CN105709727B - A kind of preparation method for the catalyst for dehydrogenation of low-carbon paraffin that platinum Grain size distribution is concentrated - Google Patents
A kind of preparation method for the catalyst for dehydrogenation of low-carbon paraffin that platinum Grain size distribution is concentrated Download PDFInfo
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- CN105709727B CN105709727B CN201410723845.3A CN201410723845A CN105709727B CN 105709727 B CN105709727 B CN 105709727B CN 201410723845 A CN201410723845 A CN 201410723845A CN 105709727 B CN105709727 B CN 105709727B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 title claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title description 45
- 238000009826 distribution Methods 0.000 title description 11
- 229910052799 carbon Inorganic materials 0.000 title description 8
- 239000012188 paraffin wax Substances 0.000 title description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000001294 propane Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000001802 infusion Methods 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 51
- 229910052700 potassium Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052718 tin Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 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 7
- 239000012072 active phase Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 11
- 239000008246 gaseous mixture Substances 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002309 gasification Methods 0.000 description 5
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 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 aluminum oxide Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 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
- 238000006555 catalytic reaction Methods 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000012071 phase 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
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of preparation method of propane dehydrogenation catalyst, including following process：Using aluminum oxide containing Sn as carrier, alkali metal promoter K is impregnated first, it is carried out using hydroxyl organic matter solvent to be heated to reflux surface modification treatment after drying and roasting, reflux temperature is less than 5 DEG C ~ 10 DEG C of solvent for use or mixed solvent boiling point；Return time is 2h ~ 12h；After the modified sample drying containing Sn and alkali metal in surface, using infusion process load active component Pt, roasting process is omitted, processing costs obtains propane dehydrogenation catalyst directly under the mixed atmosphere containing hydroxyl organic matter and hydrogen after drying.Catalyst prepared by this method can avoid excessive alkali metal from being lost in, and realize controllable Pt particles, form more secondary active phases, activity, stability and the Sulfur tolerance of the final selectivity and catalyst for improving target product propylene.
Description
Technical field
A kind of preparation method for the catalyst for dehydrogenation of low-carbon paraffin concentrated the present invention relates to platinum Grain size distribution, specifically
It is related to a kind of preparation method for the catalyst for preparing propylene with propane dehydrogenation that platinum crystal grain distribution is concentrated.
Background technology
The development and application of North America shale gas make Gas Prices declining to a great extent relative to crude oil price, while also cause second
The raw material lighting of alkene cracker, the yield for the byproduct propylene that oil is raw material is caused to decline to a great extent.And with oil
The increasingly scarcity of resource, the production of propylene is that raw material turns to the diversified technology path of raw material sources from the simple oil that relies on
Become, be increasingly becoming a kind of trend.By natural gas（Conventional gas, shale gas, coal bed gas, combustible ice etc.）The propane of middle by-product
It is the effective way for solving this problem to carry out dehydrogenation reaction and produce propylene.In recent years, the technology of dehydrogenating propane production propylene
Large development is achieved, has become the third-largest propylene production.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, carbon deposit and activity
Metal sintering is always the reason for influenceing catalyst activity and stability.Due to relatively low conversion of propane and harsh reaction bar
The shortening of catalyst life under part, makes PDH methods be restricted in commercial Application.Therefore, exploitation is with high activity, Gao Xuan
