CN102441374A - Selective hydrogenation catalyst and its preparation method and application - Google Patents

Selective hydrogenation catalyst and its preparation method and application Download PDF

Info

Publication number
CN102441374A
CN102441374A CN201010504887XA CN201010504887A CN102441374A CN 102441374 A CN102441374 A CN 102441374A CN 201010504887X A CN201010504887X A CN 201010504887XA CN 201010504887 A CN201010504887 A CN 201010504887A CN 102441374 A CN102441374 A CN 102441374A
Authority
CN
China
Prior art keywords
catalyst
graphene
precursor
selective
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201010504887XA
Other languages
Chinese (zh)
Inventor
谢亮亮
唐博合金
杨志宁
徐福书
徐菁利
赵家昌
唐敖民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANGHAI XINNIAN PETROCHEMICAL ADJUVANT CO Ltd
Original Assignee
SHANGHAI XINNIAN PETROCHEMICAL ADJUVANT CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANGHAI XINNIAN PETROCHEMICAL ADJUVANT CO Ltd filed Critical SHANGHAI XINNIAN PETROCHEMICAL ADJUVANT CO Ltd
Priority to CN201010504887XA priority Critical patent/CN102441374A/en
Publication of CN102441374A publication Critical patent/CN102441374A/en
Pending legal-status Critical Current

Links

Landscapes

  • Catalysts (AREA)

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

A kind of selective hydrocatalyst
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.
Figure BSA00000300467100061
Figure BSA00000300467100062
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
Figure BSA00000300467100064
The diolefin hydrogenation of table 3 embodiment 3 catalyst is active
Figure BSA00000300467100065
The monoene hydrogenation activity of table 4 embodiment 3 catalyst
Figure BSA00000300467100066
The monoene hydrogenation activity of table 5 embodiment 3 catalyst (T=70 ℃)
Figure BSA00000300467100071
The monoene hydrogenation activity of table 6 embodiment 3 catalyst (T=180 ℃)
Figure BSA00000300467100072
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.
CN201010504887XA 2010-10-12 2010-10-12 Selective hydrogenation catalyst and its preparation method and application Pending CN102441374A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010504887XA CN102441374A (en) 2010-10-12 2010-10-12 Selective hydrogenation catalyst and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010504887XA CN102441374A (en) 2010-10-12 2010-10-12 Selective hydrogenation catalyst and its preparation method and application

Publications (1)

Publication Number Publication Date
CN102441374A true CN102441374A (en) 2012-05-09

Family

ID=46004606

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010504887XA Pending CN102441374A (en) 2010-10-12 2010-10-12 Selective hydrogenation catalyst and its preparation method and application

Country Status (1)

