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CN106799263B - Multistage pore catalyst of a kind of high intensity for methane tri-reforming and preparation method thereof - Google Patents

Multistage pore catalyst of a kind of high intensity for methane tri-reforming and preparation method thereof Download PDF

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CN106799263B
CN106799263B CN201710124445.4A CN201710124445A CN106799263B CN 106799263 B CN106799263 B CN 106799263B CN 201710124445 A CN201710124445 A CN 201710124445A CN 106799263 B CN106799263 B CN 106799263B
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catalyst
reforming
temperature
pore
preparation
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CN106799263A (en
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孙予罕
袁昌坤
张军
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Shanghai Advanced Research Institute of CAS
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Shanghai Advanced Research Institute of CAS
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    • 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
    • B01J35/613—10-100 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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

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  • General Health & Medical Sciences (AREA)
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Abstract

The present invention provides a kind of high intensity multistage pore catalyst and preparation method thereof for methane tri-reforming, 1) support precursor, composite pore-forming agent, binder, lubricant the following steps are included: be sufficiently mixed by the preparation method after, is pressed and molded with press；2) after aging, drying, low-temperature bake and high-temperature roasting, shaping carrier is prepared；3) shaping carrier is passed through into one or many circular treatments, obtains finished catalyst；Wherein, the circular treatment successively includes that the shaping carrier is placed in the salting liquid of metal to impregnate, dry, roasting.The present invention forms the high-temperature stable shaping carrier with high-intensitive hierarchical porous structure through treatment of different temperature by composite pore-forming agent, and carrier has 10-100m after high-temperature roasting2The reasonable gradient hierarchical porous structure of the specific surface area and ratio of/g is conducive to the dispersion of active component, carrier hole stable structure and high mechanical strength, and Compressive Strength is in 1000N or more on rear side of high-temperature roasting.

Description

A kind of multistage pore catalyst of high intensity for methane tri-reforming and its preparation Method
Technical field
The present invention relates to the preparation method fields of catalyst, more particularly to a kind of for the high-strength of methane tri-reforming Spend multistage pore catalyst and preparation method thereof.
Background technique
The purpose based on environmental protection and industrial development, reforming of methane on Ni-Ce or hydrogen cause industry in recent years The extensive concern on boundary.Methane-steam reforming, methane-CO 2 reformation, methane-carbon dioxide-vapor mixing reforming, Methane-carbon dioxide-vapor-oxygen tri-reforming etc. is the main path of current methane reforming process.Wherein, methane-water steams Gas reforms industrial applications, but steam/hydrocarbons ratio height causes energy consumption high and H in reaction process2/ CO is than high；Methane-carbon dioxide weight Although whole can obtain low H2The synthesis gas but catalyst carbon deposit deactivation prob of/CO ratio are extremely serious；And methane-carbon dioxide-water Steam-oxygen tri-reforming can obtain H2Synthesis gas of/CO the ratio between 1.5-2.0, the synthesis gas be fully compatible for manufacture methanol, The downstream product such as dimethyl ether, and H in synthesis gas can be made by adjusting vapor/carbon dioxide ratio in unstripped gas2/CO Ratio is adjustable, and therefore, the technological operation is flexibly and vapor consumption is far below methane-steam reforming technique, while water steams The elimination of gas and oxygen being passed through and can react and be conducive to carbon deposit on catalyst with the carbon deposit of catalyst surface, thus Extend catalyst service life.Therefore, methane-carbon dioxide-vapor-oxygen tri-reforming can be practical in conjunction with energy industry, Effective use oven gas, periodic off-gases, flue gas etc. be difficult in the past efficiently using tail gas, exhaust gas as raw material, make full use of work Factory's waste heat realizes that exhaust gas-heat sourcesization utilize, reduces operation cost of enterprises as reforming process heat source.