The catalyst for preparing propylene with propane dehydrogenation of selecting property and high stability turns into the key of the technology.Patent CN1201715, which is disclosed, to be used for
Low-carbon alkanes（C1~C5）The Pt-Sn-K/Al of dehydrogenation2O3The preparation method of catalyst.Patent CN101066532 discloses one kind and adopted
Sn is incorporated into the method for ZSM-5 molecular sieve skeleton with Hydrothermal Synthesiss, and is used for propane dehydrogenation catalyst carrier, obtained catalysis
Agent runs 100h, conversion of propane 30%, Propylene Selectivity more than 99%.CN1579616 patents provide one kind with macropore, low heap
Than, have double-pore structure γ-Al2O3Bead is carrier, for the catalyst of linear alkanes dehydrogenation, by the modulation of catalyst,
The reactivity worth of dehydrogenating low-carbon alkane can be improved.USP4,914,075 discloses propane and other dehydrogenating low-carbon alkane aluminum oxide are
The Pt base catalyst of carrier, there is high alkane conversion and olefine selective.USP6,103,103 discloses one kind with borosilicate
Hydrochlorate and alkali metal are carrier, and platinum group metal active metal, zinc is the dehydrogenation of auxiliary agent, shows preferable dehydrogenation
Energy.Although catalyst of the prior art can show certain performance under some reaction conditions, catalyst activity,
Stability, selectivity of product and preparation economy etc. tend not to take into account.In traditional technology, in order to improve catalyst
Stability and selectivity, often using the method for high-temperature vapor dechlorination after leaching Pt.But high-temperature vapor dechlorination can cause to carry
Surface area per unit volume product, the destruction of pore structure, PtSn interactions are weakened, the agglomeration of Pt particles is ultimately resulted in, reduces third
Alkane conversion ratio.Pt particles how are controlled, improve its Sulfur tolerance, so as to improve the work of the selectivity of target product olefins and catalyst
Property stability be research focus.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of propane dehydrogenation catalyst, prepared by this method
Catalyst excessive alkali metal can be avoided to be lost in, realize controllable Pt particles, form more secondary active phases, finally
Improve the selectivity of target product propylene and activity, stability and the Sulfur tolerance of catalyst.
The preparation method of propane dehydrogenation catalyst of the present invention, including following process：Using aluminum oxide containing Sn as carrier,
Alkali metal promoter K is impregnated first, and it be heated to reflux at the modification of surface using hydroxyl organic matter solvent after drying and roasting
Reason, reflux temperature are less than 5 DEG C ~ 10 DEG C of solvent for use or mixed solvent boiling point；Return time is 2h ~ 12h, preferably 4h ~ 8h；Table
After the modified sample drying containing Sn and alkali metal in face, using infusion process load active component Pt, roasting process is omitted, is dried
Directly processing costs obtains propane dehydrogenation catalyst under the mixed atmosphere containing hydroxyl organic matter and hydrogen afterwards, and treatment temperature is
260 DEG C ~ 360 DEG C, preferably 280 DEG C ~ 340 DEG C, processing time is 0.5h ~ 8h, preferably 1h ~ 4h, and processing pressure is not more than
150kPa（Absolute pressure）, the kPa of preferably 5 kPa ~ 130（Absolute pressure）, mixed gas air speed is 200h-1~2500h-1, it is preferably
500h-1~2000h-1, the concentration of hydroxyl organic matter is 5v% ~ 30v%, preferably 10v% ~ 25v% in mixed gas；Hydrogen it is dense
Spend for 20v% ~ 70v%, preferably 30v% ~ 60v%.Gas phase hydroxyl is removed in the mixed atmosphere of above-mentioned hydroxyl organic matter and hydrogen
Outside organic matter and hydrogen, also contain inert gas.
The present invention relates to alumina support containing Sn, can be existing product, can also be ripe by professional and technical personnel in the field
It is prepared by the method known.Above-mentioned alumina support containing Sn can be spherical, bar shaped, microballoon or abnormity, particle equivalent diameter 0.1
Mm ~ 5mm, preferably 0.5 mm ~ 2mm.Carrying alumina surface area per unit volume is 200 m2/g ~240 m2/ g, pore volume are 0.60 cm3/
g ~0.80 cm3/g.Sn in above-mentioned alumina support containing Sn can be introduced during aluminum oxide conclusion of the business, can also be by negative
The mode of load introduces, and kneading can also be introduced in aluminum oxide forming process.
