CN107008255B - Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene - Google Patents
Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene Download PDFInfo
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- CN107008255B CN107008255B CN201710264249.7A CN201710264249A CN107008255B CN 107008255 B CN107008255 B CN 107008255B CN 201710264249 A CN201710264249 A CN 201710264249A CN 107008255 B CN107008255 B CN 107008255B
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- normal butane
- butylene
- platinum catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002113 nanodiamond Substances 0.000 title claims abstract description 55
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 25
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000004280 Sodium formate Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 11
- 235000019254 sodium formate Nutrition 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- SYRIRLOOSKFSFC-UHFFFAOYSA-N butane Chemical compound CCCC.CCCC SYRIRLOOSKFSFC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- -1 propylene, ethylene, butylene Chemical group 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The Nano diamond platinum catalyst and its preparation method and application that the invention discloses a kind of for normal butane direct dehydrogenation butylene, belongs to organic chemical industry's raw material preparation technical field.The method comprises the steps of firstly, preparing Nano diamond carriers, then Pt particle is supported on Nano diamond by the method for formic acid sodium reduction, obtain the Nano diamond platinum catalyst.The Nano diamond platinum catalyst is used for the reaction of normal butane direct dehydrogenation, the use temperature of catalyst is 400~500 DEG C；Catalytic reaction condition are as follows: 1000~18000ml/gh of air speed, normal butane volumetric concentration 1~5%, normal butane and hydrogen volume ratio 1:(0.5~5)；The catalyst performance stabilised, catalytic activity is good, can effectively be catalyzed normal butane dehydrogenation, no pollution to the environment, environment-friendly high-efficiency at a lower temperature.
Description
Technical field
The present invention relates to organic chemical industry's raw material preparation technical fields, and in particular to one kind is used for normal butane direct dehydrogenation system
Nano diamond platinum catalyst of butylene and its preparation method and application.
Background technique
Low olefine such as propylene, ethylene, butylene are important industrial chemicals, wherein butylene is the centre of important chemical
Product is the important petrochemical industry base stock for being only second to ethylene and propylene for producing rubber, plastics and other polymers.
As Downstream Market especially auto manufacturing constantly expands scale, the market demand of butylene increases year by year.So (just butane
Butane or iso-butane) to become alkene significant for dehydrogenation.It is steam cracking and fluid catalytic cracking (FCC) naphtha, light-duty
Diesel oil and other petroleum by-products are to obtain low olefine most popular method.But the production process energy consumption height of these methods,
Low yield, easy carbon distribution, and face oil reserve and reduce and the problems such as rise in price, so finding more economical raw material and opening
Sending out more effective technique becomes urgent problem to be solved.
Nowadays, with the promotion of the oil plant level of crude oil processing and increasing substantially for ethylene production capacity, by-product
C4Paraffin production increases rapidly, and normal butane has as one of its main component by catalytic material dehydrogenation production of normal butane
The butylene and butadiene of high added value have high economic value.But current domestic most enterprises, China are to cracking C4The change of hydrocarbon
Work utilization rate only has 30% or so and concentrates on butadiene therein, part isobutene and a small amount of n-butene, most of C4Alkane
Hydrocarbon resource is wasted as fuel.And the U.S. is to C4The chemical utilization rate of hydrocarbon early has reached 80%~90%, and Japan is 64%,
West Europe is 60%, therefore how rationally efficiently to utilize C4Alkane has become the research hotspot of domestic and international catalyst operation person.
Butane direct dehydrogenation is strong endothermic reaction by thermodynamic (al) limitation, to obtain high conversion and need high reaction temperature
And low butane partial pressure.Under 1bar, 550-750 DEG C of temperature range the conversion ratio of butane dehydrogenation alkene can >=50%, so
Butane dehydrogenation temperature is generally at 500 DEG C or more.But high temperature will lead to the generation of high energy consumption and cracking and coking, make selective drop
It is low.Therefore, it is particularly significant to develop the catalyst that highly selective and anti-carbon is had excellent performance.
