CN107537482A - Porous complex catalyst and its application method - Google Patents
Porous complex catalyst and its application method Download PDFInfo
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- CN107537482A CN107537482A CN201610495838.1A CN201610495838A CN107537482A CN 107537482 A CN107537482 A CN 107537482A CN 201610495838 A CN201610495838 A CN 201610495838A CN 107537482 A CN107537482 A CN 107537482A
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Abstract
The present invention relates to a kind of porous complex catalyst and its application method, mainly solves the problems, such as that activity is low, selectivity of product is poor and stability is bad in existing porous complex catalyst.The present invention is by using porous complex catalyst, including following components：(A) inert component：At least one of silica, aluminum oxide, magnesia and zirconium oxide；(B) active component：At least one of platinum, rhodium, palladium, ruthenium, nickel, iron, cobalt and copper；(C) auxiliary agent：Molybdenum, zinc, at least one of the oxide of gallium and tin；The porous complex catalyst specific surface area is more than 1 meters squared per gram, pore space is more than 0.005 cubic centimetre/gram, and preparation method thereof technical scheme, preferably resolve not high catalyst activity, stability and anti-sintering property is poor and the problems such as easy carbon distribution, can be used in the catalysis industry production process of F- T synthesis, synthesis gas methanation and methane reforming.
Description
Technical field
The present invention relates to porous complex catalyst and its application method, can be especially useful for F- T synthesis, synthesis gas first
A kind of porous complex catalyst and preparation method of alkanisation and methane reforming.
Background technology
The trans-utilization of synthesis gas is significant under the energy background of the few gas of middle national wealth coal oil starvation.F- T synthesis,
And synthesis gas methanation be all synthesized using synthesis gas as raw material under the conditions of catalyst and appropriate reaction with liquid fuel or
The technical process of methane.On the other hand, developed with the exploitation of Chinese Unconventional gas particularly coal bed gas, shale gas etc.,
The chemical utilization of natural gas also has attracted increasing attention, and wherein methane reforming is a kind of important work that gas chemical industry utilizes
Skill, methane reforming refer to the technique that methane is made into synthesis gas using water vapour, carbon dioxide or oxygen etc..Above-mentioned two skills
Still there is many technical barriers in the application of art large-scale industrialization, wherein the most key is how targetedly to enter
Row Catalyst Design, to improve the utilization ratio of catalyst, the yield of target product and selectivity.Therefore high performance urge is developed
Agent, the exploitation for techniques such as F- T synthesis, synthesis gas methanation and methane reformings are significant.
At present, many porous complex catalysts are applied to above-mentioned technique.Such as Patent No.
In ZL200410056853.3 Chinese patent, a kind of ternary composite metal oxide porous catalyst and its preparation side are disclosed
Method, using porous honeycomb ceramic as carrier, by the way that inside and outside two layers of oxide is respectively coated on ceramic matrix, internal layer includes metal oxygen
Compound and aluminum oxide, outer layer are metal oxide containing precious metals, and gained catalyst achieves preferable effect for purifying vehicle exhaust processing
Fruit.But coating processes are complicated, and in the catalyst active component particle it is larger, use range is limited.Chinese patent
CN103143364A discloses a kind of nano-complex catalyst of high degree of dispersion and preparation method and application, utilizes co-precipitation
Complex precipitate is made in mixing salt solution and alkaline precipitating agent by method, is obtained after backflow, aging and roasting nano combined
Thing catalyst, the catalyst are used in methane reforming, have good performance.But the preparation method of the nano-composite catalyst
In must use zirconium oxide presoma, use range receives limitation.And the nano-composite catalyst needs to be further processed
Catalytic reaction could be used for.The Chinese patent of Application No. 201010575387.5 discloses a kind of porous silica carried metal
Or the preparation method of oxide, in the method, impregnated by porous silica, the synthesis of non-polar solven and Support Silica
Porous silica/metal oxygen can be just obtained after the multi-steps such as metal precursor, the removal of non-polar solven and drying and roasting
Compound composite.Because having used non-polar solven and infusion process in the patent, so as to cause preparation process cumbersome, and produce
Interaction in thing between metal oxide and silica is weaker, causes the particle size of metal oxide more than 200nm.In
State patent CN101005892 discloses a kind of composite oxide catalysts, and the catalyst contains Mo, V, alkaline-earth metal or dilute
The particle of earth elements and silica carrier, the patent do not announce gained the porous property of catalyst granules architectural feature, but by
In its preparation method be precipitation-calcination method, it is therefore contemplated that the porous of gained catalyst granules is poor.Moreover, on
The infusion process of complex steps has all been used in the patent stated, has so not only increased cost, and has made preparation technology more multiple
It is miscellaneous.