The present invention relates in the preparation method of propane dehydrogenation catalyst, alkali metal promoter K carrying method is this area skill
Dipping method known to art personnel.K predecessor is soluble salt containing K, can be inorganic salts or organic salt, excellent
Elect potassium nitrate as.The method for loading K is as follows：Weigh a certain amount of potassium nitrate to be dissolved in deionized water, then add solution to one
Quantitatively in alumina support containing Sn, aging 2h ~ 16h, preferably 4h ~ 8h, then through 40 DEG C ~ 160 DEG C dry 2h ~ 16h at room temperature are excellent
Elect 80 DEG C ~ 120 DEG C dry 4h ~ 8h as, then 300 DEG C ~ 800 DEG C be calcined 2h ~ 16h, preferably 400 DEG C ~ 700 DEG C roasting 4h ~
8h。
Hydroxy-containing compounds are the one or more in methanol, ethanol, propyl alcohol, isopropanol in the inventive method, are preferably
Methanol, ethanol or the two mixed solvent.Specific Process of Surface Modification is as follows：The heating of Sn, K alumina support will be contained and vacuumize place
Reason, temperature are 60 DEG C ~ 100 DEG C, and preferably 70 DEG C ~ 90 DEG C, pressure is less than 30kPa in vacuum system（Absolute pressure）, it is preferably less than
20 kPa（Absolute pressure）, processing time is 0.5h ~ 8h, preferably 1h ~ 4h.Room temperature is down to, hydroxyl is added under negative pressure state to be had
Machine thing solvent, stops vacuumizing, is heated to reflux.Add the pore volume that solvent volume is more than handled sample.Then backflow is stopped,
Solvent evaporated.
The present invention relates to the active metal component Pt of propane dehydrogenation catalyst to be carried on carrying alumina containing Sn using infusion process
In body, loading process is method well known to those skilled in the art.Such as：First using oxidation of the aqueous solution dipping containing Sn containing Pt
Alumina supporter, preferably ageing time 1h ~ 16h, 4h ~ 8h.After dipping dry, drying temperature be 60 DEG C ~ 150 DEG C, drying time be 1h ~
24h, 4h ~ 8h is dried at preferably 80 DEG C ~ 120 DEG C.The above-mentioned aqueous solution containing Pt is prepared by the inorganic metal salt containing Pt, wherein institute
It is preferably chloroplatinic acid to state the inorganic metal salt containing Pt.
A kind of propane dehydrogenation catalyst prepared using the above method, Pt weight percentages in terms of element are in catalyst
0.1% ~ 1.0%, preferably 0.4% ~ 0.8%；Sn counts weight percentage as 0.5% ~ 10% using element, and preferably 1% ~ 3%；K is with member
Plain weight meter percentage composition is 0.5% ~ 10%, and preferably 1% ~ 3%, Pt particle size is in 2 ~ 10nm, preferably 4 ~ 8nm, 4nm ~ 8nm
The particle diameter distribution of scope Pt crystal grain is 80% ~ 100%, preferably 90% ~ 100%.
The application of above-mentioned propane dehydrogenation catalyst, using propane as raw material, sulfur-containing compound is in terms of sulfur content in propane feed
For 30ppm -150ppm, preferably 50ppm-120ppm.
In the present invention, preferentially load on the alumina support, preferably controls the acidic site of carrier surface to alkali metal,
It it also avoid the loss of alkaline components in course of reaction.Use oxidation of the hydroxyl organic matter solvent to load Sn and alkali metal
Alumina supporter carries out surface modification, and the competitive adsorbates such as hydrochloric acid are introduced when reducing supporting Pt.In addition, after load active component Pt
Sample need not be calcined, it is not required that vapor dechlorination processing be carried out, directly using hydroxyl organic matter and the gaseous mixture of hydrogen
Handled, by modulation process temperature and the composition of gaseous mixture, using remaining a small amount of halogen in skeleton to hydroxyl organic matter
Nucleophilic displacement of fluorine and hydrogen reduction, can not only control Pt particle sizes, improve selectivity, the stability of catalyst
And resistance to SO_2, and more secondary active phases are formd, such as the side of Pt particles, platform, face, the activity of catalyst is improved, is made
For without dechlorination and the dehydrogenation of reduction process.Method for preparing catalyst of the present invention is simple, mature technology, favorably
In the industrial production of catalyst.
