CN102441374A - Selective hydrogenation catalyst and its preparation method and application - Google Patents
Selective hydrogenation catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention relates to a selective hydrogenation catalyst and its preparation method and application. The catalyst comprises a catalyst carrier and metal active ingredients, prepared by the following steps: pickling graphene and then washing the pickled graphene with water to neutral, then immersing the neutral graphene in weak ammonia and drying at a high temperature to obtain the catalyst carrier, preparing active metal into a precursor solution of the active metal, then steeping or spraying the precursor solution on the catalyst carrier to obtain a supported graphene catalyst precursor precursor, drying and then reducing to obtain a product. The catalyst can be used in selective hydrogenation catalytic reaction. Compared with the prior art, the catalyst can be used for a one-stage selective hydrogenation reaction of cracked gasoline and can be simultaneously used for a selective hydrogenation reaction of C2-C4. The catalyst has the advantages of high hydrogenation activity and good diolefin hydrogenation selectivity, and is beneficial for prolonging the regeneration period of the catalyst.
Description
Technical field
The present invention relates to a kind of selective hydrocatalyst of catalyst of petroleum hydrocarbon product, especially relate to a kind of selective hydrocatalyst.
Background technology
Drippolene is the byproduct C in the ethylene production
5The general name of～220 ℃ of cuts, it is low from the anxious water-cooling tower of ethylene cracker, the low condensate liquid that reaches between compressor section of debutanizing tower.The composition of drippolene is quite complicated, and wherein arene content is up to more than 70%, and the performance of unsaturated component is extremely unstable in the oil product, in depositing process, is prone to polymerization and generates low polymerization degree compound (green oil) and colloid, can not directly use.Current, the processing drippolene generally adopts the two-stage hydrogenation method in the industry.The one-stage hydrogenation reaction comparatively relaxes, and is main in order to remove the big diolefin of reactivity.The secondary hydrogenation reaction condition is comparatively fierce, is in order to remove the compound of monoolefine and sulfur-bearing, nitrogen and oxygen.
The drippolene one-stage hydrogenation is widely used to be Pd/Al
2O
3Type catalyst, reactive metal palladium content be below 0.5%, has very big superiority though overcome the diene polymerization during to the hydrofinishing drippolene, also exists reaction temperature height, poor selectivity, defective such as carbon deposit easily.
Japanese (disclosing) 80-23-165,81-88-493 and CN1071443A, CN1266085A adopts Pd-Cr/Al
2O
3Be pyrolysis gasoline hydrogenation catalyst, after adding Cr or Cu, activity and selectivity all have obvious improvement.
U.S. Phillips oil company patent [U.S.5475173, U.S.5489565] has described Pt-supported catalyst and under the Ag promoting catalysis, has carried out selective hydrogenation, and catalyst has stability and regenerability preferably.
CN01106018.2 adopts advanced hydrogen arc plasma process to prepare metal nano powders such as palladium, nickel, nickel cerium; Make current-carrying gas with certain high-pressure inert gas then; Through nozzle, on carrier, deposit film forming, handle through a series of common process again and process the nano thin-film catalyst.This catalyst has activity and selectivity preferably.The clear 47-35670 of CN1071443A, CN1056068A, CN1071443A, CN02111016.6, CN200810102240.7 and japanese has also introduced and has been used for the one-stage selective hydrogenation of gasoline splitting catalyst.They all are that aluminium oxide loaded palladium metal by different crystalline phases constitutes, and the diolefin hydrogenation activity makes moderate progress, but that selectivity improves is not obvious.
Diolefin in the drippolene is prone to polymerization at high temperature or dehydrogenative condensation; Therefore the one-stage hydrogenation catalyst hydrogenation activity is unsuitable too high, and has higher diolefin hydrogenation selectivity, and is excessive to reduce because monoolefin hydrogenation induces reaction temperature rise; And then acceleration carbonaceous and the deposition of burnt matter on catalyst; Simultaneously catalyst should have bigger appearance glue ability, and prolonging the regeneration period of catalyst, the existing just Pd/ aluminium oxide catalyst of above-mentioned condition is failed the problem of fine solution.
