CN105709727A - Preparation method for low-carbon alkane dehydrogenation catalyst with concentrated platinum grain size distribution - Google Patents
Preparation method for low-carbon alkane dehydrogenation catalyst with concentrated platinum grain size distribution Download PDFInfo
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- CN105709727A CN105709727A CN201410723845.3A CN201410723845A CN105709727A CN 105709727 A CN105709727 A CN 105709727A CN 201410723845 A CN201410723845 A CN 201410723845A CN 105709727 A CN105709727 A CN 105709727A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009826 distribution Methods 0.000 title claims description 15
- 229910052799 carbon Inorganic materials 0.000 title claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title description 36
- 229910052697 platinum Inorganic materials 0.000 title description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 74
- 239000001294 propane Substances 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 230000008569 process Effects 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 21
- 229910052700 potassium Inorganic materials 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 235000010333 potassium nitrate Nutrition 0.000 claims description 12
- 239000004323 potassium nitrate Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 2
- 239000012072 active phase Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- 239000008246 gaseous mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alkane aluminium oxide Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method for a propane dehydrogenation catalyst. The preparation method comprises the following steps: with Sn-containing alumina as a carrier, dipping the carrier in an alkali metal auxiliary agent K, carrying out drying and roasting, and then subjecting the carrier to heating reflux surface modification treatment with an organic matter solvent containing a hydroxyl group, wherein reflux temperature is 5 to 10 DEG C lower than the boiling point of the used solvent or mixed solvent and reflux time is 2 to 12 h; and after drying of a surface-modified sample containing Sn and alkali metal, loading an active component Pt by using an impregnation method and carrying out treatment in a mixed atmosphere of the hydroxyl-containing organic matter and hydrogen after drying so as to obtain the propane dehydrogenation catalyst, wherein the procedure of roasting is omitted. The catalyst prepared by using the method can prevent excess loss of alkali metal, obtain controllable Pt particles and form more secondary active phases, so the selectivity of the target product propylene and the activity, stability and sulfur resistance of the catalyst are improved eventually.
Description
Technical field
The preparation method that the present invention relates to the catalyst for dehydrogenation of low-carbon paraffin that a kind of platinum Grain size distribution is concentrated, the preparation method relating in particular to the catalyst for preparing propylene with propane dehydrogenation that the distribution of a kind of platinum crystal grain is concentrated.
Background technology
The exploitation application of North America shale gas makes Gas Prices declining to a great extent relative to crude oil price, also makes the raw material lighting of ethylene cracker simultaneously, and the yield of the side-product propylene causing oil to be raw material declines to a great extent.And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, is increasingly becoming a kind of trend.The propane of by-product in natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.) is carried out dehydrogenation reaction and produces the effective way that propylene is this problem of solution.In recent years, dehydrogenating propane produced the technology of propylene and achieved large development, had become as the third-largest propylene production.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, and carbon deposit is always up affecting the reason of catalyst activity and stability with active metal sintering.Due to the shortening of catalyst life under relatively low conversion of propane and harsh reaction condition, PDH method is made to be restricted when commercial Application.Therefore, develop the catalyst for preparing propylene with propane dehydrogenation with high activity, high selectivity and high stability and become the key of this technology.Patent CN1201715 discloses the Pt-Sn-K/Al for low-carbon alkanes (C1 ~ C5) dehydrogenation2O3The preparation method of catalyst.Patent CN101066532 discloses a kind of method adopting Hydrothermal Synthesis that Sn is incorporated into ZSM-5 molecular sieve skeleton, and for propane dehydrogenation catalyst carrier, the catalyst obtained runs 100h, conversion of propane 30%, Propylene Selectivity more than 99%.CN1579616 patent provide a kind of with macropore, low heap ratio, there is the γ-Al of double-pore structure2O3Bead is carrier, for the catalyst of linear alkanes dehydrogenation, by the modulation of catalyst, can improve the reactivity worth of dehydrogenating low-carbon alkane.USP4,914,075 disclose propane and Pt that other dehydrogenating low-carbon alkane aluminium oxide is carrier is catalyst based, have high alkane conversion and olefine selective.USP6,103,103 disclose a kind of with borosilicate and alkali metal for carrier, and platinum group metal active metal, zinc is the dehydrogenation of auxiliary agent, shows good dehydrogenation.Although catalyst of the prior art can show certain performance under some reaction condition, but tends not to take into account in catalyst activity, stability, selectivity of product and preparation economy etc..In traditional technology, in order to improve stability and the selectivity of catalyst, the often method of high-temperature vapor dechlorination after employing leaching Pt.But high-temperature vapor dechlorination can cause the destruction of carrier specific surface area, pore structure, weaken PtSn and interact, ultimately result in the agglomeration of Pt granule, reduce conversion of propane.How to control Pt granule, improve its Sulfur tolerance, thus the activity stability of the selectivity and catalyst improving target product olefins is the focus of research.
