CN109261175A - A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst and its preparation method and application - Google Patents
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst and its preparation method and application Download PDFInfo
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- CN109261175A CN109261175A CN201811216239.7A CN201811216239A CN109261175A CN 109261175 A CN109261175 A CN 109261175A CN 201811216239 A CN201811216239 A CN 201811216239A CN 109261175 A CN109261175 A CN 109261175A
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- alf
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- dechlorination
- hydrogenation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 40
- 238000011068 loading method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000004411 aluminium Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 146
- 229910052763 palladium Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003746 yttrium Chemical class 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- MKPKCNXKRRNKMM-UHFFFAOYSA-J zirconium(4+);tetrachlorate Chemical compound [Zr+4].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O MKPKCNXKRRNKMM-UHFFFAOYSA-J 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- -1 compound aluminum fluoride Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910007928 ZrCl2 Inorganic materials 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- 229910009523 YCl3 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JYHHXQKTNJXLFU-UHFFFAOYSA-N C(C)Cl.[F] Chemical class C(C)Cl.[F] JYHHXQKTNJXLFU-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Abstract
The invention discloses a kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst and its preparation method and application.Al in the catalyst2O3Preparation process are as follows: P123 template is dissolved in dehydrated alcohol, and be added dropwise nitric acid to solution ph be 6.5~7.5；Then aluminium alcoholates is added and metal promoter is reacted, reaction solution is subjected to crystallization after reaction, finally the compound Al of high-specific surface area can be obtained in roasting under the conditions of 300~500 DEG C2O3.Pd/AlF prepared by the present invention3Catalyst is while guaranteeing highly selective and high catalytic activity, the performance of catalyst is improved, the service life of especially catalyst is significantly extended, it is recycled even across prolonged, its selectivity and catalytic activity still with higher, the service life and stability of catalyst are significantly improved, after the use of 800h, the conversion ratio of raw material is still maintained at 98.7% or more, is conducive to quick, efficient, the inexpensive carry out hydrogenation-dechlorination catalysis reaction of chlorinated organics.
Description
Technical field
The present invention relates to chlorinated organics catalytic hydrogenation and dechlorination recycling fields, negative more particularly, to a kind of hydrogenation-dechlorination
Load type Pd/AlF3Catalyst and its preparation method and application.
Background technique
The processing method of chlorinated organics mainly has incineration method, plasma method, supercritical water method, explosion method, catalysis point
Solution (catalysis oxidation, catalyzing hydrolysis), catalytic hydrogenation and dechlorination method etc., wherein front or easily causes secondary pollution at several method, or
Technology is immature or excessively high etc. reasons of processing cost, application it is less；And then can will to contain chlorine organic for catalytic hydrogenation and dechlorination technology
Object selectivity is converted into high added value substance, turns waste into wealth, and is that processing chlorinated organics are most economical, green, and before most having
The method of scape.
Studies have shown that loading type Pd/AlF3With Pd/C catalyst catalysis chlorinated organics hydrogenation-dechlorination reaction in due to
With highly selective and good stability, thus obtain extensive concern.But the AlF of commercialization3Specific surface area is smaller to be led
Cause Pd/AlF3Catalyst activity is told somebody what one's real intentions are, and Pd/AlF is limited3The application of catalyst.Therefore, Pd/AlF is improved3AlF in catalyst3
The specific surface area of carrier, it is ensured that while catalyst has highly selective, catalytic activity also with higher.And Pd/AlF3
Catalyst is the higher cost using precious metals pd as active constituent, and catalyst is easy inactivation in use, not only increases
The cost of the catalytic hydrogenation and dechlorination processing of chlorinated organics, while also reducing treatment effeciency.
Patent CN101745409A discloses a kind of orient for CFC-115 hydrogenation-dechlorination and is converted to HFC-125 catalyst
Preparation and application, be described improve AlF3The method of specific surface area, to be prepared what catalytic activity significantly improved
Pd/AlF3Catalyst.But the invention does not refer to the service life situation of its catalyst, i.e. catalyst is recycled for a long time
During whether can still guarantee highly selective and high catalytic activity.