Existing patent literature report is mostly individually used for methane-CO 2 reformation, methane-steam reforming etc., It is less about methane-carbon dioxide-vapor mixing reforming report.Patent CN101112692A, CN1011122693A report Mainly using Ni as active component, MgxTi1-xO is the Ni/Mg of carrierxTi1-xO methane-vapor-carbon dioxide-oxygen tri-reforming Catalyst, wherein x is adjustable between 0.05-0.95.But this two patents are primarily upon the preparation of catalyst raw powder and are preparing Add a variety of surfactants in the process and increase preparation cost, to the preparation process of industrial preformed catalyst without reference to.Specially Sharp CN103949265A discloses a kind of methane-vapor-carbon dioxide-oxygen tri-reforming catalyst, contains in the catalyst The CeO of Ni, 1-3wt% of 11-13wt%2, 1-3wt% La2O3And the carrier that average grain diameter is 425-700 microns.This is specially Benefit is equally the preparation for paying close attention to catalyst powder, is not directed to the preparation flow of industrial preformed catalyst.
Industrial actual methane reforming catalyst need 800-1300 DEG C of high temperature, high gas velocity harsh operating condition under carry out, There is this catalyst raw powder for just not requiring nothing more than preparation good catalytic performance also to guarantee its carrier structure stabilization, specific surface area Industrial requirement is all needed to meet with pore structure, moulding process and mechanical strength.Based on this, need to develop a kind of mechanical strength Height, high temperature high voltage resistant thermal and hydric environment have a higher specific surface area, and the gradient hierarchical porous structure with suitable proportion is urged Agent is to meet industrial requirements.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind to be used for methane tri-reforming The multistage pore catalyst of high intensity and preparation method thereof, which has 10-100m2The specific surface area of/g and rational proportion Gradient hierarchical porous structure is conducive to the dispersion of active component, pore structure stabilization and high mechanical strength.
In order to achieve the above objects and other related objects, the present invention provides a kind of high intensity for methane tri-reforming The preparation method of multistage pore catalyst, comprising the following steps:
1) after support precursor, composite pore-forming agent, binder, lubricant being sufficiently mixed, pressing mold molding；
2) after aging, drying, low-temperature bake and high-temperature roasting, shaping carrier is prepared.
3) shaping carrier is passed through into 1 time or multiple circular treatment, obtains finished catalyst；Wherein, at the circulation Reason successively includes that the shaping carrier is placed in the salting liquid of metal to impregnate, dry, roasting.
Preferably, before step 1), the support precursor need to be pre-processed, the pretreatment selection is following to appoint A kind of mode of anticipating carries out:
A, it is dried；
B, pre-preg is carried out to the support precursor powder using the salting liquid of metal, then dried；
C, pre-preg is carried out to the support precursor powder using the salting liquid of metal, then dry, roasting.
It is highly preferred that metal includes one or two kinds of combinations of nickel and lanthanum in the salting liquid of the metal in b) mode, Salting liquid includes one of nitrate solution and chlorination salting liquid in the salting liquid of the metal.
It is highly preferred that the concentration of metal ion is 1-3g/mL in the salting liquid of the metal in b) mode.
It is highly preferred that metal includes one or two kinds of combinations of nickel and lanthanum, institute in the salting liquid of the metal in c) mode Stating salting liquid in the salting liquid of metal includes one of nitrate solution and chlorination salting liquid.
It is highly preferred that the concentration of metal ion is 1-3g/mL in the salting liquid of the metal in c) mode.
Preferably, in step 1), the support precursor, the composite pore-forming agent, the binder and lubricant Weight ratio is (90-130): (1-50): (0.1-50): (0.1-10).
It is highly preferred that in step 1), the support precursor, the composite pore-forming agent, the binder and lubricant Weight ratio be (100-120): (15-30): (5-20): (0.5-5).
Preferably, in step 1), the support precursor include magnesia, magnesium aluminate spinel, zirconium oxide, cerium oxide, Zinc oxide, titanium oxide, gama-alumina, Alpha-alumina, rich calcium aluminium oxide, aluminium hydroxide, aluminium salt, hexa-aluminate, boehmite and At least one of boehmite or multiple combinations.