Summary of the invention
For the deficiencies in the prior art, the preparation method that the present invention provides a kind of propane dehydrogenation catalyst, catalyst prepared by the method is it can be avoided that too much alkali metal runs off, realize controlled Pt granule, define more secondary activity phase, finally improve selectivity and the activity of catalyst, stability and the Sulfur tolerance of target product propylene.
The preparation method of the propane dehydrogenation catalyst that the present invention relates to, including following process: with containing Sn aluminium oxide for carrier, first dipping alkali metal promoter K, adopting hydroxyl Organic substance solvent that it is heated reflow surface modification after drying and roasting, reflux temperature is lower than solvent for use or mixed solvent boiling point 5 DEG C ~ 10 DEG C；Return time is 2h ~ 12h, it is preferred to 4h ~ 8h；After surface modification containing after Sn and alkali-metal sample drying, adopt infusion process load active component Pt, omitting roasting process, directly under the mixed atmosphere containing hydroxyl Organic substance and hydrogen, processing costs obtains propane dehydrogenation catalyst after drying, and treatment temperature is 260 DEG C ~ 360 DEG C, it is preferably 280 DEG C ~ 340 DEG C, the process time is 0.5h ~ 8h, it is preferred to 1h ~ 4h, and processing pressure is not more than 150kPa(absolute pressure), it is preferably 5kPa ~ 130kPa(absolute pressure), mixing gas space velocity is 200h-1~2500h-1, it is preferred to 500h-1~2000h-1, in mixing gas, the organic concentration of hydroxyl is 5v% ~ 30v%, it is preferred to 10v% ~ 25v%；The concentration of hydrogen is 20v% ~ 70v%, it is preferred to 30v% ~ 60v%.In the mixed atmosphere of above-mentioned hydroxyl Organic substance and hydrogen outside degasification phase hydroxyl Organic substance and hydrogen, possibly together with noble gas.
The present invention relates to containing Sn alumina support, it is possible to for existing product, it is also possible to prepared by the method known by professional and technical personnel in the field.Above-mentioned can be spherical, bar shaped, microsphere or abnormity containing Sn alumina support, and particle equivalent diameter is 0.1mm ~ 5mm, it is preferred to 0.5mm ~ 2mm.Carrying alumina surface area per unit volume is 200m2/g~240m2/ g, pore volume is 0.60cm3/g~0.80cm3/ g.Above-mentioned can introduce in aluminium oxide conclusion of the business process containing the Sn in Sn alumina support, it is also possible to introduced by the mode of load, it is also possible in aluminium oxide forming process, kneading introduces.