Therefore, to realize chlorinated organics more rapidly, higher efficiency, and the catalytic hydrogenation and dechlorination processing that cost is less expensive,
It is necessary to improve Pd/AlF while guaranteeing catalytic activity and selectivity3The service life of catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of hydrogenation-dechlorination that catalytic life is more permanent loading type Pd/AlF3Catalyst.
Loading type Pd/AlF of the present invention3Catalyst is by preparing high-specific surface area AlF3During joined metal promoter, from
And make the Pd/AlF of preparation3Catalyst also has more longlasting catalysis while guaranteeing highly selective and high catalytic activity
In the service life, after the use of 800h, the conversion ratio of raw material is still maintained at 98.7% or more.
Another object of the present invention is to provide the hydrogenation-dechlorination loading type Pd/AlF3The preparation method of catalyst.
A further object of the present invention is to provide the hydrogenation-dechlorination loading type Pd/AlF3Catalyst chlorinated organics
Application in hydrogenation-dechlorination reaction.
Above-mentioned purpose of the invention is achieved by following scheme:
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, high-specific surface area Al2O3It is prepared by following procedure: by P123
Template is dissolved in dehydrated alcohol, and it is 6.5~7.5 that nitric acid to solution ph, which is added dropwise,；Then be added aluminium alcoholates and metal promoter into
Row reaction, carries out crystallization for reaction solution after reaction, and finally high-ratio surface can be obtained in roasting under the conditions of 300~500 DEG C
The compound Al of product2O3；
Wherein, the metal promoter is one of soluble magnesium salts, cobalt salt, yttrium salt, zirconates or a variety of；The aluminium alcoholates is different
Aluminium propoxide or aluminium butoxide；
The molar ratio of the P123 template and aluminium alcoholates is 1:30~90；In the aluminium alcoholates in metal and metal promoter metal matter
Amount is than being 100:0.1~6.
Pd/AlF is prepared in patent CN101745409A3In catalyst process, in high-specific surface area Al2O3The basis of preparation
On, the present invention is by joined specific metal promoter, so that the Pd/AlF of preparation3In catalyst, not only there is high catalysis to live
Property and highly selective, and the performance of the catalyst is improved, and the service life of especially catalyst is significantly prolonged
It is long, it is recycled even across prolonged, selectivity and catalytic activity still with higher, the service life of catalyst
It is significantly improved with stability, quick, efficient, the inexpensive carry out hydrogenation-dechlorination catalysis for being conducive to chlorinated organics is anti-
It answers.
Preferably, the aluminium alcoholates is aluminium isopropoxide.
Preferably, the metal promoter is the chlorate or nitrate of magnesium, cobalt, yttrium, zirconium.
It is highly preferred that the metal promoter is the chlorate of magnesium, cobalt, yttrium, zirconium.
Preferably, the molar ratio of the P123 template and aluminium alcoholates is 1:50~80；Metal and metal promoted in the aluminium alcoholates
The mass ratio of metal is 100:0.5~5 in agent.
Preferably, after nitric acid being added dropwise, the pH value of solution is 7.
Preferably, the revolving speed that the reaction is stirred during carrying out is 300r/min.
Preferably, the crystallization temperature is 60 DEG C, time 48h.
Preferably, the maturing temperature is 400 DEG C, and the time is 2~4h.It is highly preferred that the calcining time is 3h.
Preferably, by the Al of preparation2O3It is soluble in water, HF solution, and the water-bath at 50~70 DEG C is added dropwise, is sunk
It forms sediment, is then roasted at 180~250 DEG C in atmosphere of inert gases, obtain the compound AlF of high specific area3；Finally again by AlF3With chlorine
Palladium acid solution is first reacted at 35~55 DEG C using infusion process, then is warming up to 55~80 DEG C of reactions, after reaction does sample
After dry after 300~400 DEG C of roastings, that is, Pd/AlF is prepared3Catalyst.The AlF prepared with this condition3Specific surface area
It is larger, in 146m2/ g or more.
Preferably, in AlF3In preparation process, the mass concentration of the HF solution is 35%；The bath temperature is 60 DEG C；
The maturing temperature is 200 DEG C；The inert gas is nitrogen.
Preferably, during impregnation, the quality of palladium is AlF in the chlorine palladium acid solution3The 1%~5% of quality；It is described
Bath temperature is first 40 DEG C, is being warming up to 80 DEG C；The maturing temperature is 350 DEG C.