The catalyst that industrial butane direct dehydrogenation uses be usually noble metal base (such as Pt system, Rh system, Ir system, Pd system) and
Metal oxide base (such as V2O、Cr2O3、Fe2O3、MoO3, ZnO) catalyst, wherein carried noble metal Pt, metal oxide
CrOX, Ga, In etc. be widely studied.Pt is the transition metal of the low paraffin dehydrogenation of most effective catalysis, industrially uses Pt-
Sn/Al2O3Catalyst, while K or Li are added as auxiliary agent.Due to Al2O3For the support type monometallic Pt catalyst of carrier
Selectivity and stability are poor, and need to adding the second metal and auxiliary agent, (common co-catalyst is mainly alkali metal, alkaline-earth metal and dilute
Soil metal oxide is such as: Sr, K, Na, Ca, Cr) it is respectively used to improve carrier surface pH value, electron density, reduce Pt particle
Coking and the acidic site for neutralizing carrier surface, to improve the carbon accumulation resisting ability and catalytic efficiency of catalyst.Optimization Pt system urges
The method of agent is mainly improved carrier, the second metal of addition and addition auxiliary agent, so, the report about Pt catalyst system at present
Road focuses primarily upon on the study on the modification of carrier and auxiliary agent.
Others be catalyzed the catalyst of low paraffin dehydrogenation there are also chromated oxide base catalyst, vanadium oxide-based catalyst,
Gallium oxide base catalyst.500~600 DEG C of the reaction temperature for the catalyst reported at present, conversion ratio about 20~55%, react
Testing time was at 5~10 hours.In recent years, Carbon Materials were because of its high-specific surface area, good carbon accumulation resisting ability, low cost, lightweight
And it is environmental-friendly and be used as catalyst and as catalyst carrier.By the optimization to catalyst, it is catalyzed the effect of butane dehydrogenation
Rate has obtained certain raising, but develops efficient catalyst and be still an important issue project.
Summary of the invention
For current catalytic dehydrogenation required temperature height, the easy coking of catalyst, the not high problem of catalytic efficiency, mesh of the invention
Be to provide a kind of Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene,
When the catalyst is used for normal butane direct dehydrogenation butylene, it is added without the second metal and auxiliary agent, and can have at a lower temperature
The catalysis normal butane dehydrogenation of effect is butylene.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of Nano diamond platinum catalyst for normal butane direct dehydrogenation butylene, which is by nanogold
Hard rock carrier and Pt particle composition, Pt particle is with small size uniform load in Nano diamond carrier surface.
In the Nano diamond platinum catalyst, the content of platinum is 0.5~1.0wt.%.
The size of the Pt particle is 1~1.5nm.
The Nano diamond platinum catalyst the preparation method comprises the following steps: prepare Nano diamond carrier first, then pass through
Pt particle is supported on Nano diamond carrier to arrive the Nano diamond platinum carried catalysis by the method for formic acid sodium reduction
Agent.This method specifically comprises the following steps:
(1) preparation of Nano diamond carrier:
Nano diamond raw material is subjected to high-temperature roasting processing, the Nano diamond after obtaining functionalization is nanometer Buddha's warrior attendant
Stone carrier；High-temperature roasting treatment process are as follows: Nano diamond raw material is placed in 900~1300 DEG C (can select difference as needed
Temperature), handled in the argon atmosphere of 80~100ml/min, handle the time 3~4 hours, nanometer obtained after calcination process
Diamond carrier；
(2) sodium formate restoring method:
It gained Nano diamond carrier (Nano diamond powder) will be mixed with deionized water after step (1) calcination process
It is made into suspension, is heated to 100 DEG C under stirring condition in oil bath pan, then sodium formate solid is added in suspension, stirs 1h
After be added dropwise chloroplatinic acid, cool down after reaction 1~2 hour and stand, filter it is dry after obtain the Nano diamond and carry platinum urging
Agent.
In above-mentioned steps (2), the molar ratio of the sodium formate and chloroplatinic acid is 1800:1, the additional amount of the chloroplatinic acid
It is calculated according to the amount of the Pt of load required on carrier, the deionized water is for dissolving sodium formate solid.
The Nano diamond platinum catalyst prepares butylene for normal butane direct dehydrogenation, the butylene be 1- butylene,
2- butylene and/or butadiene.
In the normal butane direct dehydrogenation reaction process, the use temperature of catalyst is 450~500 DEG C；Catalysis reaction item
Part are as follows: the volume ratio of 1000~18000ml/gh of air speed, normal butane volumetric concentration 1~5%, normal butane and hydrogen is 1:(0.5
~5).
After carrying out regeneration treatment after the catalyst use, the performance of catalyst is restored substantially, being capable of multiple Reusability.