The present invention relates in the preparation method of propane dehydrogenation catalyst, the carrying method of alkali metal promoter K is dipping method well known to those skilled in the art.The predecessor of K is that solubility is containing K salt, it is possible to be inorganic salt, it is also possible to be organic salt, it is preferred to potassium nitrate.The method of load K is as follows: weighs a certain amount of potassium nitrate and is dissolved in deionized water, then solution is added to a certain amount of containing in Sn alumina support, aged at room temperature 2h ~ 16h, it is preferably 4h ~ 8h, then through 40 DEG C ~ 160 DEG C dry 2h ~ 16h, it is preferably 80 DEG C ~ 120 DEG C dry 4h ~ 8h, then at 300 DEG C ~ 800 DEG C roasting 2h ~ 16h, it is preferred to 400 DEG C ~ 700 DEG C roasting 4h ~ 8h.
In the inventive method, hydroxy-containing compounds is one or more in methanol, ethanol, propanol, isopropanol, it is preferred to methanol, ethanol or the two mixed solvent.Concrete Process of Surface Modification is as follows: heating evacuation containing Sn, K alumina support and process, temperature is 60 DEG C ~ 100 DEG C, it is preferred to 70 DEG C ~ 90 DEG C, in vacuum system, pressure is lower than 30kPa(absolute pressure), it is preferably less than 20kPa(absolute pressure), the process time is 0.5h ~ 8h, it is preferred to 1h ~ 4h.It is down to room temperature, under negative pressure state, adds hydroxyl Organic substance solvent, stop evacuation, be heated to reflux.Add the solvent volume pore volume more than handled sample.Then turn off backflow, solvent evaporated.
The present invention relates to the active metal component Pt of propane dehydrogenation catalyst adopts infusion process to be carried on containing in Sn alumina support, and loading process is method well known to those skilled in the art.Such as: first adopt the alumina support containing Sn of the aqueous impregnation containing Pt, ageing time 1h ~ 16h, it is preferable that 4h ~ 8h.Drying after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, it is preferred to dry 4h ~ 8h at 80 DEG C ~ 120 DEG C.The above-mentioned aqueous solution containing Pt is prepared by the inorganic metal salt containing Pt, and the wherein said inorganic metal salt containing Pt is preferably chloroplatinic acid.
A kind of propane dehydrogenation catalyst adopting said method to prepare, in catalyst, Pt counts weight percentage for 0.1% ~ 1.0% with element, it is preferred to 0.4% ~ 0.8%；Sn counts weight percentage for 0.5% ~ 10% with element, it is preferable that 1% ~ 3%；K is with element wt meter percentage composition for 0.5% ~ 10%, it is preferable that 1% ~ 3%, and the particle size of Pt is at 2 ~ 10nm, it is preferred to the particle size distribution of 4 ~ 8nm, 4nm ~ 8nm scope Pt crystal grain is 80% ~ 100%, it is preferred to 90% ~ 100%.
The application of above-mentioned propane dehydrogenation catalyst, with propane for raw material, in propane feed, sulfur-containing compound is calculated as 30ppm-150ppm with sulfur content, it is preferred to 50ppm-120ppm.
In the present invention, the preferential load of alkali metal on the alumina support, better controls the acidic site of carrier surface, it also avoid the loss of alkaline components in course of reaction.Use hydroxyl Organic substance solvent that load Sn and alkali-metal alumina support are carried out surface modification, when reducing supporting Pt, introduce the competitive adsorbates such as hydrochloric acid.Additionally, sample after load active component Pt does not need roasting, also without carrying out steam dechlorination process, the gaseous mixture of hydroxyl Organic substance and hydrogen is directly used to process, composition by modulation process temperature and gaseous mixture, utilize remaining a small amount of halogen reduction to the organic nucleophilic displacement of fluorine of hydroxyl and hydrogen in skeleton, not only can control Pt particle size, improve selectivity of catalyst, stability and resistance to SO_2, and define more secondary activity phase, limit such as Pt granule, platform, face, improve the activity of catalyst, it is prepared for the dehydrogenation without dechlorination and reduction process.Method for preparing catalyst of the present invention is simple, and mature technology is conducive to the commercial production of catalyst.
Accompanying drawing explanation
Fig. 1 is embodiment 6 gained catalyst transmission electron microscope picture.
Detailed description of the invention
Below by the enforcement of dehydrogenating propane, the technology of the present invention is described further.