Brief description of the drawings
Fig. 1 is the gained catalyst transmission electron microscope picture of embodiment 6.
Embodiment
The technology of the present invention is described further below by the implementation of dehydrogenating propane.
Example 1
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 80 DEG C of dry 8h,
4h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 70 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 1h, add 100mL methanol, reply normal pressure, be heated to reflux, 55 DEG C of heating-up temperature, processing time
4h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 4h, 80 DEG C of dry 8h.After drying
Sample is placed in tubular heater, is warming up to 280 DEG C in a nitrogen atmosphere, is mixed after methanol gasifying with hydrogen, nitrogen, wherein first
Determining alcohol is 20v%, density of hydrogen 50v%, is cut into heating furnace, and gaseous mixture volume space velocity is 1000h-1, control system pressure
Power is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Catalyst C-1 is obtained, is urged
The content of each component is in agent：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.The particle diameter of 4nm-8nm scope Pt crystal grain point
Cloth is 91%.Appreciation condition：At 610 DEG C, the mass space velocity of propane is 3h-1, pressure 0.1MPa（Gauge pressure）Under the conditions of carry out propane take off
Hydrogen reacts, catalyst usage amount 3g, sulfur-bearing 90ppm in propane feed.Evaluation result is shown in Table 1.
Example 2
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 6h, 100 DEG C of dry 6h,
6h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, add 100mL methanol, reply normal pressure, be heated to reflux, 60 DEG C of heating-up temperature, processing time
4h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 4h, 100 DEG C of dry 6h.Dry
Sample is placed in tubular heater afterwards, is warming up to 340 DEG C in a nitrogen atmosphere, is mixed after methanol gasifying with hydrogen, nitrogen, wherein
Methanol concentration is 20v%, density of hydrogen 50v%, is cut into heating furnace, and gaseous mixture volume space velocity is 1000h-1, control system
Pressure is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Catalyst C-2 is obtained,
The content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.The particle diameter of 4nm-8nm scope Pt crystal grain
It is distributed as 97%.Appreciation condition is with embodiment 1, and difference is in the sulfur-bearing 80ppm in propane feed.Evaluation result is shown in Table 1.
Example 3
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 8h, 120 DEG C of dry 4h,
8h is calcined in 400 DEG C.Sample is placed in Rotary Evaporators after roasting, 70 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 15kPa, cool after handling 4h, add 100mL ethanol, reply normal pressure, be heated to reflux, 70 DEG C of heating-up temperature, processing time
4h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 6h, 120 DEG C of dry 4h.Dry
Sample is placed in tubular heater afterwards, is warming up to 280 DEG C in a nitrogen atmosphere, is mixed after methanol gasifying with hydrogen, nitrogen, wherein
Methanol concentration is 10v%, density of hydrogen 60v%, is cut into heating furnace, and gaseous mixture volume space velocity is 2000h-1, control system
Pressure is 120kPa（Absolute pressure）, constant temperature 4h, after constant temperature terminates, switch to nitrogen atmosphere to drop to room temperature.Catalyst C-3 is obtained,
The content of each component is in catalyst：Pt 0.4wt%, Sn 1.0wt%, K 2.0wt%.The particle diameter of 4nm-8nm scope Pt crystal grain
It is distributed as 93%.Appreciation condition is with embodiment 1, and difference is in the sulfur-bearing 80ppm in propane feed.Evaluation result is shown in Table 1.
Example 4
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 6h, 120 DEG C of dry 4h,
4h is calcined in 700 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, it is 3 to add 100mL mol ratios:1 methanol, alcohol mixed solvent, reply normal pressure, heating
Backflow, 66 DEG C of heating-up temperature, processing time 6h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K
Product.A certain amount of chloroplatinic acid is weighed again to be dissolved in deionized water, is settled to 27mL, is added to the above-mentioned alumina sample containing Sn, K
In, aging 4h, 100 DEG C of dry 4h.Sample is placed in tubular heater after drying, is warming up to 300 DEG C in a nitrogen atmosphere, methanol
Mixed after gasification with hydrogen, nitrogen, wherein methanol concentration is 25v%, density of hydrogen 50v%, is cut into heating furnace, gaseous mixture
Volume space velocity is 500h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch under nitrogen atmosphere
It is down to room temperature.Obtain catalyst C-4, the content of each component is in catalyst：Pt 0.4wt%, Sn 1.0wt%, K 1.0wt%.