The catalyst is pre-processed before use, preprocessing process are as follows: in 400~500 DEG C, flow velocity is 80~100ml/min
It is pre-processed 1~2 hour in hydrogen atmosphere.The specific surface area of hydrogen treat rear catalyst is 350~420m2/ g, pore volume 1.4
~1.5cm3/g。
The invention has the advantages that and the utility model has the advantages that
1. catalyst of the present invention is using novel carbon material-Nano diamond carries out functionalization as raw material, through high-temperature roasting
After obtain Nano diamond carrier, then Pt particle is supported on Nano diamond by the method for formic acid sodium reduction and is catalyzed
Agent.The advantages of preparation process is that Pt can be uniformly dispersed in Nano diamond surface with small size, can be had at 450 DEG C
To butylene, and after regeneration treatment catalyst, the performance of catalyst is restored substantially for the catalysis normal butane dehydrogenation of effect, can make repeatedly
With.
2. when using catalyst of the present invention, under conditions of being added without the second metal and auxiliary agent, (450 at lower temperature
DEG C) catalytic activity is good.Reaction initial conversion is up to dropping to 28% after 40%, 10 hour, and the selectivity of alkene is stablized
95% or more.After catalyst after reaction is regenerated, the ability of catalyst normal butane direct dehydrogenation is substantially extensive
It is multiple.
3. catalyst of the present invention is reusable, no pollution to the environment, environment-friendly high-efficiency.
Detailed description of the invention
Fig. 1 is that catalyst of the present invention is lived again performance summary figure.
Specific embodiment
The present invention is described in detail below in conjunction with attached drawing and embodiment.
The preparation process of used catalyst is as follows in following embodiment:
1. the preparation of Nano diamond carrier:
Nano diamond raw material is subjected to high-temperature roasting processing, the Nano diamond after obtaining functionalization is nanometer Buddha's warrior attendant
Stone carrier；High-temperature roasting treatment process are as follows: Nano diamond raw material is placed in the argon of 900~1300 DEG C and 80~100ml/min
It is handled, is handled the time 3~4 hours in gas atmosphere, Nano diamond carrier is obtained after calcination process
2. sodium formate restoring method:
To be fired processing after gained Nano diamond carrier (Nano diamond powder) mixed with deionized water be made into it is outstanding
Turbid is heated to 100 DEG C in oil bath pan under stirring condition, then sodium formate solid is added in suspension, after stirring 1h dropwise
Chloroplatinic acid is added, cools down after reaction 1~2 hour and stands, obtains the Nano diamond platinum catalyst after suction filtration is dry.Institute
The molar ratio for stating sodium formate and chloroplatinic acid is 1800:1, the additional amount of the chloroplatinic acid according to load required on carrier Pt
Amount calculate, the deionized water is for dissolving sodium formate solid.
Following embodiment 1-2 are different hydrogen treated catalyst catalytic performances.Embodiment 3-4 is living again for catalyst
Performance, total performance of living again are summarised in Fig. 1 in the form of catalyst performance figure.
Embodiment 1:
Catalyst performance test is carried out using fixed-bed reactor, before test first by catalyst in H2Under atmosphere
500 DEG C of reductase 12 hours.It is packed into silica wool in quartz glass reactor, weighs 50mg catalyst and is put into the middle part of silica wool, catalysis
Reactor is put into reaction unit there are about one centimetre of height by agent, is heated by Three-section type heating to catalyst bed, is first passed through He and blows
It sweeps 30 minutes, then heats to 450 DEG C.It is 18000ml/gh, nC in air speed4:H2It is passed through under conditions of=1:1, He balance anti-
Answer solid/liquid/gas reactions 10 hours.The composition of gas-chromatography on-line analysis reaction product is used during reaction.After reaction 10 minutes and 10 hours
As a result such as the following table 1:
N-butane conversion=(whole production concentrations after reaction/concentration for the normal butane being passed through) × 100%；
Butylene selectivity=(n-butene and butadiene concentration/whole production concentration after reaction) × 100%.
1 embodiment of table, 1 reaction process and result:
In table 1: Xi/Xf is conversion ratio after reaction 10 minutes/10 hours, and Si/Sf is selected after being reaction 10 minutes/10 hours
Property.