Example 1
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 80 DEG C of dry 8h, roasting 4h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 70 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowers the temperature, adds 100mL methanol, reply normal pressure, be heated to reflux, heating-up temperature 55 DEG C, process time 4h after processing 1h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 4h, 80 DEG C of dry 8h.Dried sample is placed in tubular heater, is warming up to 280 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after methanol gasifying, and wherein methanol concentration is 20v%, and density of hydrogen is 50v%, is cut in heating furnace, and gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-1, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 91%.Appreciation condition: at 610 DEG C, the mass space velocity of propane is 3h-1, pressure 0.1MPa(gauge pressure) and carry out dehydrogenating propane reaction under condition, catalyst makes consumption 3g, sulfur-bearing 90ppm in propane feed.Evaluation result is in Table 1.
Example 2
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 6h, 100 DEG C of dry 6h, roasting 6h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowers the temperature, adds 100mL methanol, reply normal pressure, be heated to reflux, heating-up temperature 60 DEG C, process time 4h after processing 2h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 4h, 100 DEG C of dry 6h.Dried sample is placed in tubular heater, is warming up to 340 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after methanol gasifying, and wherein methanol concentration is 20v%, and density of hydrogen is 50v%, is cut in heating furnace, and gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-2, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 97%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 80ppm.Evaluation result is in Table 1.
Example 3
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 8h, 120 DEG C of dry 4h, roasting 8h in 400 DEG C.After roasting, sample is placed in Rotary Evaporators, and 70 DEG C of evacuation process, and system absolute pressure controls at below 15kPa, lowers the temperature, adds 100mL ethanol, reply normal pressure, be heated to reflux, heating-up temperature 70 DEG C, process time 4h after processing 4h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 6h, 120 DEG C of dry 4h.Dried sample is placed in tubular heater, is warming up to 280 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after methanol gasifying, and wherein methanol concentration is 10v%, and density of hydrogen is 60v%, is cut in heating furnace, and gaseous mixture volume space velocity is 2000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 4h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-3, in catalyst, the content of each component is: Pt0.4wt%, Sn1.0wt%, K2.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 93%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 80ppm.Evaluation result is in Table 1.
Example 4
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 6h, 120 DEG C of dry 4h, roasting 4h in 700 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowering the temperature after processing 2h, adding 100mL mol ratio is the methanol of 3:1, alcohol mixed solvent, replys normal pressure, it is heated to reflux, heating-up temperature 66 DEG C, processes time 6h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 4h, 100 DEG C of dry 4h.Dried sample is placed in tubular heater, is warming up to 300 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after methanol gasifying, and wherein methanol concentration is 25v%, and density of hydrogen is 50v%, is cut in heating furnace, and gaseous mixture volume space velocity is 500h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-4, in catalyst, the content of each component is: Pt0.4wt%, Sn1.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 95%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
Example 5
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 80 DEG C of dry 8h, roasting 6h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowering the temperature after processing 2h, adding 100mL mol ratio is the methanol of 1:1, alcohol mixed solvent, replys normal pressure, it is heated to reflux, heating-up temperature 62 DEG C, processes time 4h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 8h, 80 DEG C of dry 8h.Dried sample is placed in tubular heater, is warming up to 300 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after the gasification of methanol, ethanol, wherein methanol concentration is 10v%, and concentration of alcohol is 10v%, and density of hydrogen is 50v%, being cut in heating furnace, gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-5, in catalyst, the content of each component is: Pt0.8wt%, Sn3.0wt%, K2.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 95%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
Example 6