The content of the invention
The technical problems to be solved by the invention be catalyst preparation step present in prior art it is cumbersome, for Fischer-Tropsch
Synthesis, synthesis gas methanation and selectivity of product difference and the problem of poor catalyst stability during methane reforming reaction；Provide one
The porous complex catalyst of kind, the catalyst are used for having product when F- T synthesis, synthesis gas methanation and methane reforming reaction
The advantages of selectivity height and good catalyst stability.
The two of the technical problems to be solved by the invention are to provide a kind of porous compound for solving one of technical problem and urged
The preparation method of agent.
The three of the technical problems to be solved by the invention are to provide a kind of porous compound for solving one of technical problem and urged
The purposes of agent.
To solve one of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：
A kind of porous complex catalyst, in terms of parts by weight, including following components：
A) 30~100 parts are selected from least one of aluminum oxide, silica, magnesia and zirconium oxide inert component；
B) 0~20 part is selected from least one of platinum, ruthenium, rhodium and palladium element；
C) 0~20 part is selected from least one of nickel, iron, cobalt and copper element or its oxide；
D) 0~5 part is selected from：Molybdenum, zinc, at least one of the oxide of gallium and tin；
The content of wherein component (b) and component (c) is not all 0.
In above-mentioned technical proposal, it is preferred that component a) is in aluminum oxide, silica, magnesia, zirconium oxide and cerium oxide
One kind；It is furthermore preferred that the one kind of component a) in magnesia, zirconium oxide and cerium oxide.
In above-mentioned technical proposal, it is preferred that component a) is selected from least one of aluminum oxide and silica and magnesia
Mixture；It is furthermore preferred that the presoma of at least one of aluminum oxide and/or silica and the ratio of magnesia presoma are
(50：1)~(8：1).
In above-mentioned technical proposal, it is preferred that in terms of parts by weight, component b) content is 0.1~15 part.
In above-mentioned technical proposal, it is preferred that in terms of parts by weight, component c) content is 0.1~15 part.
In above-mentioned technical proposal, it is preferred that in terms of parts by weight, component d) content is 0.5~2 part.
In above-mentioned technical proposal, it is preferred that component b) is preferably ruthenium.
In above-mentioned technical proposal, it is preferred that component b) is preferably nickel.
In above-mentioned technical proposal, it is preferred that the ratio of presoma containing ruthenium and nickeliferous presoma is (1:4)~(4:1).
In above-mentioned technical proposal, it is preferred that 0.1~1 part of gallium and/or indium is also included in terms of parts by weight, in catalyst
Element or its oxide.
In above-mentioned technical proposal, it is preferred that the microscopic particles size of the porous complex catalyst is received in 10-1000
Rice, average pore size in 2-200 nanometers, specific surface area in 1-400 meters squared per grams, pore volume 0.005-1 cubic centimetres/gram；It is more excellent
Choosing, average pore size in 3-120 nanometers, specific surface area in 50-330 meters squared per grams, pore volume 0.05-0.6 cubic centimetres/gram.
In above-mentioned technical proposal, preferably but it is not limited to：Microscopic particles size is in 20-200 nanometers.
In above-mentioned technical proposal, the preparation method of the porous complex catalyst, comprise the following steps：
A) after inert component predecessor is uniformly mixed with surfactant in water, burin-in process, burin-in process are carried out
Temperature is 70~270 DEG C, and the time is 3~200 hours, and the precursor A of porous complex catalyst is made；
B) by component b)~d) predecessor, and above-mentioned porous complex catalyst precursor A uniformly mixing after, then
Secondary carry out burin-in process, temperature are 50~230 DEG C, and the time is 5~220 hours, obtains the presoma of porous complex catalyst
The mass ratio of each material is in B, wherein precursor B：Precursor A：Component b)~c) predecessor：Component d) predecessor=1：
(0.003~0.25)：(0.001~0.15)；
C) after the precursor B of above-mentioned porous complex catalyst being dried processing, is calcined porous compound is obtained to urge
The presoma C of agent；
D) the presoma C of above-mentioned porous complex catalyst is subjected to reduction treatment, temperature is 480-850 DEG C, the time 2
~30 hours, obtain porous complex catalyst.