Embodiment 2:
Operation and catalyst amount by embodiment 1, in addition to the temperature of hydrogen treat catalyst is changed to 400 DEG C, remaining
Condition remains unchanged, reaction result such as the following table 2:
2 embodiment of table, 2 reaction process and result:
Embodiment 3:
Reaction in embodiment 1 is cooled down after carrying out 10 hours, while reaction gas is switched under He gas to catalysis
Agent is protected, until cooling to room temperature.Reactor both ends are dismantled with line connection, are exposed to catalyst in air,
300 DEG C are heated to, reactor connected back into pipeline after handling catalyst 1.5 hours in air, according to the operation of embodiment 1,
In addition to the reaction time becomes 8 hours, remaining each condition is constant, reaction result such as the following table 3:
3 embodiment of table, 3 reaction process and result:
In table 3: Xi/Xf: conversion ratio after reaction 10 minutes/8 hours, Si/Sf: selectivity after reaction 10 minutes/8 hours.
Embodiment 4:
In the present embodiment, catalyst using used catalyst in embodiment 3, remaining condition with 1 phase of embodiment
Together, reaction result such as the following table 4:
4 embodiment of table, 4 reaction process and result:
Examples detailed above only refers to, and has technical side that is similar with the present invention or extending from this patent thinking
Case, in protection scope of the present invention.
Claims (4)
1. a kind of application of the Nano diamond platinum catalyst for normal butane direct dehydrogenation butylene, it is characterised in that: institute
It states Nano diamond platinum catalyst to be made of Nano diamond carrier and Pt particle, Pt uniform particle is carried on a nanometer Buddha's warrior attendant
Stone carrier surface；The Nano diamond platinum catalyst prepares butylene for normal butane direct dehydrogenation；
In the normal butane direct dehydrogenation reaction process, the use temperature of catalyst is 450~500 DEG C；Catalytic reaction condition are as follows:
The volume ratio of 1000~18000ml/gh of air speed, normal butane volumetric concentration 1~5%, normal butane and hydrogen is 1:(0.5~5)；
In the Nano diamond platinum catalyst, the content of platinum is 0.5~1.0wt.%, and the size of the Pt particle is 1nm
~1.5nm；
The preparation process of the catalyst are as follows: Nano diamond carrier is prepared first, then by the method for formic acid sodium reduction by Pt
Particle is supported on Nano diamond carrier to arrive the Nano diamond platinum catalyst；Preparing for the catalyst is specific
Include the following steps:
(1) preparation of Nano diamond carrier:
Nano diamond raw material is subjected to high-temperature roasting processing, the Nano diamond after obtaining functionalization is that Nano diamond carries
Body；High-temperature roasting treatment process are as follows: Nano diamond raw material is placed in 900~1300 DEG C and 80~100ml/min of argon gas gas
It is handled, is handled the time 3~4 hours in atmosphere, Nano diamond carrier is obtained after calcination process；
(2) sodium formate restoring method:
Gained Nano diamond carrier it will be mixed with deionized water after step (1) calcination process and be made into suspension, in oil bath pan
It is heated to 100 DEG C under middle stirring condition, then sodium formate solid is added in suspension, chloroplatinic acid is added dropwise after stirring 1h, instead
Cool down after answering 1~2 hour and stand, obtains the Nano diamond platinum catalyst after filtering drying.
2. the Nano diamond platinum catalyst according to claim 1 for normal butane direct dehydrogenation butylene is answered
With, it is characterised in that: in step (2), the molar ratio of the sodium formate and chloroplatinic acid is 1800:1, the addition of the chloroplatinic acid
Amount is calculated according to the amount of the Pt of load required on carrier.
3. the Nano diamond platinum catalyst according to claim 1 for normal butane direct dehydrogenation butylene is answered
With, it is characterised in that: after carrying out regeneration treatment after the catalyst use, the performance of catalyst is restored substantially, can be repeatedly anti-
It is multiple to use.
4. the Nano diamond platinum catalyst according to claim 1 for normal butane direct dehydrogenation butylene is answered
With, it is characterised in that: the butylene is 1- butylene, 2- butylene and/or butadiene.
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| CN112403512B (en) * | 2020-11-27 | 2023-08-15 | 中科南京绿色制造产业创新研究院 | Platinum-based catalyst loaded by nano titanium-silicon molecular sieve, preparation method and application thereof |
| CN113694921B (en) * | 2021-05-28 | 2022-10-25 | 中国科学院金属研究所 | Nano-diamond/graphene composite carrier loaded atomic-scale dispersed iridium cluster catalyst and preparation method and application thereof |
| CN113398908B (en) * | 2021-05-28 | 2022-09-13 | 中国科学院金属研究所 | Monatomic iridium-based nano diamond/graphene composite material catalyst and preparation method and application thereof |
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