Summary of the invention
The object of the invention is exactly the long selective hydrocatalyst of regeneration period that a kind of more avtive spots, catalyst are provided for the defective that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme:
A kind of selective hydrocatalyst is characterized in that, this catalyst is made up of catalyst carrier and metal active constituent, and described catalyst carrier is a Graphene, and metal active constituent is selected from one or more among Pt, Pd, Cu, the Ni.
The content of described metal active constituent Pt, Pd is 0.05～1.15wt%, preferred 0.2～0.5wt%.
The content of described metal active constituent Cu, Ni is 10～30wt%, preferred 15～25wt%.
A kind of preparation method of selective hydrocatalyst is characterized in that, this method may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 1～4h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of drying 3～6h promptly get the Graphene carrier again;
(2) reactive metal is made into the precursor solution of reactive metal, with solution impregnation or be sprayed onto on the Graphene carrier, processes the graphen catalyst precursor of support type, restore after the drying to handle and obtain product.
Described Graphene adopts following method preparation: after being cooled to the concentrated sulfuric acid about 0 ℃, add graphite powder, under vigorous stirring, slowly add potassium permanganate; The maintenance system temperature is no more than 20 ℃; Put into 35 ℃ water-bath after stirring and react 2h, add deionized water again, make system temperature be no more than 98 ℃; Continue to stir 15min, add deionized water and 30wt%H respectively
2O
2, filter while hot, use 1mol/L
-1The abundant washing leaching cake of HCl to filtrating in can not measure SO
4 2-, washing neutrality with deionized water again, gained sample dry 12h in 50 ℃ of vacuum drying chambers gets final product.
The precursor solution activity of described reactive metal can be chloride or soluble-salt for metal precursor; The Pt precursor solution preferably uses chloroplatinic acid; The Pd precursor solution preferably uses acid of chlorine palladium or acid chloride, and Cu, Ni precursor solution preferably use chloride or nitrate.
The pH value of Pt, Pd precursor solution is 1～7, preferred 3～4; The pH value of Cu, Ni precursor solution is 4～8, preferred 6～7.
Described reduction is handled the graphen catalyst precursor that adopts to support type and is dripped KBH
4, NaBH
4, KH
2PO
4-KOH mixed solution or NaH
2PO
4-NaOH mixed solution produces to there being gas, specifically may further comprise the steps: the graphen catalyst precursor of support type is put into the three-necked bottle that has ice-water bath, behind the feeding nitrogen, dropwise add KBH
4, NaBH
4, KH
2PO
4-KOH mixed solution or NaH
2PO
4The reduction of-NaOH mixed solution; In system, no longer include till the gas release, the black solid Pt-B/ graphen catalyst that obtains is behind the distilled water cyclic washing; Putting into absolute ethyl alcohol preserves subsequent use; Amorphous alloy has the unordered arrangement architecture with shortrange order of long-range, and its surface is evenly distributed as the atom at catalytic reaction activity center, and character is identical; And can control its electronic property effectively, obtain suitable catalytic active center through its composition of modulation.
Described reduction is handled and is adopted hydrogen to reduce, and the catalyst reduction treatment temperature that contains Pt, Pd is 110～180 ℃, and the processing time is 3～5h; The catalyst reduction treatment temperature that contains Cu, Ni is 350～450 ℃, and the processing time is 4～7h.
Described catalyst can be pinched compressing tablet or sheet, bar shaped, annular, wheel shape, clover or bunge bedstraw herb shape are processed in extrusion modling through mixing.
A kind of application of selective hydrocatalyst is characterized in that, this catalyst is used in the selective hydrogenation, and the selective hydrogenation temperature is 35～180 ℃, and the reactive hydrogen dividing potential drop is 1.0～6.0MPa, and volume space velocity is 6～10h during liquid
-1, hydrogen to oil volume ratio is 40～400.