In the preparation method, preferably but be not limited to, 1) burin-in process temperature be 100~200 DEG C, the time 5
~90 hours；2) burin-in process temperature is 70~130 DEG C again, and the time is 8~120 hours, the quality of each material in precursor B
Than for：Precursor A：The predecessor of active component：Predecessor=1 of auxiliary agent：(0.03~0.15)：(0.01~0.12)；3) do
Dry treatment temperature is 60~120 DEG C, and the time is 3~80 hours；Calcination processing temperature is 500~700 DEG C, and the time is 4~20 small
When；4) reduction treatment temperature is 200-660 DEG C, and the time is 4~15 hours.
In the preparation method, the type difference of predecessor is as follows：Inert component predecessor be selected from boehmite, diatomite,
At least one of silica gel and silicate, aluminate, aluminium salt, magnesium salts, the oxide of magnesium and zirconates；Active component predecessor is selected from
At least one of nitrate, sulfate, halide salt, acetate, carbonate and basic salt；Auxiliary agent predecessor be selected from halide salt,
At least one of nitrate, acetate, sulfate, molybdate and carbonate；Surfactant is selected from alkylbenzenesulfonate, alkane
In base sulfonate, soap, polyoxyethylene, Pluronic F68, polyethylene glycol or polyvinyl alcohol at least
It is a kind of.
In such scheme, preferably but be not limited to, inert component predecessor be selected from boehmite, diatomite, silica gel and
At least one of silicate, aluminate, aluminium salt, magnesium salts, the oxide of magnesium and cerium salt；Active component predecessor is selected from nitric acid
At least one of salt, acetate, carbonate and basic salt；Auxiliary agent predecessor is selected from nitrate, acetate, molybdate and halogenation
At least one of salt；Surfactant is selected from soap, polyoxyethylene, Pluronic F68, poly- second two
At least one of alcohol or polyvinyl alcohol.
In above-mentioned technical proposal, it is preferred that inert component predecessor is for magnesium salts/magnesium oxide and selected from boehmite and/or silicon
At least one of diatomaceous earth.
In above-mentioned technical proposal, it is preferred that inert component predecessor is for magnesium salts/magnesium oxide and selected from boehmite and/or silicon
One kind in diatomaceous earth.
In above-mentioned technical proposal, it is preferred that inert component predecessor is magnesia/magnesium carbonate and boehmite/diatomite.
In above-mentioned technical proposal, it is furthermore preferred that the mass ratio of boehmite/diatomite and magnesia/magnesium carbonate is (50：1)
~(8：1).
A kind of method that F- T synthesis prepares C5~C20 hydrocarbon, using synthesis gas as raw material, raw material contacts instead with above-mentioned catalyst
C5~C20 hydrocarbon should be obtained.
A kind of method of synthesis gas methanation, using synthesis gas as raw material, raw material obtains first with above-mentioned catalyst haptoreaction
Alkane.
A kind of method of reforming of methane on Ni-Ce, using methane and carbon dioxide as raw material, raw material connects with above-mentioned catalyst
Tactile reaction obtains synthesis gas.
In above-mentioned technical proposal, raw material is generally acknowledged that with the reaction condition residing for catalyst for those skilled in the art can be real
The reaction condition now converted.
In the present invention, the presoma for being primarily due to inert component forms the skeleton knot of stable opening after burin-in process
Structure, the skeleton structure of this opening can carry the predecessor of active component and auxiliary agent, while this stable opening as carrier
Skeleton structure pass through calcination processing, the hydroxyl on surface is relatively more, therefore in loading active component and when auxiliary agent,
Both can form stronger chemical bond, so as to form stable compound.Additionally, due to active component presoma and help
The hybrid mode of the presoma of agent is mixing in situ, after burin-in process, active component is formed with auxiliary agent homogeneous compound
Thing；In addition, inert component, active component and the in situ of auxiliary agent presoma add in preparation process, after avoiding complex steps
Loading process.Due to the presence of surfactant, the specific surface area of compound is improved, also enables active component more uniformly
It is distributed in inert component, while also improves the voids content of compound and the decentralization of active component.