The particle diameter distribution of 4nm-8nm scope Pt crystal grain is 95%.Appreciation condition is containing with embodiment 1, difference in propane feed
Sulphur 120ppm.Evaluation result is shown in Table 1.
Example 5
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 80 DEG C of dry 8h,
6h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, it is 1 to add 100mL mol ratios:1 methanol, alcohol mixed solvent, reply normal pressure, heating
Backflow, 62 DEG C of heating-up temperature, processing time 4h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K
Product.A certain amount of chloroplatinic acid is weighed again to be dissolved in deionized water, is settled to 27mL, is added to the above-mentioned alumina sample containing Sn, K
In, aging 8h, 80 DEG C of dry 8h.Sample is placed in tubular heater after drying, is warming up to 300 DEG C in a nitrogen atmosphere, methanol,
Mixed after ethanol gasification with hydrogen, nitrogen, wherein methanol concentration is 10v%, concentration of alcohol 10v%, density of hydrogen 50v%, is cut
Enter into heating furnace, gaseous mixture volume space velocity is 1000h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, constant temperature knot
Shu Hou, nitrogen atmosphere is switched to drop to room temperature.Obtain catalyst C-5, the content of each component is in catalyst：Pt 0.8wt%,
Sn 3.0wt%, K 2.0wt%.The particle diameter distribution of 4nm-8nm scope Pt crystal grain is 95%.Appreciation condition with embodiment 1, difference
It is in the sulfur-bearing 120ppm in propane feed.Evaluation result is shown in Table 1.
Example 6
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 100 DEG C of dry 6h,
4h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, add 100mL methanol, reply normal pressure, be heated to reflux, 58 DEG C of heating-up temperature, processing time
6h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dry
Sample is placed in tubular heater afterwards, is warming up to 320 DEG C in a nitrogen atmosphere, is mixed after methanol, ethanol gasification with hydrogen, nitrogen
Close, wherein methanol concentration is 15v%, concentration of alcohol 5v%, density of hydrogen 50v%, is cut into heating furnace, gaseous mixture volume
Air speed is 1000h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to decline
To room temperature.Obtain catalyst C-6, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.4nm-
The particle diameter distribution of 8nm scope Pt crystal grain is 96%.Appreciation condition is with embodiment 1, and difference is in the sulfur-bearing in propane feed
120ppm.Evaluation result is shown in Table 1.
Example 7
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 100 DEG C of dry 6h,
4h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, add 100mL methanol, reply normal pressure, be heated to reflux, 58 DEG C of heating-up temperature, processing time
6h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dry
Sample is placed in tubular heater afterwards, is warming up to 320 DEG C in a nitrogen atmosphere, is mixed after methanol, ethanol gasification with hydrogen, nitrogen
Close, wherein methanol concentration is 5v%, concentration of alcohol 15v%, density of hydrogen 40v%, is cut into heating furnace, gaseous mixture volume
Air speed is 1000h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to decline
To room temperature.Obtain catalyst C-7, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.4nm-
The particle diameter distribution of 8nm scope Pt crystal grain is 96%.Appreciation condition is with embodiment 1, and difference is in the sulfur-bearing in propane feed
120ppm.Evaluation result is shown in Table 1.
Comparative example 1
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 100 DEG C of dry 6h,
4h is calcined in 600 DEG C, obtains the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in deionized water,
27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h, dry roasting.Roasting
Sample is placed in tubular heater afterwards, is warming up to 260 DEG C in a nitrogen atmosphere, is mixed after methanol, ethanol gasification with hydrogen, nitrogen
Close, wherein methanol concentration is 15v%, concentration of alcohol 5v%, density of hydrogen 50v%, is cut into heating furnace, gaseous mixture volume
Air speed is 1000h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, after constant temperature terminates, switch to nitrogen atmosphere to decline
To room temperature.Obtain catalyst D-1, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.4nm-
The particle diameter distribution of 8nm scope Pt crystal grain is 43%.Appreciation condition is with embodiment 1, and difference is in the sulfur-bearing in propane feed
120ppm.Evaluation result is shown in Table 1.
