311250A (en) | 2015-06-19 | 2015-06-19 | Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106311250A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723101A (en) * | 1996-10-15 | 1998-03-03 | Rhone-Poulenc Inc. | Method for producing cerium and zirconium oxides, mixed oxides and solid solutions having improved thermal stability |
| CN1449863A (en) * | 2003-04-28 | 2003-10-22 | 华东理工大学 | Nano Cerium-zirconium base compound oxide and preparation process thereof |
| 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 |
| CN102247826A (en) * | 2011-05-27 | 2011-11-23 | 济南大学 | Cubic phase cerium and zirconium based composite oxide with high specific surface area and preparation method thereof |
| CN102258995A (en) * | 2011-05-12 | 2011-11-30 | 湖北航特科技有限责任公司 | Ternary-cerium-based oxygen storage material and preparation method thereof |
| CN102335609A (en) * | 2011-07-15 | 2012-02-01 | 华东师范大学 | Nickel-based catalyst as well as preparation method and application thereof |
| CN102527394A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Nickel-based catalyst and preparation method thereof |
| CN103769075A (en) * | 2014-01-26 | 2014-05-07 | 内蒙古科技大学 | Novel three-way catalytic nano heavy-rare-earth oxygen-storage material and preparation method thereof |
-
2015
- 2015-06-19 CN CN201510346603.1A patent/CN106311250A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723101A (en) * | 1996-10-15 | 1998-03-03 | Rhone-Poulenc Inc. | Method for producing cerium and zirconium oxides, mixed oxides and solid solutions having improved thermal stability |
| CN1449863A (en) * | 2003-04-28 | 2003-10-22 | 华东理工大学 | Nano Cerium-zirconium base compound oxide and preparation process thereof |
| 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 |
| CN102258995A (en) * | 2011-05-12 | 2011-11-30 | 湖北航特科技有限责任公司 | Ternary-cerium-based oxygen storage material and preparation method thereof |
| CN102247826A (en) * | 2011-05-27 | 2011-11-23 | 济南大学 | Cubic phase cerium and zirconium based composite oxide with high specific surface area and preparation method thereof |
| CN102335609A (en) * | 2011-07-15 | 2012-02-01 | 华东师范大学 | Nickel-based catalyst as well as preparation method and application thereof |
| CN102527394A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Nickel-based catalyst and preparation method thereof |
| CN103769075A (en) * | 2014-01-26 | 2014-05-07 | 内蒙古科技大学 | Novel three-way catalytic nano heavy-rare-earth oxygen-storage material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《APPLIED CATALYSIS A: GENERAL》 * |
| 《材料导报》 * |
| 《燃料化学学报》 * |
| 汪多仁: "《绿色纳米化学品》", 31 July 2007, 科学技术文献出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Methanation of carbon dioxide over Ni/CeO2 catalysts: Effects of support CeO2 structure | |
| Ding et al. | Superior catalytic activity of a Pd catalyst in methane combustion by fine-tuning the phase of ceria-zirconia support | |
| Chen et al. | Effect of Mg-modified mesoporous Ni/Attapulgite catalysts on catalytic performance and resistance to carbon deposition for ethanol steam reforming | |
| CN113209976B (en) | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction | |
| Arslan et al. | Effect of calcination/reduction temperature of Ni impregnated CeO2–ZrO2 catalysts on hydrogen yield and coke minimization in low temperature reforming of ethanol | |
| Wang et al. | Effect of synthesis method on the properties of ceria–zirconia modified alumina and the catalytic performance of its supported Pd-only three-way catalyst | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| CN109433192A (en) | A kind of noble metal single atomic dispersion type cleaning catalyst and preparation method thereof | |
| CN108525676A (en) | A kind of Ru-Ni/Ce-Zr composite oxide catalysts and preparation method thereof | |
| CN107570162B (en) | Nickel-based catalyst for reverse water gas shift reaction and preparation method thereof | |
| CN109420484A (en) | A kind of metal oxide solid solution catalyst and preparation and application | |
| CN109731579A (en) | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof | |
| CN113649022B (en) | Catalyst for catalytic combustion of organic volatile waste gas and preparation method thereof | |
| Liu et al. | Engineering Morphology and Ni Substitution of Ni x Co3–x O4 Spinel Oxides to Promote Catalytic Combustion of Ethane: Elucidating the Influence of Oxygen Defects | |
| CN102407164A (en) | Cerium zirconium aluminum nanometer composite with mesoporous structure and preparation method and use thereof | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| Gosavi et al. | Catalytic preferential oxidation of carbon monoxide over platinum supported on lanthanum ferrite–ceria catalysts for cleaning of hydrogen | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| Sun et al. | Yolk-shell structured Pt-CeO2@ Ni-SiO2 as an efficient catalyst for enhanced hydrogen production from ethanol steam reforming | |
| CN104437501B (en) | A kind of cobalt-base catalyst and the preparation method and application thereof | |
| Huo et al. | Promoting the generation of active oxygen species on 3DOM K/LaMnO3 interface by introducing CeO2 to boost the NOx-assisted soot combustion | |
| Zhao et al. | Catalytic decomposition of methanol to carbon monoxide and hydrogen over palladium supported on Ce0. 65Zr0. 30La0. 05O2 and La–Al2O3 | |
| CN108499568B (en) | Nickel-based catalyst for reforming methane by pressurizing carbon dioxide | |
| CN109847756A (en) | A kind of nickel base nanometer catalyst of hollow structure and the preparation method and application thereof | |
| CN102319560A (en) | Preparation method of manganese titanium catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170111 |
|
| RJ01 | Rejection of invention patent application after publication |