The above measure, solve unstable composite structure in traditional preparation methods, carrier and activearm and divide it
Interaction Force is small, active component easy-sintering, voids content are low and the problems such as preparation process is cumbersome, obtains efficient, stably
Porous compound, thus be accordingly used in the catalysis industry production process of F- T synthesis, synthesis gas methanation and methane reforming, make
Catalyst activity and stability and life-span are all significantly improved.
Below by embodiment and comparative example, the present invention is further elaborated, but the porous compound and preparation method
It is not limited to following embodiments.
Brief description of the drawings：
The transmission electron microscope photo of Fig. 1 embodiments 1.
The transmission electron microscope photo of Fig. 2 comparative examples 1.
Embodiment
【Embodiment 1】
After 100 grams of boehmites are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, burin-in process, processing temperature are carried out
Spend for 120 DEG C, the time is 15 hours, and precursor A is made；By 13.6 grams of platinum chlorides (equivalent to 10g platinum), 6.9 grams of ammonium molybdate (phases
When in 5g molybdenum oxides) and above-mentioned precursor A after uniformly mix, carry out burin-in process again, temperature is 160 DEG C, the time 20
Hour, precursor B is obtained, processing then is dried in above-mentioned precursor B, temperature is 120 DEG C, and the time is 20 hours；Then
Calcination processing, temperature are 550 DEG C, and the time is 10 hours；Obtain presoma C；Above-mentioned presoma C is subjected to reduction treatment, temperature
For 600 DEG C, the time is 5 hours, you can obtains porous complex catalyst, preparation process condition such as table 1, catalyst physical property is shown in Table
2。
The catalyst is used for F- T synthesis, reaction temperature is 230 DEG C, volume space velocity 600h-1, pressure 1.8MPa,
Hydrogen-carbon ratio is 2 in raw material, and the selectivity that CO conversion reaches 19%, C5-C20 reaches 79%, stability (conversion ratio>
90%) 300h is reached.
The catalyst is used in catalyst synthesis gas methanation, 350 DEG C of reaction temperature, volume space velocity 2200h-1,
Pressure 1.8MPa, hydrogen-carbon ratio is 2 in raw material, and CO conversion reaches 50%, and methane selectively reaches 71%.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material, and the conversion ratio of methane is 93%, and the selectivity of hydrogen is 92%.
【Embodiment 2~5】
The synthesis step as described in embodiment 1, change inert component presoma, active component presoma and surfactant
Species and quality, preparation condition is adjusted, can synthesize to obtain the porous complex catalyst of the present invention, preparation process condition is shown in Table
1, catalyst physical property is shown in Table 2.
The catalyst is respectively used to F- T synthesis, synthesis gas methanation and methane reforming reaction, reaction condition and reality
Apply that example 1 is identical, and catalytic performance is shown in Table 2.
【Embodiment 6】
After 98 grams of boehmites, 2 grams of magnesia are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, carry out at aging
Reason, treatment temperature are 120 DEG C, and the time is 15 hours, and precursor A is made；By 13.6 grams of platinum chlorides (equivalent to 10g platinum), 6.9 grams
After ammonium molybdate (equivalent to 5g molybdenum oxides) and above-mentioned precursor A uniformly mix, burin-in process is carried out again, temperature is 160 DEG C,
Time is 20 hours, obtains precursor B, and above-mentioned precursor B then is dried into processing, and temperature is 120 DEG C, and the time is 20 small
When；Then calcination processing, temperature are 550 DEG C, and the time is 10 hours；Obtain presoma C；Above-mentioned presoma C is subjected to also original place
Reason, temperature are 600 DEG C, and the time is 5 hours, you can obtains porous complex catalyst, preparation process condition such as table 1, catalyst
Physical property is shown in Table 2.
The catalyst is used for F- T synthesis, reaction temperature is 230 DEG C, volume space velocity 600h-1, pressure 1.8MPa,
Hydrogen-carbon ratio is 2 in raw material, and reactivity worth is shown in Table 2.