Comparative example 2
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Weigh a certain amount of nitre
Sour potassium is dissolved in deionized water, is settled to 27mL, is added into 30g alumina samples containing Sn, aging 4h, 100 DEG C of dry 6h,
4h is calcined in 600 DEG C.Sample is placed in Rotary Evaporators after roasting, 80 DEG C of vacuumize processs, and the control of system absolute pressure exists
Below 10kPa, cool after handling 2h, add 100mL methanol, reply normal pressure, be heated to reflux, 58 DEG C of heating-up temperature, processing time
6h.Then stop backflow, solvent evaporated, obtain the alumina support sample containing Sn, K.A certain amount of chloroplatinic acid is weighed again to be dissolved in
In deionized water, 27mL is settled to, is added into the above-mentioned alumina sample containing Sn, K, aging 6h, 100 DEG C of dry 6h.Dry
Sample is placed in tubular heater afterwards, is warming up to 260 DEG C in a nitrogen atmosphere, cuts the mixed gas of hydrogen and nitrogen, hydrogen
Concentration is 60v%, and gaseous mixture volume space velocity is 1000h-1, control system pressure is 120kPa（Absolute pressure）, constant temperature 2h, constant temperature terminates
Afterwards, nitrogen atmosphere is switched to drop to room temperature.Obtain catalyst D-2, the content of each component is in catalyst：Pt 0.6wt%, Sn
3.0wt%, K 1.0wt%.The particle diameter distribution of 4nm-8nm scope Pt crystal grain is 38%.Appreciation condition is the same as embodiment 1, difference
In the sulfur-bearing 120ppm in propane feed.Evaluation result is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (17)
- A kind of 1. preparation method of propane dehydrogenation catalyst, it is characterised in that：Including following process：Using aluminum oxide containing Sn as load Body, alkali metal promoter K is impregnated first, it is carried out using hydroxyl organic matter solvent after drying and roasting to be heated to reflux surface modification Processing, reflux temperature are less than 5 DEG C ~ 10 DEG C of solvent for use or mixed solvent boiling point；Return time is 2h ~ 12h；Surface is modified After carrier drying containing Sn and alkali metal K, using infusion process load active component Pt, roasting process is omitted, is directly existed after drying Handled under mixed atmosphere containing hydroxyl organic matter and hydrogen and propane dehydrogenation catalyst is made, treatment temperature is 260 DEG C ~ 360 DEG C, processing time is 0.5h ~ 8h, and processing pressure is not more than 150kPa in terms of absolute pressure, and mixed gas air speed is 200h-1~2500h-1, the concentration of hydroxyl organic matter is 5v% ~ 30v% in mixed gas, and the concentration of hydrogen is 20v% ~ 70v%；The hydroxyl organic matter is the one or more in methanol, ethanol, propyl alcohol, isopropanol.
- 2. according to the method for claim 1, it is characterised in that：Return time is 4h ~ 8h；Treatment temperature is 280 DEG C ~ 340 DEG C, processing time is 1h ~ 4h, and processing pressure is calculated as the kPa of 5 kPa ~ 130 with absolute pressure, and mixed gas air speed is 500h-1~ 2000h-1, the concentration of hydroxyl organic matter is 10v% ~ 25v% in mixed gas；The concentration of hydrogen is 30v% ~ 60v%.
- 3. according to the method for claim 1, it is characterised in that：Alumina support containing Sn is spherical, bar shaped, microballoon or different Shape, particle equivalent diameter are 0.1 mm ~ 5mm.