It is highly preferred that the quality of palladium is AlF in the chlorine palladium acid solution3The 4.5% of quality.
The present invention also protects the hydrogenation-dechlorination loading type Pd/AlF simultaneously3Catalyst adds hydrogen de- in catalysis chlorinated organics
Application in chlorine reaction.
Compared with prior art, the invention has the following advantages:
The present invention is preparing high-specific surface area Al2O3When joined specific metal promoter so that preparation Pd/AlF3It urges
While guaranteeing highly selective and high catalytic activity, the performance of catalyst is improved agent, especially the use of catalyst
Service life is significantly extended, and is recycled even across prolonged, selectivity and catalytic activity still with higher,
The service life and stability of catalyst are significantly improved, and after the use of 800h, the conversion ratio of raw material is still tieed up
It holds 98.7% or more, is conducive to quick, efficient, the inexpensive carry out hydrogenation-dechlorination catalysis reaction of chlorinated organics.
Detailed description of the invention
Fig. 1 is Pd/AlF prepared by embodiment 1 and comparative example 13The catalytic activity of catalyst changes with time situation.
Specific embodiment
The present invention is made combined with specific embodiments below and further being elaborated, the embodiment is served only for explaining this
Invention, is not intended to limit the scope of the present invention.Test method as used in the following examples is normal unless otherwise specified
Rule method；Used material, reagent etc., unless otherwise specified, for the reagent and material commercially obtained.
Embodiment 1
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 20.0g P123 template and be dissolved in 400mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value be 7, be then added 40.85 g aluminium isopropoxides,
1.06g MgCl2、0.69g ZrCl2, it is stirred to react 5h strongly at room temperature and is placed on crystallization 48h in 60 DEG C of baking ovens, the Huang after drying
Color solid dry gel 400 DEG C of roasting 3h in air atmosphere obtain the compound Al of high-specific surface area after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 5g A1 is weighed2O3It dissolves in 50mL distilled water, is added dropwise dropwise
The HF solution 10.5mL of 35wt.%, stirs 10h under 60 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality,
50 DEG C of vacuum drying, in N2200 DEG C of roasting 5h in atmosphere, it is 162.3m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 2.5g3, the accurate chlorine palladium acid solution (palladium in solution for moving respective volume
Concentration be 0.010g/mL, the quality of palladium is AlF in solution3The 4.5% of quality), after 40 DEG C of stirring in water bath impregnate 1h, increase
Bath temperature continues to be evaporated after impregnating 8h；Sample drying is placed on 350 DEG C of roasting 3h in roaster, obtains Pd/AlF3It is compound
Catalyst.
Pd/AlF manufactured in the present embodiment3The load capacity of middle Pd is 4.5%.Similarly, aluminium butoxide substitution isopropanol can be used
The Pd/AlF that the load capacity of Pd is 4.5% is prepared in aluminium3Catalyst.
Embodiment 2
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 15.0g P123 template and be dissolved in 200mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value is 7.5, and 40.85 g isopropanols are then added
Aluminium, 0.11g MgCl2、0.59g CoCl2, it is stirred to react 4h strongly at room temperature and is placed on crystallization 36h in 50 DEG C of baking ovens, after dry
Yellow solid xerogel 400 DEG C of roasting 3h in air atmosphere, the compound Al of high-specific surface area is obtained after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 4g A1 is weighed2O3It dissolves in 50mL distilled water, is added dropwise dropwise
The HF solution 12mL of 35wt.%, stirs 8h under 60 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality, 70
DEG C vacuum drying, N2180 DEG C of roasting 4h in atmosphere, it is 145.7m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 3.0g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 4.5% of quality), after 50 DEG C of stirring in water bath impregnate 2h, increase water
Bath temperature continues to be evaporated after impregnating 6h；Sample drying is placed on 400 DEG C of roasting 2h in roaster, obtains Pd/AlF3It is compound to urge
Agent, wherein the load capacity of Pd is 4.5%.
Similarly, aluminium butoxide substitution aluminium isopropoxide can be used, the Pd/AlF that the load capacity of Pd is 4.5% is prepared3Catalysis
Agent.