The catalyst is used in catalyst synthesis gas methanation, 350 DEG C of reaction temperature, volume space velocity 2200h-1,
Pressure 1.8MPa, hydrogen-carbon ratio is 2 in raw material, and reactivity worth is shown in Table 2.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material, and reactivity worth is shown in Table 2.
【Embodiment 7】
Preparation technology, raw material dosage, treatment conditions are all same as Example 6.It is simply 89 grams by boehmite Mass adjust- ment,
Magnesia quality is adjusted to 11 grams, and complex catalyst, preparation process condition such as table 1 is prepared, and catalyst physical property is shown in Table 2.
The catalyst is respectively used to F- T synthesis, synthesis gas methanation and methane reforming reaction, reaction condition and reality
Apply that example 9 is identical, and catalytic performance is shown in Table 2.
【Embodiment 8】
Preparation technology, raw material dosage, treatment conditions are all same as Example 6.Boehmite is simply adjusted to diatomite, matter
Amount is still 98 grams, complex catalyst, preparation process condition such as table 1 is prepared, catalyst physical property is shown in Table 2.
The catalyst is respectively used to F- T synthesis, synthesis gas methanation and methane reforming reaction, reaction condition and reality
Apply that example 6 is identical, and catalytic performance is shown in Table 2.
【Embodiment 9】
Preparation technology, raw material dosage, treatment conditions are all same as Example 6.Diatomite quality is simply adjusted to 89 grams,
Magnesia quality is adjusted to 11 grams, and complex catalyst, preparation process condition such as table 1 is prepared, and catalyst physical property is shown in Table 2.
The catalyst is respectively used to F- T synthesis, synthesis gas methanation and methane reforming reaction, reaction condition and reality
Apply that example 6 is identical, and catalytic performance is shown in Table 2.
【Embodiment 10】
After 100 grams of boehmites are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, burin-in process, processing temperature are carried out
Spend for 120 DEG C, the time is 15 hours, and precursor A is made；By 13.6 grams of platinum chlorides (equivalent to 10g platinum), 6.9 grams of ammonium molybdate (phases
When in 5g molybdenum oxides), 0.5 gram of gallium nitrate and above-mentioned precursor A be after uniformly mix, carry out burin-in process, temperature 160 again
DEG C, the time is 20 hours, obtains precursor B, and above-mentioned precursor B then is dried into processing, and temperature is 120 DEG C, and the time is
20 hours；Then calcination processing, temperature are 550 DEG C, and the time is 10 hours；Obtain presoma C；Above-mentioned presoma C is gone back
Original place is managed, and temperature is 600 DEG C, and the time is 5 hours, you can obtains porous complex catalyst, preparation process condition such as table 1, urges
Agent physical property is shown in Table 2.
The catalyst is used for F- T synthesis, reaction temperature is 230 DEG C, volume space velocity 600h-1, pressure 1.8MPa,
Hydrogen-carbon ratio is 2 in raw material, and the selectivity that CO conversion reaches 19%, C5-C20 reaches 79%, stability (conversion ratio>
90%) 300h is reached.
The catalyst is used in catalyst synthesis gas methanation, 350 DEG C of reaction temperature, volume space velocity 2200h-1,
Pressure 1.8MPa, hydrogen-carbon ratio is 2 in raw material, and CO conversion reaches 50%, and methane selectively reaches 71%.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material, and the conversion ratio of methane is 93%, and the selectivity of hydrogen is 92%.
【Embodiment 11】
After 100 grams of boehmites are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, burin-in process, processing temperature are carried out
Spend for 120 DEG C, the time is 15 hours, and precursor A is made；By 13.6 grams of platinum chlorides (equivalent to 10g platinum), 6.9 grams of ammonium molybdate (phases
When in 5g molybdenum oxides), 1.5 grams of indium nitrates and above-mentioned precursor A be after uniformly mix, carry out burin-in process, temperature 160 again
DEG C, the time is 20 hours, obtains precursor B, and above-mentioned precursor B then is dried into processing, and temperature is 120 DEG C, and the time is
20 hours；Then calcination processing, temperature are 550 DEG C, and the time is 10 hours；Obtain presoma C；Above-mentioned presoma C is gone back
Original place is managed, and temperature is 600 DEG C, and the time is 5 hours, you can obtains porous complex catalyst, preparation process condition such as table 1, urges
Agent physical property is shown in Table 2.