Compared with prior art, the present invention has the following advantages:
(1) Graphene is a kind of carbonaceous new material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape lattice structure. compare with CNT; Has bigger theoretical specific area; Because the degree that reactive metal disperses on Graphene is better; Under identical carrying capacity, the active surface area of performance is bigger, has more avtive spot;
(2) catalyst surface acidity is low, and carbonaceous and the little deposit of burnt matter on catalyst are so help prolonging the regeneration period of catalyst;
(3) catalyst according to the invention can be used for the one-stage selective hydrogenation of gasoline splitting reaction.Simultaneously can also be used for C
2, C
3Selective hydrogenation, C
4Selective hydrogenation; The olefine aldehydr selective hydrogenation; The hydrogenation of anthraquinone selective hydrogenation, reformation back end hydrogenation and various meticulous organic products etc.
The specific embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
At first the Graphene of preparation being used mass fraction is that 10% nitric acid was washed 3 hours, is washed with water to neutrality then, with 2% weak aqua ammonia immersion 1 hour, after 5 hours, promptly gets the Graphene carrier through 120 ℃ of dryings again.
The preparation of Pd/ Graphene (0.5% percentage by weight): the palladium bichloride of metering is dissolved in the pure water; Limit heating edge dripping hydrochloric acid to whole dissolving also transfers to 3 with the pH value of solution; Be immersed in above-mentioned treated Graphene in the palladium chloride solution that is made into by metering; Soak after 12 hours,, process the graphen catalyst precursor of support type through 120 ℃ of dryings.
Graphen catalyst precursor by the support type of preparing Pd/ Graphene (0.3% percentage by weight), Pd/ Graphene (0.2% percentage by weight) with quadrat method.
Embodiment 2
To carry out the electroless plating method reduction by 3 kinds of catalyst precarsors of embodiment 1 preparation, obtain the Pd/ graphen catalyst of different activities tenor.Concrete grammar is:
Pd/ graphen catalyst precursor is put into the three-necked bottle that has ice-water bath, behind the feeding nitrogen, dropwise add the KBH of metering
4The reduction of-KOH mixed solution no longer includes till the gas release black solid Pd-B/ graphen catalyst that obtains in system.Behind the distilled water cyclic washing, put into absolute ethyl alcohol and preserve subsequent use.
Embodiment 3
To carry out hydrogen reducing by 3 kinds of catalyst precarsors of embodiment 1 preparation, obtain the Pd/ graphen catalyst of different activities tenor.Concrete grammar is:
Pd/ graphen catalyst precursor is directly put into tubular reactor, feed hydrogen reducing down at 120 ℃ and promptly obtained the Pd/ graphen catalyst in 3～5 hours.
Embodiment 4
Using the Graphene carrier among the embodiment 1, is the presoma (nitric acid acid adjustment degree) of palladium with the palladium nitrate, processes Pd/ graphen catalyst precursor (0.3% percentage by weight) with method of the same race.Prepare the Pd-B/ graphen catalyst by the method for embodiment 2 again.
Embodiment 5
Using the Graphene carrier among the embodiment 1, is the presoma of platinum with the chloroplatinic acid, processes Pt/ graphen catalyst precursor (0.3% percentage by weight) with method of the same race.Prepare the Pt-B/ graphen catalyst by the method for embodiment 2 again.
Embodiment 6
Using the Graphene carrier among the embodiment 1, is the presoma of platinum with four triphenylphosphine platinum, processes Pt/ graphen catalyst precursor (0.3% percentage by weight) with method of the same race.Prepare the Pt-B/ graphen catalyst by the method for embodiment 2 again.
Embodiment 7
Using the Graphene carrier among the embodiment 1, is the presoma of nickel with the nickel nitrate, processes Ni/ graphen catalyst precursor (20% percentage by weight) with method of the same race.Prepare the Ni-B/ graphen catalyst by the method for embodiment 2 again.
Embodiment 8
Using the Graphene carrier among the embodiment 1, is the presoma of nickel with the nickel nitrate, processes Ni/ graphen catalyst precursor (20% percentage by weight) with method of the same race.Press the method for embodiment 3 again, under 400 ℃ of conditions, reduce, prepare the Ni/ graphen catalyst.