Preferably, in step 1), the composite pore-forming agent includes inorganic pore creating material and organic pore-forming agents, described inorganic to make The mass ratio of hole agent and the organic pore-forming agents is 0.1-10；The inorganic compounding pore creating material include 80-120 mesh graphite powder, 750-850 mesh graphite powder, 1200-3000 mesh graphite powder, 4000-8000 mesh graphite powder, ammonium carbonate, calcium hydroxide, ammonium hydrogen carbonate With any one or more combination in calcium carbonate；The organic pore-forming agents include starch, beta-cyclodextrin, carboxymethyl cellulose, Polyvinylpyrrolidone, polyethylene glycol, polymethyl methacrylate, polystyrene, polyvinyl butyral, polyvinyl alcohol, acetic acid Any one or more combination in ammonium, lactic acid, propionic acid and positive valeric acid.
Preferably, in step 1), the binder includes water soluble starch, aluminous cement, clay, polymethyl Any one or more combination in sour methyl esters, carboxymethyl cellulose, polyvinyl alcohol, paraffin, boehmite powder and Aluminum sol.
Preferably, in step 1), the lubricant includes any in magnesium stearate, talcum powder, graphite and positive valeric acid One or more combinations.
Preferably, in step 2), the aging includes following procedure: the shaping carrier is placed at 10-40 DEG C 20-100h。
Preferably, in step 2), the drying includes following procedure: the stream by the shaping carrier at 110-130 DEG C Dry 10-24h under dynamic air or nitrogen atmosphere.
Preferably, in step 2), the temperature of the low-temperature bake is 400 DEG C -900 DEG C, the time of the low-temperature bake For 3-8h.
It is highly preferred that in step 2), the temperature of the low-temperature bake is 840 DEG C -860 DEG C, the low-temperature bake when Between be 4-6h.
Preferably, in step 2), the temperature of the high-temperature roasting is 1000 DEG C -1500 DEG C, the high-temperature roasting when Between be 3-8h.
It is highly preferred that the temperature of the high-temperature roasting is 1100 DEG C -1400 DEG C, the high-temperature roasting in step 2) Time is 4-6h.
Preferably, in step 3), the number of the circular treatment is 1-4 times；
Preferably, in step 3), metal includes one or two kinds of combinations of nickel and lanthanum, institute in the salting liquid of the metal Stating salting liquid in the salting liquid of metal includes any one in nitrate solution and chlorination salting liquid.
Preferably, in step 3), the concentration of metal ion is 1-3g/mL in the salting liquid of the metal.
Preferably, in step 3), it is 1-3h that the shaping carrier is placed in the time impregnated in the salting liquid of metal.
Preferably, in step 3), the drying includes following procedure: the shaping carrier is flowed at 100-140 DEG C Dry 3-20h in air or nitrogen atmosphere.
It is highly preferred that the drying includes following procedure in step 3): the shaping carrier is flowed at 110-130 DEG C Dry 3-5h in dynamic air or nitrogen atmosphere.
Preferably, in step 3), the temperature of the roasting is 400 DEG C -900 DEG C, and the time of the roasting is 3-8h.
It is highly preferred that the temperature of the roasting is 450 DEG C -650 DEG C in step 3), the time of the roasting is 4-6h.
Preferably, in step 3), after circular treatment, the finished catalyst with 10-20wt% NiO and The La of 0.1-10wt%2O3。
Invention additionally discloses a kind of by the multistage pore catalyst of the high intensity for methane tri-reforming as described above The catalyst for preparing of preparation method.
Invention additionally discloses a kind of purposes of catalyst as described above, for catalyst is used for methane tri-reforming In.
Preferably, before the catalyst is used for methane tri-reforming, also original place need to be carried out to the catalyst Manage step, the reduction treatment step are as follows: the catalyst is placed in reducing gas atmosphere and is restored, the reduction treatment Temperature is 600-800 DEG C, and the time of the reduction treatment is 2-12h, and the reducing gas is H2With inert gas mixed gas, H2Molar ratio with inert gas is (0.5-1.5): (0.5-1.5).