The catalyst is used for F- T synthesis, reaction temperature is 230 DEG C, volume space velocity 600h-1, pressure 1.8MPa,
Hydrogen-carbon ratio is 2 in raw material, and the selectivity that CO conversion reaches 19%, C5-C20 reaches 79%, stability (conversion ratio>
90%) 300h is reached.
The catalyst is used in catalyst synthesis gas methanation, 350 DEG C of reaction temperature, volume space velocity 2200h-1,
Pressure 1.8MPa, hydrogen-carbon ratio is 2 in raw material, and CO conversion reaches 50%, and methane selectively reaches 71%.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material, and the conversion ratio of methane is 93%, and the selectivity of hydrogen is 92%.
【Embodiment 12】
After 100 grams of boehmites are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, burin-in process, processing temperature are carried out
Spend for 120 DEG C, the time is 15 hours, and precursor A is made；By 13.6 grams of platinum chlorides (equivalent to 10g platinum), 6.9 grams of ammonium molybdate (phases
When in 5g molybdenum oxides), 0.3 gram of gallium nitrate and 0.2 gram of indium nitrate and above-mentioned precursor A be after uniformly mix, carry out aging again
Processing, temperature are 160 DEG C, and the time is 20 hours, obtains precursor B, above-mentioned precursor B then is dried into processing, temperature
For 120 DEG C, the time is 20 hours；Then calcination processing, temperature are 550 DEG C, and the time is 10 hours；Obtain presoma C；Will be above-mentioned
Presoma C carries out reduction treatment, and temperature is 600 DEG C, and the time is 5 hours, you can obtains porous complex catalyst, preparation technology
Condition such as table 1, catalyst physical property are shown in Table 2.
The catalyst is used for F- T synthesis, reaction temperature is 230 DEG C, volume space velocity 600h-1, pressure 1.8MPa,
Hydrogen-carbon ratio is 2 in raw material, and the selectivity that CO conversion reaches 19%, C5-C20 reaches 79%, stability (conversion ratio>
90%) 300h is reached.
The catalyst is used in catalyst synthesis gas methanation, 350 DEG C of reaction temperature, volume space velocity 2200h-1,
Pressure 1.8MPa, hydrogen-carbon ratio is 2 in raw material, and CO conversion reaches 50%, and methane selectively reaches 71%.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material, and the conversion ratio of methane is 93%, and the selectivity of hydrogen is 92%.
【Comparative example 1~4】
Compound is prepared using infusion process.100 grams of boehmites, 25 grams of polyethylene glycol are mixed and added in 200 grams of water first,
And homogeneous phase solution is evenly stirred until, product is then subjected to burin-in process, treatment temperature is 120 DEG C, and the time is 15 hours, then
Dried 10 hours at 100 DEG C, and 550 DEG C of calcinings can obtain carrier in 10 hours in air atmosphere.By 13.6 grams of platinum chlorides
After (equivalent to 10g platinum), 6.9 grams of ammonium molybdates (equivalent to 5g molybdenum oxides) and 20g water are made into mixed solution, incipient impregnation is utilized
Method is loaded to above-mentioned carrier, and 550 DEG C of calcinings carry out reduction treatment again after 10 hours in air atmosphere again, and temperature is 600 DEG C,
Time is 5 hours, you can obtains the porous complex catalyst in comparative example 1.It is feed change proportion of composing, preparation technology, lazy
The species and quality of property component presoma, active component presoma and surfactant, can obtain porous complex catalyst,
Its structure composition feature is shown in Table 3 and table 4 with catalytic performance.
【Comparative example 5-8】
After 100 grams of boehmites are uniformly mixed with 25 grams of polyethylene glycol in 200 grams of water, burin-in process, processing temperature are carried out
Spend for 120 DEG C, the time is 15 hours, and precursor A is made；6.9 grams of ammonium molybdates (equivalent to 5g molybdenum oxides) and above-mentioned precursor A
Uniformly after mixing, carry out burin-in process again, temperature is 160 DEG C, and the time is 20 hours, obtains precursor B, then will be above-mentioned before
Drive body B and processing is dried, temperature is 120 DEG C, and the time is 20 hours；Then calcination processing, temperature are 550 DEG C, the time 10
Hour；Obtain presoma C；Above-mentioned presoma C is subjected to reduction treatment, temperature is 600 DEG C, and the time is 5 hours, you can is obtained more
Hole complex catalyst.