Embodiment 9
Using the Graphene carrier among the embodiment 1, is the presoma of copper with the copper nitrate, processes Cu/ graphen catalyst precursor (20% percentage by weight) with method of the same race.Prepare the Cu-B/ graphen catalyst by the method for embodiment 2 again.
Embodiment 10
Using the Graphene carrier among the embodiment 1, is the presoma of copper with the copper nitrate, processes Cu/ graphen catalyst precursor (20% percentage by weight) with method of the same race.Press the method for embodiment 3 again, under 400 ℃ of conditions, reduce, prepare the Cu/ graphen catalyst.
Evaluating catalyst:
Catalyst activity representes that with the diolefin hydrogenation rate selectivity representes that with the monoene hydrogenation rate the low catalyst of diolefin hydrogenation rate height monoene hydrogenation rate then has high hydrogenation selectivity, if monoene hydrogenation rate height then selection of catalysts property is low.
Pt, Pd evaluating catalyst use little anti-isothermal reaction device, and the catalyst loading amount is 10ml.Reaction condition is a hydrogen to oil volume ratio=40: 1, volume space velocity=8h during liquid
-1, pressure=2.1MPa, T=35～70 ℃.
Cu, Ni evaluating catalyst use little anti-isothermal reaction device, and the catalyst loading amount is 10ml.Reaction condition is a hydrogen to oil volume ratio=40: 1, volume space velocity=8h during liquid
-1, pressure=2.1MPa, T=180 ℃.
Above embodiment evaluating catalyst result is following:
The diolefin hydrogenation of table 1 embodiment 2 catalyst is active
The monoene hydrogenation activity of table 2 embodiment 1 catalyst
The diolefin hydrogenation of table 3 embodiment 3 catalyst is active
The monoene hydrogenation activity of table 4 embodiment 3 catalyst
The monoene hydrogenation activity of table 5 embodiment 3 catalyst (T=70 ℃)
The monoene hydrogenation activity of table 6 embodiment 3 catalyst (T=180 ℃)
Embodiment 11
A kind of selective hydrocatalyst, this catalyst is made up of catalyst carrier Graphene and metal active constituent Pt, Cu, is benchmark with the percentage by weight of catalyst, and Pt content is 0.05wt%, and Cu content is 10wt%.
The Preparation of catalysts method may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 1h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of dry 3h promptly get the Graphene carrier again;
(2) chloroplatinic acid, copper nitrate are made into the precursor solution of reactive metal by proportioning, the pH value of chloroplatinic acid is 3, and the pH value of copper nitrate is 7, and solution impregnation to the Graphene carrier, is processed the graphen catalyst precursor of support type;
(3) the graphen catalyst precursor of the support type that obtains is put into the three-necked bottle that has ice-water bath, behind the feeding nitrogen, dropwise add the KBH of metering
4Reduction; In system, no longer include till the gas release, the black solid graphen catalyst that obtains is behind the distilled water cyclic washing; Putting into absolute ethyl alcohol preserves subsequent use; Amorphous alloy has the unordered arrangement architecture with shortrange order of long-range, and its surface is evenly distributed as the atom at catalytic reaction activity center, and character is identical; And can control its electronic property effectively, obtain suitable catalytic active center through its composition of modulation.
The catalyst prod that obtains can be processed sheet through extrusion modling, and this catalyst is used in the selective hydrogenation, and the selective hydrogenation temperature is 35 ℃, and the reactive hydrogen dividing potential drop is 1.0MPa, and volume space velocity is 6h during liquid
-1, hydrogen to oil volume ratio is 40.
Embodiment 12
A kind of selective hydrocatalyst, this catalyst is made up of catalyst carrier Graphene and metal active constituent Pd, Ni, is benchmark with the percentage by weight of catalyst, and Pd content is 1.15wt%, and Ni content is 30wt%.