Preferably, the methane tri-reforming condition are as follows: reaction pressure 0.1-4MPa, reaction temperature 600-1300 DEG C, gas space velocity 1000-150000ml/gh.
As described above, the present invention provide it is a kind of for the multistage pore catalyst of high intensity of methane tri-reforming and its preparation Method has the advantages that
(1) catalyst that the present invention obtains is suitable for natural gas or oven gas, periodic off-gases, flue gas etc. rich in methane Tail gas, methane-carbon dioxide-vapor-oxygen tri-reforming technique that exhaust gas is raw material, manufacture craft flexible operation, synthesis gas H2/CO ratio is adjustable.
(2) present invention forms the height with high-intensitive gradient hierarchical porous structure through treatment of different temperature by composite pore-forming agent Warm stable molding carrier, wherein aperture is sprocket hole in the duct of 15-1000nm, and conducive to the interior diffusion of gas component, aperture exists The duct of 1-50nm is active hole, and carrier has the specific surface area of 10-100m2/g after high-temperature roasting, is conducive to active component Dispersion, carrier hole stable structure, high pressure resistant thermal and hydric environment and high mechanical strength, the side pressure strength through high-temperature roasting rear catalyst exist 1000N or more.
(3) present invention can be practical in conjunction with energy industry, and effective use oven gas, periodic off-gases, flue gas etc. are difficult in the past Efficiently using tail gas, exhaust gas as raw material, make full use of factory's waste heat as heat source, realize that exhaust gas-heat sourcesization utilize, Reduce operation cost of enterprises.
Detailed description of the invention
Fig. 1 is shown as in embodiment 1 Raschig ring shape shaping carrier figure before aging.
The same batch Raschig ring shape shaping carrier that Fig. 2 is shown as embodiment 1 is surveyed in the side pressure strength in different disposal stage Test result figure.
Fig. 3 is shown as methane-carbon dioxide-vapor mixing reforming reaction evaluating result figure of embodiment 1.
Fig. 4 is shown as the finished catalyst of the embodiment 2 nitrogen adsorption desorption isothermal curve figure in BET test.
Fig. 5 is shown as the finished catalyst of the embodiment 2 gradient multi-stage porous distribution results figure in BET test.
Fig. 6 is shown as methane-carbon dioxide-vapor mixing reforming reactivity curve graph of embodiment 2.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from Various modifications or alterations are carried out under spirit of the invention.
It should be noted that the basic conception that only the invention is illustrated in a schematic way is illustrated provided in the present embodiment, Then only shown in schema with it is of the invention in related component rather than component count, shape and size when according to actual implementation draw System, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its assembly layout kenel can also It can be increasingly complex.
Embodiment 1
Raw material: support precursor: magnesia 80g, gama-alumina 20g amount to 100g.Inorganic pore creating material: 750-850 mesh Graphite powder 8g, ammonium carbonate 8g；Organic pore-forming agents: beta-cyclodextrin 4g, polystyrene 4g.Binder: aluminous cement 10g, poly- first Base methyl acrylate 2g.Lubricant: magnesium stearate 1g, positive valeric acid 2g.
The nitrate solution -1 of metal: Nickelous nitrate hexahydrate 24g, lanthanum nitrate hexahydrate 3g, deionized water 15ml.
The nitrate solution -2 of metal: Nickelous nitrate hexahydrate 70g, lanthanum nitrate hexahydrate 5g, deionized water 50ml.
Preparation method:
1. Vehicle element: being sufficiently mixed 80g magnesia and 20g gama-alumina with high-speed mixer, gold is added in spray The nitrate solution -1 of category is simultaneously sufficiently spare through 120 DEG C of dry 12h after kneading.