Embodiment 3
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 20.0g P123 template and be dissolved in 250mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value is 6.5, and 20.42 g isopropanols are then added
Aluminium, 0.12g CoCl2、0.30g YCl3, it is stirred to react 5h strongly at room temperature and is placed on crystallization 48h in 60 DEG C of baking ovens, after dry
Yellow solid xerogel 350 DEG C of roasting 4h in air atmosphere, the compound Al of high-specific surface area is obtained after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 5g A1 is weighed2O3It dissolves in 60mL distilled water, is added dropwise dropwise
The HF solution 13mL of 35wt.%, stirs 12h under 65 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality, 50
DEG C vacuum drying, N2200 DEG C of roasting 6h in atmosphere, it is 152.4m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 3.5g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 3.0% of quality), after 55 DEG C of stirring in water bath impregnate 3h, increase water
Bath temperature continues to be evaporated after impregnating 8h；Sample drying is placed on 350 DEG C of roasting 4h in roaster, obtains Pd/AlF3It is compound to urge
Agent, wherein the load capacity of Pd is 3.0%.
Similarly, aluminium butoxide substitution aluminium isopropoxide can be used, the Pd/AlF that the load capacity of Pd is 3.0% is prepared3Catalysis
Agent.
Embodiment 4
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 15.0g P123 template and be dissolved in 300mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value be 7, be then added 20.42 g aluminium isopropoxides,
0.59g YCl3、0.34g ZrCl2, it is stirred to react 6h strongly at room temperature and is placed on crystallization 60h in 70 DEG C of baking ovens, the Huang after drying
Color solid dry gel 450 DEG C of roasting 3h in air atmosphere obtain the compound Al of high-specific surface area after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 3.5g A1 is weighed2O3It dissolves in 65mL distilled water, drips dropwise
The HF solution 12mL for adding 35wt.%, stirs 10h under 55 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality,
60 DEG C of vacuum drying, N2220 DEG C of roasting 7h in atmosphere, it is 149.8m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 3.0g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 4.5% of quality), after 35 DEG C of stirring in water bath impregnate 1h, increase water
Bath temperature continues to be evaporated after impregnating 7h；Sample drying is placed on 300 DEG C of roasting 3h in roaster, obtains Pd/AlF3It is compound to urge
Agent, wherein the load capacity of Pd is 4.5%.
Similarly, aluminium butoxide substitution aluminium isopropoxide can be used, the Pd/AlF that the load capacity of Pd is 4.5% is prepared3Catalysis
Agent.
Embodiment 5
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 25.0g P123 template and be dissolved in 300mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value is 6.5, and 40.85 g isopropanols are then added
Aluminium, 0.06g CoCl2、0.34g ZrCl2, it is stirred to react 4h strongly at room temperature and is placed on crystallization 72h in 50 DEG C of baking ovens, after dry
Yellow solid xerogel 350 DEG C of roasting 4h in air atmosphere, the compound Al of high-specific surface area is obtained after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 5g A1 is weighed2O3It dissolves in 55mL distilled water, is added dropwise dropwise
The HF solution 14mL of 35wt.%, stirs 8h under 70 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality, 70
DEG C vacuum drying, N2240 DEG C of roasting 8h in atmosphere, it is 154.1m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 3.0g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 3.5% of quality), after 50 DEG C of stirring in water bath impregnate 2h, increase water
Bath temperature continues to be evaporated after impregnating 6h；Sample drying is placed on 350 DEG C of roasting 4h in roaster, obtains Pd/AlF3It is compound to urge
Agent, wherein the load capacity of Pd is 3.5%.
Similarly, aluminium butoxide substitution aluminium isopropoxide can be used, the Pd/AlF that the load capacity of Pd is 3.5% is prepared3Catalysis
Agent.
Embodiment 6
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process are as follows:
(1) the compound Al of high-specific surface area2O3Preparation: weigh 25.0g P123 template and be dissolved in 400mL dehydrated alcohol, it is complete
Concentrated nitric acid (wt%=67%) is slowly added dropwise after fully dissolved to stir evenly, control pH value be 7, be then added 61.27 g aluminium isopropoxides,
1.59g MgCl2、0.89g YCl3, it is stirred to react 5h strongly at room temperature and is placed on crystallization 36h in 60 DEG C of baking ovens, the Huang after drying
Color solid dry gel 400 DEG C of roasting 2h in air atmosphere obtain the compound Al of high-specific surface area after roasting2O3。
(2) high-specific surface area AlF3The preparation of carrier: above-mentioned 6gA1 is weighed2O3It dissolves in 60mL distilled water, is added dropwise dropwise
The HF solution 13mL of 35wt.%, stirs 10h under 50 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality, 60
DEG C vacuum drying, N2250 DEG C of roasting 6h in atmosphere, it is 147.2m that surface area, which is made,2The compound aluminum fluoride of/g.