The Preparation of catalysts method may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 4h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of dry 6h promptly get the Graphene carrier again;
(2) chlorine palladium acid, nickel chloride are made into the precursor solution of reactive metal by proportioning, the pH value of chlorine palladium acid is 4, and the pH value of nickel chloride is 6, and spray solution to the Graphene carrier, is processed the graphen catalyst precursor of support type;
(3) the graphen catalyst precursor of support type is put into the three-necked bottle that has ice-water bath, behind the feeding nitrogen, dropwise add KH
2PO
4The reduction of-KOH mixed solution; In system, no longer include till the gas release, the black solid graphen catalyst that obtains is behind the distilled water cyclic washing; Putting into absolute ethyl alcohol preserves subsequent use; Amorphous alloy has the unordered arrangement architecture with shortrange order of long-range, and its surface is evenly distributed as the atom at catalytic reaction activity center, and character is identical; And can control its electronic property effectively, obtain suitable catalytic active center through its composition of modulation.
Catalyst is pinched compressing tablet and processes cloverleaf pattern through mixing, and this catalyst is used in the selective hydrogenation, and the selective hydrogenation temperature is 180 ℃, and the reactive hydrogen dividing potential drop is 6.0MPa, and volume space velocity is 10h during liquid
-1, hydrogen to oil volume ratio is 400.
Embodiment 13
A kind of selective hydrocatalyst, this catalyst is made up of catalyst carrier Graphene and metal active constituent Pd, is benchmark with the percentage by weight of catalyst, and Pd content is 0.5wt%.
The preparation method of selective hydrocatalyst may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 2h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of dry 4h promptly get the Graphene carrier again;
(2) be that 3 chloroplatinic acid is impregnated on the Graphene carrier with the pH value, process the graphen catalyst precursor of support type, restore after the drying to handle and obtain product.
Graphene adopts following method preparation: after being cooled to the 23mL concentrated sulfuric acid about 0 ℃; Add the graphite powder of 1g, under vigorous stirring, slowly add 3g potassium permanganate, the maintenance system temperature is no more than 20 ℃; Put into 35 ℃ water-bath after stirring and react 2h; Add the 46mL deionized water again, make system temperature be no more than 98 ℃, continue to stir 15min; Add 140mL deionized water and 10mL30% (w) H respectively
2O
2, filter while hot, use 1mol/L
-1The abundant washing leaching cake of HCl to filtrating in can not measure SO
4 2-, washing neutrality with deionized water again, gained sample dry 12h in 50 ℃ of vacuum drying chambers gets final product.
Reduction is handled and is adopted hydrogen to reduce, and the reduction treatment temperature is 110 ℃, and the processing time is 3h; Obtain catalyst and can process bar shaped through extrusion modling, catalyst is used in the selective hydrogenation, and the selective hydrogenation temperature is 100 ℃; The reactive hydrogen dividing potential drop is 4.0MPa, and volume space velocity is 8h during liquid
-1, hydrogen to oil volume ratio is 100.
Embodiment 14
A kind of selective hydrocatalyst; This catalyst is made up of catalyst carrier Graphene and metal active constituent Pt, Pd, Cu, Ni; Percentage by weight with catalyst is a benchmark; The content of Pt is that the content of 0.2wt%, Pd is 0.5wt%, and the content of Cu is that the content of 15wt%, Ni is 25wt%.
The preparation method of selective hydrocatalyst may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 3h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of dry 5h promptly get the Graphene carrier again;
(2) be that 3 chloroplatinic acid, pH value are that 1 acid chloride, pH value are that 6 copper chloride, pH value are 8 nickel nitrate dipping or are sprayed onto on the Graphene carrier with the pH value, process the graphen catalyst precursor of support type;
(3) the graphen catalyst precursor of support type is put into the three-necked bottle that has ice-water bath, behind the feeding nitrogen, dropwise add the NaH of metering
2PO
4The reduction of-NaOH mixed solution; In system, no longer include till the gas release, obtain graphen catalyst, behind the distilled water cyclic washing; Putting into absolute ethyl alcohol preserves subsequent use; Amorphous alloy has the unordered arrangement architecture with shortrange order of long-range, and its surface is evenly distributed as the atom at catalytic reaction activity center, and character is identical; And can control its electronic property effectively, obtain suitable catalytic active center through its composition of modulation.