2. with high-speed mixer that pretreated carrier, inorganic pore creating material, organic pore-forming agents, binder, lubricant is abundant It is pressed and molded (Raschig ring shape) with tablet machine after mixing, obtains Raschig ring shape shaping carrier.Room temperature is old under moving air atmosphere Change 50h, the dry 12h of lower 120 DEG C of subsequent moving air atmosphere, carrier transfer is then referred to that 5 DEG C/min of high temperature furnace is warming up to 850 DEG C Cooling is spare after being continuously heating to 1200 DEG C and the above constant temperature 5h after constant temperature 5h.
Fig. 1 is shown as Raschig ring shape shaping carrier figure before aging, and Fig. 1 can illustrate, catalyst is in certain solid shape, and And there is good mechanical strength.Fig. 2 is shown as same batch Raschig ring shape shaping carrier in aged at room temperature 50h, 120 DEG C of dryings The side pressure strength test result figure of 12h and 1200 DEG C of roasting 5h.As can be seen from Figure 2, the catalysis after 1200 DEG C roast 5h The side pressure strength of agent in 1000N or more, side pressure strength be significantly larger than before side pressure strength, mechanical performance reaches to be mentioned well It is high.
It dries and 3. the shaping carrier after high-temperature roasting is put into after metal component nitrate solution -2 impregnates 3h in flowing sky Lower 120 DEG C of gas atmosphere dry 3h are subsequently transferred to 5 DEG C/min of high temperature furnace and are warming up to 500 DEG C of roasting 5h, repeat above-mentioned behaviour after cooling Make to obtain finished catalyst 3 times.
Above-mentioned complete Raschig ring shape catalyst granules is carried out single catalyst in the single hose system of 100g loadings to comment Valence uses H at 700 DEG C of furnace temperature2/N2Mixed gas (H2With N2Molar ratio be 1:1) can be used to methane three within in-situ reducing 3 hours Reforming reaction, in 800 DEG C of furnace temperature, air speed 40000cm3/ gh, reaction pressure 5bar, unstrpped gas CH4/CO2/H2O/O2Molar ratio 1/1.4/1/0.05 the performance of catalyst is tested under conditions of, result is as shown in Figure 3.From figure 3, it can be seen that at runtime Between in 50h, the conversion ratio and H of raw material2The volume ratio of/CO is sufficiently stable, illustrates that the pore structure of catalyst is stable and urges The high mechanical strength of agent.
Embodiment 2
Raw material: support precursor: zirconium oxide 60g, magnesium aluminate spinel 40g amount to 120g.Inorganic pore creating material: 80-120 mesh Graphite powder 12g, calcium carbonate 3g.Organic pore-forming agents: starch 4g, carboxymethyl cellulose 6g.Binder: Aluminum sol 15g.Lubricant: Magnesium stearate 1g.
The nitrate solution of metal: Nickelous nitrate hexahydrate 100g, lanthanum nitrate hexahydrate 10g, deionized water 50ml.
Preparation method:
1. Vehicle element: through 120 DEG C of dry 12h after being sufficiently mixed zirconium oxide and magnesium aluminate spinel with high-speed mixer It is spare afterwards.
2. with high-speed mixer that pretreated carrier, inorganic pore creating material, organic pore-forming agents, binder, lubricant is abundant It is pressed and molded (Raschig ring shape) with tablet machine after mixing, obtains shaping carrier and the aged at room temperature 100h under moving air atmosphere, Carrier transfer for 24 hours, is then referred to that 5 DEG C/min of high temperature furnace is warming up to 700 DEG C of constant temperature 3h by the lower 120 DEG C of dryings of subsequent moving air atmosphere After be continuously heating to 1200 DEG C and the above constant temperature 5h after cooling it is spare.
3. the shaping carrier after high-temperature roasting dries after being put into metal component nitrate solution dipping 3h, and in moving air Lower 120 DEG C of atmosphere dry 6h are subsequently transferred to 5 DEG C/min of high temperature furnace and are warming up to 500 DEG C of roasting 5h, repeat aforesaid operations after cooling Obtain finished catalyst 2 times.