The catalyst is used for methane reforming reaction, 750 DEG C of reaction temperature, volume space velocity 1400h-1, pressure
0.2MPa, methane and carbon dioxide mol ratio is 2 in raw material.
Comparative example 6 is that boehmite is adjusted into diatomite, and other conditions are identical with comparative example 6.
Comparative example 7 is that boehmite is adjusted into magnesia, and other conditions are identical with comparative example 6.
Comparative example 8 be by boehmite be adjusted to boehmite/magnesia mixture (wherein boehmite quality be 89 grams, oxygen
Change magnesia amount as 11 grams), other conditions are identical with comparative example 6.
Comparative example 5-8 structure composition feature is shown in Table 3 and table 4 with catalytic performance.
Table 1
Table 2
Table 3
Table 4
Claims (11)
1. a kind of porous complex catalyst, in terms of parts by weight, including following components：
A) 30~100 parts are selected from least one of aluminum oxide, zirconium oxide, magnesia and silica inert component；
B) 0~20 part is selected from least one of platinum, ruthenium, rhodium and palladium element；
C) 0~20 part is selected from least one of nickel, iron, cobalt and copper element or its oxide；
D) 0~5 part selected from molybdenum, zinc, gallium and tin at least one of oxide；
The content of wherein component (b) and component (c) is not all 0.
2. porous complex catalyst according to claim 1, it is characterised in that component a) be selected from aluminum oxide, magnesia,
One kind in zirconium oxide, cerium oxide and silica.
3. porous complex catalyst according to claim 1, it is characterised in that in terms of parts by weight, component b) content
For 0.1~15 part.
4. porous complex catalyst according to claim 1, it is characterised in that in terms of parts by weight, component c) content
For 0.1~15 part.
5. porous complex catalyst according to claim 1, it is characterised in that in terms of parts by weight, component d) content
For 0.5~2 part.
6. porous complex catalyst according to claim 1, it is characterised in that the porous complex catalyst it is micro-
Particle size is seen in 10-1000 nanometers, average pore size in 2-200 nanometers, specific surface area in 1-400 meters squared per grams, pore volume to exist
0.005-1 cubic centimetres/gram.
7. porous complex catalyst according to claim 6, it is characterised in that average pore size compares table in 3-120 nanometers
Area in 50-330 meters squared per grams, pore volume 0.05-0.6 cubic centimetres/gram.
8. the preparation method of the porous complex catalyst described in claim any one of 1-7, comprises the following steps：
A) after inert component predecessor is uniformly mixed with surfactant in water, burin-in process, burin-in process temperature are carried out
For 70~270 DEG C, the time is 3~200 hours, and the precursor A of porous complex catalyst is made；
B) by component b)~d) predecessor, and above-mentioned porous complex catalyst precursor A uniformly mixing after, enter again
Row burin-in process, temperature are 50~230 DEG C, and the time is 5~220 hours, obtains the precursor B of porous complex catalyst, its
The mass ratio of each material is in middle precursor B：Precursor A：Component b)~c) predecessor：Component d) predecessor=1：
(0.003~0.25)：(0.001~0.15)；
C) porous complex catalyst is obtained after the precursor B of above-mentioned porous complex catalyst being dried into processing, roasting
Presoma C；
D) the presoma C of above-mentioned porous complex catalyst is subjected to reduction treatment, temperature is 480-850 DEG C, and the time is 2~30
Hour, obtain porous complex catalyst.
9. a kind of method that F- T synthesis prepares C5~C20 hydrocarbon, using synthesis gas as raw material, raw material and any one of claim 1~7
The catalyst haptoreaction obtains C5~C20 hydrocarbon.
10. a kind of method of synthesis gas methanation, using synthesis gas as raw material, raw material and the catalysis of any one of claim 1~7
Agent haptoreaction obtains methane.
A kind of 11. method of methane reforming, using methane and carbon dioxide as raw material, described in raw material and any one of claim 1~7
Catalyst haptoreaction obtains synthesis gas.
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