The catalyst that obtains can be pinched compressing tablet and processes annular through mixing, and this catalyst is used in the selective hydrogenation, and the selective hydrogenation temperature is 90 ℃, and the reactive hydrogen dividing potential drop is 3.0MPa, and volume space velocity is 7h during liquid
-1, hydrogen to oil volume ratio is 200.
Claims (9)
1. a selective hydrocatalyst is characterized in that, this catalyst is made up of catalyst carrier and metal active constituent, and described catalyst carrier is a Graphene, and metal active constituent is selected from one or more among Pt, Pd, Cu, the Ni.
2. a kind of selective hydrocatalyst according to claim 1 is characterized in that, the content of described metal active constituent Pt, Pd is 0.05～1.15wt%, preferred 0.2～0.5wt%.
3. a kind of selective hydrocatalyst according to claim 1 is characterized in that, the content of described metal active constituent Cu, Ni is 10～30wt%, preferred 15～25wt%.
4. the preparation method of a selective hydrocatalyst as claimed in claim 1 is characterized in that, this method may further comprise the steps:
(1) Graphene being used mass fraction is that 10% nitric acid is washed 1～4h, is washed with water to neutrality then, soaks 1h with the 2wt% weak aqua ammonia again, and 120 ℃ of drying 3～6h promptly get the Graphene carrier again;
(2) reactive metal is made into the precursor solution of reactive metal, with solution impregnation or be sprayed onto on the Graphene carrier, processes the graphen catalyst precursor of support type, restore after the drying to handle and obtain catalyst prod.
5. the preparation method of a kind of selective hydrocatalyst according to claim 4; It is characterized in that; The precursor solution activity of described reactive metal can be chloride or soluble-salt for metal precursor; The Pt precursor solution preferably uses chloroplatinic acid, and the Pd precursor solution preferably uses acid of chlorine palladium or acid chloride, and Cu, Ni precursor solution preferably use chloride or nitrate.
6. the preparation method of a kind of selective hydrocatalyst according to claim 5 is characterized in that, the pH value of Pt, Pd precursor solution is 1～7, preferred 3～4; The pH value of Cu, Ni precursor solution is 4～8, preferred 6～7.
7. the preparation method of a kind of selective hydrocatalyst according to claim 4 is characterized in that, described reduction is treated under nitrogen atmosphere, adopts the graphen catalyst precursor to support type to drip KBH
4, NaBH
4, KH
2PO
4-KOH mixed solution or NaH
2PO
4-NaOH mixed solution does not produce to there being gas, and logical again hydrogen reduces, and the catalyst reduction treatment temperature that contains Pt, Pd is 110～180 ℃, and the processing time is 3～5h; The catalyst reduction treatment temperature that contains Cu, Ni is 350～450 ℃, and the processing time is 4～7h.
8. the preparation method of a kind of selective hydrocatalyst according to claim 5 is characterized in that, described catalyst prod can be pinched compressing tablet or sheet, bar shaped, annular, wheel shape, clover or bunge bedstraw herb shape are processed in extrusion modling through mixing.
9. the application of a selective hydrocatalyst as claimed in claim 1; It is characterized in that this catalyst is used in the selective hydrogenation, the selective hydrogenation temperature is 35～180 ℃; The reactive hydrogen dividing potential drop is 1.0～6.0MPa, and volume space velocity is 6～10h during liquid
-1, hydrogen to oil volume ratio is 40～400.
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| CN105727954A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthetic gas to natural gas |
| CN105903488A (en) * | 2016-04-27 | 2016-08-31 | 武汉凯迪工程技术研究总院有限公司 | Selective hydrogenation catalyst for producing biodiesel and preparation method and application of selective hydrogenation catalyst |
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| CN104028272B (en) * | 2014-06-26 | 2016-03-23 | 聊城大学 | Graphene-supported copper-nickel compound nanometer photocatalyst, preparation method and application |
| CN104028272A (en) * | 2014-06-26 | 2014-09-10 | 聊城大学 | Graphene-supported copper-nickel composite nanometer photocatalyst, and preparation method and application thereof |
| CN105727954A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthetic gas to natural gas |
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