Finished catalyst BET result is as shown in Figure 4, Figure 5.From fig. 4, it can be seen that as relative pressure increases, catalyst Nitrogen adsorption capacity also increasing, through derive BET=28m2/g.As can be seen from Figure 5, catalyst has the pore size distribution of gradient multistage.
Above-mentioned complete Raschig ring shape catalyst granules is carried out single catalyst in the single hose system of 100g loadings to comment Valence uses H at 700 DEG C of furnace temperature2/N2Mixed gas (H2With N2Molar ratio be 1:1) can be used to methane within in-situ reducing 3 hours Tri-reforming, in 750 DEG C of furnace temperature, air speed 40000cm3/ gh, reaction pressure 5bar, unstrpped gas CH4/CO2/H2O/O2Mole Than the performance for testing catalyst under conditions of 1/1.4/1/0.05, result is as shown in Figure 6.From fig. 6, it can be seen that at runtime Between in 180h, the conversion ratio and product H of raw material2The volume ratio of/CO is sufficiently stable, illustrates that embodiment 2 obtains catalyst The high mechanical strength of pore structure stabilization and catalyst.
Embodiment 3
Raw material: support precursor: magnesia 75g, Alpha-alumina 25g amount to 100g.Inorganic pore creating material: 80-120 mesh stone Ink powder 8g, ammonium hydrogen carbonate 8g；Organic pore-forming agents: starch 4g, polyvinyl alcohol 4g.Binder: clay 10g, paraffin 2g.Lubricant: Magnesium stearate 1g, talcum powder 2g.
The nitrate solution -1 of metal: Nickelous nitrate hexahydrate 24g, lanthanum nitrate hexahydrate 3g, deionized water 15ml.
Metal component nitrate solution -2: Nickelous nitrate hexahydrate 70g, lanthanum nitrate hexahydrate 5g, deionized water 50ml.
Preparation method:
1. Vehicle element: being sufficiently mixed support precursor with high-speed mixer, the nitrate that metal is added in spray is molten Liquid -1 is simultaneously sufficiently spare through 120 DEG C of dry 12h after kneading.
2. with high-speed mixer that pretreated carrier, inorganic pore creating material, organic pore-forming agents, binder, lubricant is abundant It is pressed and molded (Raschig ring shape) with tablet machine after mixing, obtains shaping carrier and the aged at room temperature 50h under moving air atmosphere, with Lower 110 DEG C of moving air atmosphere dry 13h afterwards, after carrier transfer is then referred to that 5 DEG C/min of high temperature furnace is warming up to 850 DEG C of constant temperature 5h Cooling is spare after being continuously heating to 1200 DEG C and the above constant temperature 4.5h.
It dries and 3. the shaping carrier after high-temperature roasting is put into after metal component nitrate solution -2 impregnates 3h in flowing sky Lower 120 DEG C of gas atmosphere dry 3h are subsequently transferred to 5 DEG C/min of high temperature furnace and are warming up to 500 DEG C of roasting 5h, repeat above-mentioned behaviour after cooling Make to obtain finished catalyst 3 times.
Embodiment 4
Raw material: support precursor: magnesia 80g, rich calcium aluminium oxide 20g amount to 100g.Inorganic pore creating material: 1200-3000 Mesh graphite powder 8g, calcium carbonate 8g；Organic pore-forming agents: carboxymethyl cellulose 4g, polystyrene 5g.Binder: aluminous cement 10g, polyvinyl alcohol 2g.Lubricant: magnesium stearate 1g, graphite 2g.
The nitrate solution -1 of metal: Nickelous nitrate hexahydrate 24g, lanthanum nitrate hexahydrate 3g, deionized water 15ml.
Metal component nitrate solution -2: Nickelous nitrate hexahydrate 70g, lanthanum nitrate hexahydrate 5g, deionized water 50ml.
Preparation method:
1. Vehicle element: being sufficiently mixed support precursor with high-speed mixer, the nitrate that metal is added in spray is molten Liquid -1 is simultaneously sufficiently spare through 120 DEG C of dry 12h after kneading.