- 4. according to the method for claim 1, it is characterised in that：Alumina support specific surface area is 200 m2/g ~240 m2/ G, pore volume are 0.60 cm3/g ~0.80 cm3/g。
- 5. according to the method for claim 1, it is characterised in that：Sn in alumina support containing Sn is in aluminum oxide plastic process Middle introducing, either it is introduced into by way of load or kneading introduces in aluminum oxide forming process.
- 6. according to the method for claim 1, it is characterised in that：Alkali metal promoter K predecessor is soluble salt containing K, Inorganic salts or organic salt.
- 7. according to the method for claim 1, it is characterised in that：The method for loading K is as follows：Weigh potassium nitrate and be dissolved in deionization In water, then solution is added in alumina support containing Sn, at room temperature aging 2h ~ 16h, then through 40 DEG C ~ 160 DEG C dry 2h ~ 16h, then it is calcined 2h ~ 16h at 300 DEG C ~ 800 DEG C.
- 8. according to the method for claim 7, it is characterised in that：Drying is 80 DEG C ~ 120 DEG C dry 4h ~ 8h, is roasted to 400 DEG C ~ 700 DEG C of roasting 4h ~ 8h.
- 9. according to the method for claim 1, it is characterised in that：Hydroxyl organic matter is that methanol, ethanol or the two mixing are molten Agent.
- 10. according to the method for claim 1, it is characterised in that：It is as follows to be heated to reflux surface modification treatment detailed process：It is first Sn, K alumina support heating vacuumize process will first be contained, temperature is 60 DEG C ~ 100 DEG C, and pressure is less than 30kPa in vacuum system, Processing time is 0.5h ~ 8h, is then down to room temperature, and hydroxyl organic matter solvent is added under negative pressure state, stops vacuumizing, adds Heat backflow, the pore volume that solvent volume is more than handled sample is added, finally stops backflow, solvent evaporated.
- 11. according to the method for claim 10, it is characterised in that：Temperature is 70 DEG C ~ 90 DEG C, and pressure is less than in vacuum system 20 kPa, processing time are 1h ~ 4h.
- 12. according to the method for claim 1, it is characterised in that：It is first modified using the aqueous solution impregnation surface containing Pt Carrier containing Sn and alkali metal K, ageing time 1h ~ 16h, dry after dipping, drying temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h~24h。
- 13. according to the method for claim 12, it is characterised in that：Ageing time 4h ~ 8h, it is to be done at 80 DEG C ~ 120 DEG C to dry Dry 4h ~ 8h.
- 14. according to the method for claim 12, it is characterised in that：The aqueous solution containing Pt is matched somebody with somebody by the inorganic metal salt containing Pt System, wherein the inorganic metal salt containing Pt is chloroplatinic acid.
- 15. catalyst prepared by claim 1 to 14 either method, it is characterised in that：Pt is with element weight calculation amount hundred in catalyst Point content is that 0.1% ~ 1.0%, Sn using element counts weight percentage the percentage composition in terms of element wt is as 0.5% ~ 10%, K 0.5% ~ 10%, Pt particle size are in 2 ~ 10nm.
- 16. the application of catalyst described in claim 15, it is characterised in that：Using propane as raw material, sulfur-bearing chemical combination in propane feed Thing is calculated as 30ppm -150ppm with sulfur content.
- 17. the application of catalyst described in claim 16, it is characterised in that：Sulfur-containing compound is calculated as with sulfur content in propane feed 50ppm-120ppm。
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| CN112007639B (en) * | 2020-09-01 | 2023-03-21 | 辽宁石油化工大学 | Preparation method of dehydrogenation catalyst with low carbon deposition rate |
| CN112007638B (en) * | 2020-09-01 | 2023-04-07 | 辽宁石油化工大学 | Preparation method of propane dehydrogenation catalyst prepared by controlling Pt grain size |
| CN112007640B (en) * | 2020-09-01 | 2022-11-18 | 辽宁石油化工大学 | A kind of preparation method of low-carbon alkane dehydrogenation catalyst |
| CN114602495B (en) * | 2020-12-09 | 2024-07-30 | 中国石油天然气股份有限公司 | A method for preparing a propane dehydrogenation Pt catalyst |
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