(3) Pd/AlF3Preparation: weigh the above-mentioned AlF of 4.0g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 4.0% of quality), after 35 DEG C of stirring in water bath impregnate 3h, increase water
Bath temperature continues to be evaporated after impregnating 10h；Sample drying is placed on 400 DEG C of roasting 2h in roaster, obtains Pd/AlF3It is compound to urge
Agent, wherein the load capacity of Pd is 4.0%.
Similarly, aluminium butoxide substitution aluminium isopropoxide can be used, the Pd/AlF that the load capacity of Pd is 4.0% is prepared3Catalysis
Agent.
Comparative example 1
Preparation Pd/AlF is carried out according to the embodiment 1 in patent CN101745409A3Catalyst, specific preparation process are as follows:
(1) AlF3The preparation of carrier: 4.5g commercialization γ-A1 is weighed2O3It dissolves in 55mL distilled water, the HF of 35wt.% is added dropwise dropwise
Solution 10.5mL, stirs 10h under 55 DEG C of water-baths strongly, obtained white precipitate is filtered, washed to neutrality, and 60 DEG C of vacuum are dry
It is dry, 220 DEG C of N25h is roasted in atmosphere, it is 115.6m that surface area, which is made,2/ g aluminum fluoride.
(2) Pd/AlF3Preparation: weigh the above-mentioned AlF of 2.5g3, accurately pipette respective volume chlorine palladium acid solution (palladium
Concentration is 0.010g/mL, and the quality of palladium is AlF in solution3The 5.0% of quality), after 40 DEG C of stirring in water bath impregnate 1h, increase water
Bath temperature continues to be evaporated after impregnating 8h；Sample drying is placed on 350 DEG C of roasting 3h in roaster, obtains Pd/AlF3Catalyst,
Wherein the load capacity of Pd is 5.0%.
Above-mentioned Pd/AlF3The preparation condition of catalyst is in the scheme that patent CN101745409A is recorded, wherein individually
Condition is different from what patent CN101745409A was recorded, for the catalytic activity, selectivity and use of finally prepd catalyst
The mass concentration that service life has no the HF solution utilized in influence, such as step (1) is 35%, different from patent 101745409A's
It records, but influence is had no for the above-mentioned performance of catalyst.
Comparative example 2
A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, specific preparation process is with embodiment 1, the difference is that in height
The compound Al of specific surface area2O3Preparation process in do not add any metal promoter, be made surface area be 147.2m2The compound fluorine of/g
Change aluminium, Pd/AlF is equally then prepared using aluminum fluoride using the condition in embodiment 13Catalyst.
Application examples 1
Pd/AlF prepared by embodiment 1, embodiment 2, embodiment 5, comparative example 1, comparative example 23Catalyst carries out CFC-115
(five fluorine monochlorethanes, i.e. R115) hydrogenation-dechlorination performance evaluation, CFC-115 hydrogenation-dechlorination are reacted in atmospheric fixed bed minisize reaction
It is carried out in device, catalyst is in gas volume ratio H2:N2In the atmosphere of=1:2,350 DEG C of pretreatment 5h, the volume ratio of reactant
H2: CFC-115=2:1, time of contact 4-6s, reaction temperature are 300-350 DEG C, evaluate experimental result such as the following table 1 institute after 10h
Show.
15 kinds of Pd/AlF of table3Catalytic performance after catalyst 10h
As can be known from Table 1, Pd/AlF prepared by comparative example 1 and 23Catalyst after 10h, although the conversion ratio of its raw material and
Selectivity is higher, but still has a declining tendency, and Pd/AlF prepared by embodiment 1,2 and 53Catalyst is even across 10h
Afterwards, it the catalytic activity of catalyst and selectively keeps very stable, especially selectively, remains as 100%, and the conversion of raw material
Rate is also above comparative example 1 and 2.