2. with high-speed mixer that pretreated carrier, inorganic pore creating material, organic pore-forming agents, binder, lubricant is abundant It is pressed and molded (Raschig ring shape) with tablet machine after mixing, obtains shaping carrier and the aged at room temperature 50h under moving air atmosphere, with Lower 120 DEG C of moving air atmosphere dry 12h afterwards, after carrier transfer is then referred to that 5 DEG C/min of high temperature furnace is warming up to 850 DEG C of constant temperature 5h Cooling is spare after being continuously heating to 1200 DEG C and the above constant temperature 5h.
It dries and 3. the shaping carrier after high-temperature roasting is put into after metal component nitrate solution -2 impregnates 3h in flowing sky Lower 120 DEG C of gas atmosphere dry 3h are subsequently transferred to 5 DEG C/min of high temperature furnace and are warming up to 500 DEG C of roasting 5h, repeat above-mentioned behaviour after cooling Make to obtain finished catalyst 3 times.
Embodiment 5
Raw material: support precursor: magnesia 80g, boehmite 20g amount to 100g.Inorganic pore creating material: 4000-8000 mesh Graphite powder 8g, ammonium carbonate 8g；Organic pore-forming agents: ammonium acetate 4g, polystyrene 4g.Binder: aluminous cement 10g, clay 2g. Lubricant: magnesium stearate 1g, graphite 2g.
The nitrate solution -1 of metal: Nickelous nitrate hexahydrate 24g, lanthanum nitrate hexahydrate 3g, deionized water 15ml.
Metal component nitrate solution -2: Nickelous nitrate hexahydrate 70g, lanthanum nitrate hexahydrate 5g, deionized water 50ml.
Preparation method:
1. Vehicle element: being sufficiently mixed support precursor with high-speed mixer, the nitrate that metal is added in spray is molten Liquid -1 is simultaneously sufficiently spare through 120 DEG C of dry 12h after kneading.
2. with high-speed mixer that pretreated carrier, inorganic pore creating material, organic pore-forming agents, binder, lubricant is abundant It is pressed and molded (Raschig ring shape) with tablet machine after mixing, obtains shaping carrier and the aged at room temperature 50h under moving air atmosphere, with Lower 120 DEG C of moving air atmosphere dry 12h afterwards, after carrier transfer is then referred to that 5 DEG C/min of high temperature furnace is warming up to 850 DEG C of constant temperature 5h Cooling is spare after being continuously heating to 1200 DEG C and the above constant temperature 5h.
It dries and 3. the shaping carrier after high-temperature roasting is put into after metal component nitrate solution -2 impregnates 3h in flowing sky Lower 120 DEG C of gas atmosphere dry 3h are subsequently transferred to 5 DEG C/min of high temperature furnace and are warming up to 500 DEG C of roasting 5h, repeat above-mentioned behaviour after cooling Make to obtain finished catalyst 3 times.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (11)

1. a kind of preparation method of the multistage pore catalyst of high intensity for methane tri-reforming, which is characterized in that including with Lower step:
1) after support precursor, composite pore-forming agent, binder, lubricant being sufficiently mixed, pressing mold molding；
2) after aging, drying, low-temperature bake and high-temperature roasting, shaping carrier is prepared；
3) shaping carrier is passed through into 1 time or multiple circular treatment, obtains catalyst；Wherein, the circular treatment is successively wrapped It includes for the shaping carrier to be placed in the salting liquid of metal and impregnate, dry, roasting；The support precursor includes magnesia, magnesium Aluminate, zirconium oxide, cerium oxide, zinc oxide, titanium oxide, gama-alumina, Alpha-alumina, rich calcium aluminium oxide, aluminium hydroxide, Any one or more combination in aluminium salt, hexa-aluminate, boehmite and boehmite；
In step 1), the composite pore-forming agent includes inorganic pore creating material and organic pore-forming agents, the inorganic pore creating material with it is described The mass ratio of organic pore-forming agents is 0.1-10；
The inorganic compounding pore creating material include 80-120 mesh graphite powder, 750-850 mesh graphite powder, 1200-3000 mesh graphite powder, Any one or more combination in 4000-8000 mesh graphite powder, ammonium carbonate, calcium hydroxide, ammonium hydrogen carbonate and calcium carbonate；
The organic pore-forming agents include starch, beta-cyclodextrin, carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, poly- first It is any in base methyl acrylate, polystyrene, polyvinyl butyral, polyvinyl alcohol, ammonium acetate, lactic acid, propionic acid and positive valeric acid One or more combinations.
2. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, Be characterized in that, before step 1), the support precursor need to be pre-processed, pretreatment selection it is following any one Mode carries out:
A, it is dried；
B, pre-preg is carried out to the support precursor powder using the salting liquid of metal, then dried；
C, pre-preg is carried out to the support precursor powder using the salting liquid of metal, then dry, roasting.
3. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, It is characterized in that, in step 1), the weight ratio of the support precursor, the composite pore-forming agent, the binder and lubricant For (90-130): (1-50): (0.1-50): (0.1-10).
4. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, It is characterized in that, in step 1), the binder includes water soluble starch, aluminous cement, clay, poly-methyl methacrylate Any one or more combination in ester, carboxymethyl cellulose, polyvinyl alcohol, paraffin, boehmite powder and Aluminum sol.
5. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, Be characterized in that, in step 1), the lubricant include in magnesium stearate, talcum powder, graphite and positive valeric acid any one or Multiple combinations.
6. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, It is characterized in that, in step 2), the aging includes following procedure: the shaping carrier is placed into 20- at 10-40 DEG C 100h；
And/or in step 2), the drying includes following procedure: the moving air by the shaping carrier at 110-130 DEG C Or dry 10-24h under nitrogen atmosphere；
And/or in step 2), the temperature of the low-temperature bake is 400 DEG C -900 DEG C, and the time of the low-temperature bake is 3- 8h；
And/or in step 2), the temperature of the high-temperature roasting is 1000 DEG C -1500 DEG C, and the time of the high-temperature roasting is 3- 8h。
7. the preparation method of the multistage pore catalyst of the high intensity according to claim 1 for methane tri-reforming, It is characterized in that, in step 3), the number of the circular treatment is 1-4 times；
And/or in step 3), it is 1-24h that the shaping carrier is placed in the time impregnated in the salting liquid of metal；
And/or in step 3), the drying includes following procedure: by the shaping carrier in 100-140 DEG C of moving air or Dry 3-20h in nitrogen atmosphere；
And/or in step 3), the temperature of the roasting is 400 DEG C -900 DEG C, and the time of the roasting is 3-8h；
And/or in step 3), metal includes one or two kinds of combinations of nickel and lanthanum, the gold in the salting liquid of the metal Salting liquid includes one of nitrate solution and chlorination salting liquid in the salting liquid of category.
8. a kind of by the multistage pore catalyst of the high intensity for methane tri-reforming as described in any one of claim 1 to 7 The catalyst for preparing of preparation method.
9. a kind of purposes of catalyst as claimed in claim 8, for the catalyst to be used in methane tri-reforming.
10. the purposes of catalyst as claimed in claim 9, it is characterised in that: the catalyst is being used for methane tri-reforming Before reaction, reduction treatment, the reduction treatment are as follows: the catalyst is placed in reducing gas need to be carried out to the catalyst It is restored in atmosphere, the temperature of the reduction treatment is 600-800 DEG C, and the time of the reduction treatment is 2-12h, the also Primordial Qi Body is H2With the mixed gas of inert gas, H2Molar ratio with inert gas is (0.5-1.5): (0.5-1.5).
11. the purposes of catalyst as claimed in claim 9, it is characterised in that: the methane tri-reforming condition are as follows: reaction Pressure is 0.1-4MPa, and reaction temperature is 600-1300 DEG C, and gas space velocity is 1000-150000mL/gh.
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