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowers the temperature, adds 100mL methanol, reply normal pressure, be heated to reflux, heating-up temperature 58 DEG C, process time 6h after processing 2h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dried sample is placed in tubular heater, is warming up to 320 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after the gasification of methanol, ethanol, wherein methanol concentration is 15v%, and concentration of alcohol is 5v%, and density of hydrogen is 50v%, being cut in heating furnace, gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-6, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 96%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
Example 7
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowers the temperature, adds 100mL methanol, reply normal pressure, be heated to reflux, heating-up temperature 58 DEG C, process time 6h after processing 2h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dried sample is placed in tubular heater, is warming up to 320 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after the gasification of methanol, ethanol, wherein methanol concentration is 5v%, and concentration of alcohol is 15v%, and density of hydrogen is 40v%, being cut in heating furnace, gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst C-7, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 96%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
Comparative example 1
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 100 DEG C of dry 6h, roasting 4h in 600 DEG C, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h, dry roasting.After roasting, sample is placed in tubular heater, is warming up to 260 DEG C in a nitrogen atmosphere, mixes with hydrogen, nitrogen after the gasification of methanol, ethanol, wherein methanol concentration is 15v%, and concentration of alcohol is 5v%, and density of hydrogen is 50v%, being cut in heating furnace, gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst D-1, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 43%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
Comparative example 2
Weigh alumina support containing a certain amount of Sn (spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g, following example all use this carrier) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.Weigh a certain amount of potassium nitrate and be dissolved in deionized water, be settled to 27mL, add to 30g containing in Sn alumina sample, aging 4h, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.After roasting, sample is placed in Rotary Evaporators, and 80 DEG C of evacuation process, and system absolute pressure controls at below 10kPa, lowers the temperature, adds 100mL methanol, reply normal pressure, be heated to reflux, heating-up temperature 58 DEG C, process time 6h after processing 2h.Then turn off backflow, solvent evaporated, it is thus achieved that the alumina support sample containing Sn, K.Weigh a certain amount of chloroplatinic acid again and be dissolved in deionized water, be settled to 27mL, add to the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dried sample is placed in tubular heater, is warming up to 260 DEG C in a nitrogen atmosphere, and the mixing gas of incision hydrogen and nitrogen, density of hydrogen is 60v%, and gaseous mixture volume space velocity is 1000h-1, controlling system pressure is 120kPa(absolute pressure), constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Obtaining catalyst D-2, in catalyst, the content of each component is: Pt0.6wt%, Sn3.0wt%, K1.0wt%.The particle size distribution of 4nm-8nm scope Pt crystal grain is 38%.Appreciation condition, with embodiment 1, is different in that in propane feed sulfur-bearing 120ppm.Evaluation result is in Table 1.
The reactivity worth of table 1 catalyst
Claims (20)
1. the preparation method of a propane dehydrogenation catalyst, it is characterized in that: include following process: with containing Sn aluminium oxide for carrier, first dipping alkali metal promoter K, adopting hydroxyl Organic substance solvent that it is heated reflow surface modification after drying and roasting, reflux temperature is lower than solvent for use or mixed solvent boiling point 5 DEG C ~ 10 DEG C；Return time is 2h ~ 12h；After surface modification containing after Sn and alkali-metal sample drying, adopt infusion process load active component Pt, omit roasting process, dried directly process under the mixed atmosphere containing hydroxyl Organic substance and hydrogen prepares propane dehydrogenation catalyst, treatment temperature is 260 DEG C ~ 360 DEG C, the process time is 0.5h ~ 8h, and processing pressure is not more than 150kPa(absolute pressure), mixing gas space velocity is 200h-1~2500h-1, in mixing gas, the organic concentration of hydroxyl is 5v% ~ 30v%, and the concentration of hydrogen is 20v% ~ 70v%.
2. method according to claim 1, it is characterised in that: return time is 4h ~ 8h；Treatment temperature is 280 DEG C ~ 340 DEG C, and the process time is 1h ~ 4h, and processing pressure is 5kPa ~ 130kPa(absolute pressure), mixing gas space velocity is 500h-1~2000h-1, in mixing gas, the organic concentration of hydroxyl is 10v% ~ 25v%；The concentration of hydrogen is 30v% ~ 60v%.