Country Link
CN (1) CN102441374A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104028293A (en) * 2014-06-24 2014-09-10 常州大学 Method for preparing low-temperature nitrogen-doped graphene supported nano Pd hydrogenation catalyst
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
CN105944752A (en) * 2016-04-27 2016-09-21 武汉凯迪工程技术研究总院有限公司 Selective hydrogenation catalyst for producing aviation kerosene and preparation method and application thereof
CN106268901A (en) * 2016-07-18 2017-01-04 刘义林 A kind of nitrogen-doped graphene load P d/Ni catalyst and preparation method thereof
CN106810419A (en) * 2015-11-30 2017-06-09 山东华鲁恒升化工股份有限公司 For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof
CN106964355A (en) * 2017-03-27 2017-07-21 江苏金聚合金材料有限公司 The preparation method and applications of the graphene-based catalyst of supported copper nickel oxide
CN109174085A (en) * 2018-09-06 2019-01-11 中国科学院金属研究所 Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application
CN109304182A (en) * 2017-07-28 2019-02-05 中国科学院宁波材料技术与工程研究所 Handle the Hydrobon catalyst and the preparation method and application thereof of inferior oil material
CN111686726A (en) * 2019-03-15 2020-09-22 中石化南京化工研究院有限公司 Preparation method and application of novel carbon-based noble metal catalyst
CN112717923A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof
CN116477610A (en) * 2023-06-09 2023-07-25 西南石油大学 Graphene nano-sheet prepared from magnesium-containing wastewater and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KOU RONG,ET AL.: "Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction", 《ELECTROCHEMISTRY COMMUNICATIONS》 *
SI YONGCHAO, ET AL.: "Exfoliated graphere separated by platinum nanoparticles", 《CHEMISTRY OF MATERIALS》 *
ZHONG JIN, ET AL.: "Decoration, Migration, and Aggregation of Palladium Nanoparticles on Graphene Sheets", 《CHEMISTRY OF MATERIALS》 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028293A (en) * 2014-06-24 2014-09-10 常州大学 Method for preparing low-temperature nitrogen-doped graphene supported nano Pd hydrogenation catalyst
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
CN105727954B (en) * 2014-12-06 2018-01-16 中国石油化工股份有限公司 A kind of preparation method of synthesis gas preparing natural gas catalyst
CN106810419A (en) * 2015-11-30 2017-06-09 山东华鲁恒升化工股份有限公司 For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof
CN106810419B (en) * 2015-11-30 2020-10-20 山东华鲁恒升化工股份有限公司 Graphene-loaded metal compound for preparing ethanol catalyst by acetic acid hydrogenation and preparation method thereof
CN105944752A (en) * 2016-04-27 2016-09-21 武汉凯迪工程技术研究总院有限公司 Selective hydrogenation catalyst for producing aviation kerosene and preparation method and application thereof
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
WO2017185928A1 (en) * 2016-04-27 2017-11-02 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 therefor
WO2017185929A1 (en) * 2016-04-27 2017-11-02 武汉凯迪工程技术研究总院有限公司 Selective hydrogenation catalyst used for producing aviation fuel, and method for preparation thereof and application thereof
CN106268901A (en) * 2016-07-18 2017-01-04 刘义林 A kind of nitrogen-doped graphene load P d/Ni catalyst and preparation method thereof
CN106964355A (en) * 2017-03-27 2017-07-21 江苏金聚合金材料有限公司 The preparation method and applications of the graphene-based catalyst of supported copper nickel oxide
CN109304182A (en) * 2017-07-28 2019-02-05 中国科学院宁波材料技术与工程研究所 Handle the Hydrobon catalyst and the preparation method and application thereof of inferior oil material
CN109174085B (en) * 2018-09-06 2021-06-25 中国科学院金属研究所 Atomic-level dispersed palladium-based nano-diamond/graphene composite material catalyst and preparation method and application thereof
CN109174085A (en) * 2018-09-06 2019-01-11 中国科学院金属研究所 Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application
CN111686726A (en) * 2019-03-15 2020-09-22 中石化南京化工研究院有限公司 Preparation method and application of novel carbon-based noble metal catalyst
CN111686726B (en) * 2019-03-15 2023-11-17 中石化南京化工研究院有限公司 Preparation method and application of carbon-based noble metal catalyst
CN112717923A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof
CN112717923B (en) * 2019-10-28 2024-05-31 中国石油化工股份有限公司 Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof
CN116477610A (en) * 2023-06-09 2023-07-25 西南石油大学 Graphene nano-sheet prepared from magnesium-containing wastewater and preparation method and application thereof
CN116477610B (en) * 2023-06-09 2023-09-12 西南石油大学 Graphene nano-sheet prepared from magnesium-containing wastewater and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN102441374A (en) Selective hydrogenation catalyst and its preparation method and application
CN101920200B (en) Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis
CN111233626B (en) Method for preparing benzhydrol by diphenyl ketone hydrogenation
CN101745389A (en) A kind of egg-shell catalyst that is used for preparation of ethylene through selective hydrogenation of acetylene
CN102220168B (en) Method for selective hydrogenation of pyrolysis gas
CN114849694B (en) Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof
CN101875009B (en) C3 fraction selective hydrogenation catalyst and preparation method thereof
CN101462051B (en) Catalyst for generating crotonyl alcohol by selective hydrogenation of gas-phase crotonaldehyde and preparation method thereof
CN1269567C (en) Novel catalyst for methanol cracking reaction to produce CO and H2
CN102908957A (en) Method for Fischer-Tropsch synthesis
CN111589464B (en) Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof
CN117772253A (en) Carbon nitride-based catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN103785411B (en) A kind of dehydrogenation with silicon oxide as carrier and preparation method thereof
CN100451044C (en) Catalyst for preparing C5 hydrogenated petroleum resin, and its preparing method
CN105732274B (en) Ethylene selective hydrogenation refining method
CN102794178A (en) Selective hydrogenation catalyst and preparation thereof
CN102633591B (en) Catalytic conversion technology for carbon tetrachloride
CN115445612A (en) Dehydrogenation catalyst, preparation method and application thereof, and method for preparing benzene ring by cyclohexane dehydrogenation
CN111569872B (en) Active carbon-palladium-gallium-tin liquid alloy composite catalyst and preparation method and application thereof
US11318446B2 (en) Activated carbon/Pd-Ga liquid alloy composite catalyst, preparation method and use thereof
CN102441387B (en) Method for preparing high-activity cobalt-based Fischer-Tropsch synthetic catalyst
CN110721681B (en) Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application
CN106582780B (en) Alloy-type heavy aromatics lightening catalyst and preparation method thereof
CN114931959B (en) Catalyst for hydrogen production by light hydrocarbon conversion
CN113368870B (en) Sulfur ligand modified monoatomic catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120509