Application examples 2
The Pd/AlF prepared with embodiment 1 and comparative example 13Catalyst is test object, according to the reaction condition in application examples 1,
Test this 2 kinds of Pd/AlF3Catalyst is during long-time use, the efficiency of fcc raw material conversion, testing time 800h,
Test result is as shown in Figure 1.
As can be known from Fig. 1, Pd/AlF prepared by embodiment 1 and comparative example 13Feed stock conversion of the catalyst in 200h compared with
For stabilization, and differ unobvious；After 200h, the Pd/AlF of embodiment 13The feed stock conversion of catalyst is still more steady
Fixed, in 800h, conversion ratio is still 98.7% or more；And the Pd/AlF of comparative example 13Catalyst is after 200h, the conversion ratio of raw material
It continues to decline, is 95%~95.5%, hence it is evident that be lower than embodiment 1 in 800h.As it can be seen that Pd/AlF prepared by embodiment 13Catalysis
The service life is longer for agent, after being recycled for a long time, catalytic activity and selectivity still with higher.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of shield range can also be made on the basis of above description and thinking for those of ordinary skill in the art
Other various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst, with high-specific surface area Al2O3It is prepared for raw material reaction, it is special
Sign is, high-specific surface area Al2O3It is prepared by following procedure: P123 template being dissolved in dehydrated alcohol, and nitre is added dropwise
Acid to solution ph is 6.5~7.5；Then aluminium alcoholates is added and metal promoter is reacted, after reaction carry out reaction solution
Crystallization, finally the compound Al of high-specific surface area can be obtained in roasting under the conditions of 300~500 DEG C2O3；
Wherein, the metal promoter is one of soluble magnesium salts, cobalt salt, yttrium salt, zirconates or a variety of；The aluminium alcoholates is different
Aluminium propoxide or aluminium butoxide；
The molar ratio of the P123 template and aluminium alcoholates is 1:30~90；In the aluminium alcoholates in metal and metal promoter metal matter
Amount is than being 100:0.1~6.
2. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that the metal promoter is
Magnesium, cobalt, yttrium, zirconium chlorate or nitrate.
3. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that the P123 template and
The molar ratio of aluminium alcoholates is 1:50~80；The mass ratio of metal is 100:0.5~5 in metal and metal promoter in the aluminium alcoholates.
4. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that after nitric acid is added dropwise, solution
PH value be 7.
5. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that the crystallization temperature is 60
DEG C, time 48h.
6. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that the maturing temperature is
400 DEG C, the time is 2~4h.
7. hydrogenation-dechlorination loading type Pd/AlF according to claim 13Catalyst, which is characterized in that by the Al of preparation2O3It is molten
HF solution is added dropwise in Yu Shuizhong, and the water-bath at 50~70 DEG C is precipitated, then 180 in atmosphere of inert gases~
It is roasted at 250 DEG C, obtains the compound AlF of high specific area3；Finally again by AlF3With chlorine palladium acid solution using infusion process first 35~55
It is reacted at DEG C, then is warming up to 55~80 DEG C of reactions, after 300~400 DEG C of roastings, that is, will prepared after sample drying after reaction
Obtain Pd/AlF3Catalyst.
8. hydrogenation-dechlorination loading type Pd/AlF according to claim 73Catalyst, which is characterized in that in AlF3Preparation process
In, the mass concentration of the HF solution is 35%；The bath temperature is 60 DEG C；The maturing temperature is 200 DEG C；The inertia
Gas is nitrogen.
9. hydrogenation-dechlorination loading type Pd/AlF according to claim 73Catalyst, which is characterized in that during impregnation,
The quality of palladium is AlF in the chlorine palladium acid solution3The 1%~5% of quality；The bath temperature is first 40 DEG C, is being warming up to 80 DEG C；
The maturing temperature is 350 DEG C.
10. claim 1 to the 9 hydrogenation-dechlorination loading type Pd/AlF3Catalyst is in catalysis chlorinated organics hydrogenation-dechlorination reaction
In application.
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| CN110586144A (en) * | 2019-08-28 | 2019-12-20 | 东莞东阳光科研发有限公司 | Film catalyst precursor, film catalyst, preparation method and application thereof |
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