3. method according to claim 1, it is characterised in that: being spherical, bar shaped, microsphere or abnormity containing Sn alumina support, particle equivalent diameter is 0.1mm ~ 5mm.
4. method according to claim 1, it is characterised in that: carrying alumina surface area per unit volume is 200m2/g~240m2/ g, pore volume is 0.60cm3/g~0.80cm3/g。
5. method according to claim 1, it is characterised in that: introduce in aluminium oxide conclusion of the business process containing the Sn in Sn alumina support, or introduced by the mode of load, or kneading introduces in aluminium oxide forming process.
6. method according to claim 1, it is characterised in that: the predecessor of alkali metal promoter K is that solubility is containing K salt, inorganic salt or organic salt.
7. method according to claim 1, it is characterized in that: the method for load K is as follows: weigh potassium nitrate and be dissolved in deionized water, then solution is added containing in Sn alumina support, aged at room temperature 2h ~ 16h, then through 40 DEG C ~ 160 DEG C dry 2h ~ 16h, then at 300 DEG C ~ 800 DEG C roasting 2h ~ 16h.
8. method according to claim 7, it is characterised in that: drying is 80 DEG C ~ 120 DEG C dry 4h ~ 8h, and roasting is 400 DEG C ~ 700 DEG C roasting 4h ~ 8h.
9. method according to claim 1, it is characterised in that: hydroxy-containing compounds is one or more in methanol, ethanol, propanol, isopropanol.
10. method according to claim 9, it is characterised in that: hydroxy-containing compounds is methanol, ethanol or the two mixed solvent.
11. method according to claim 1, it is characterized in that: be heated to reflux surface modification treatment detailed process as follows: first heating evacuation containing Sn, K alumina support and process, temperature is 60 DEG C ~ 100 DEG C, and in vacuum system, pressure is lower than 30kPa, the process time is 0.5h ~ 8h, then it is down to room temperature, under negative pressure state, adds hydroxyl Organic substance solvent, stop evacuation, it is heated to reflux, add the solvent volume pore volume more than handled sample, finally stop backflow, solvent evaporated.
12. method according to claim 11, it is characterised in that: temperature is 70 DEG C ~ 90 DEG C, and in vacuum system, pressure is lower than 20kPa, and the process time is 1h ~ 4h.
13. method according to claim 1, it is characterised in that: active metal component Pt adopts infusion process to be carried on containing in Sn alumina support.
14. method according to claim 13, it is characterised in that: first adopting the alumina support containing Sn of the aqueous impregnation containing Pt, ageing time 1h ~ 16h, dry after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h.
15. method according to claim 13, it is characterised in that: ageing time 4h ~ 8h, drying is dry 4h ~ 8h at 80 DEG C ~ 120 DEG C.
16. method according to claim 14, it is characterised in that: the aqueous solution containing Pt is prepared by the inorganic metal salt containing Pt, and the wherein said inorganic metal salt containing Pt is chloroplatinic acid.
17. catalyst prepared by claim 1 to 16 either method, it is characterized in that: in catalyst, Pt counts weight percentage for 0.1% ~ 1.0% with element, Sn counts weight percentage for 0.5% ~ 10% with element, and K is with element wt meter percentage composition for 0.5% ~ 10%, and the particle size of Pt is at 2 ~ 10nm.
18. catalyst according to claim 17, it is characterised in that: in catalyst, Pt counts weight percentage for 0.4% ~ 0.8% with element；Sn counts weight percentage for 1% ~ 3% with element；K is with element wt meter percentage composition for 1% ~ 3%, and the particle size distribution that the particle size of Pt is 4 ~ 8nm, 4nm ~ 8nm scope Pt crystal grain is 80% ~ 100%.
19. the application of catalyst described in claim 17, it is characterised in that: with propane for raw material, in propane feed, sulfur-containing compound is calculated as 30ppm-150ppm with sulfur content.
20. the application of catalyst described in claim 19, it is characterised in that: in propane feed, sulfur-containing compound is calculated as 50ppm-120ppm with sulfur content.
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