CN104588041B - Palladium/alumina catalyst and preparation method thereof - Google Patents
Palladium/alumina catalyst and preparation method thereof Download PDFInfo
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- CN104588041B CN104588041B CN201310529450.5A CN201310529450A CN104588041B CN 104588041 B CN104588041 B CN 104588041B CN 201310529450 A CN201310529450 A CN 201310529450A CN 104588041 B CN104588041 B CN 104588041B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 39
- 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 37
- 238000007598 dipping method Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002803 maceration Methods 0.000 claims description 34
- 206010013786 Dry skin Diseases 0.000 claims description 18
- 238000004073 vulcanization Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl xanthan Chemical compound 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 230000036186 satiety Effects 0.000 claims description 2
- 235000019627 satiety Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 34
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000005987 sulfurization reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract 2
- 239000012991 xanthate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 17
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical group [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AAJRIJBGDLLRAE-UHFFFAOYSA-M sodium;butoxymethanedithioate Chemical compound [Na+].CCCCOC([S-])=S AAJRIJBGDLLRAE-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical group CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a sulfuration mode Pd/Al2O3 catalyst. The method comprises the following steps: 1, preparing a sodium alkyl xanthate solution and a palladium-containing dipping liquid which is acidic; 2, dipping an alumina carrier in the palladium-containing dipping liquid, filtering, drying, spraying parts of the palladium-containing dipping liquid, and drying to obtain a catalyst intermediate; and 3, adding the catalyst intermediate to the remaining palladium-containing dipping liquid, dipping, drying, and roasting to obtain the sulfuration mode Pd/Al2O3 catalyst. A volume ratio of the palladium-containing dipping liquid used for spraying to the palladium-containing dipping liquid used for dipping is 1.0:1.0-1.0:3.0, and preferably 1.0:1.5-1.0:2.5. The catalyst obtained through the method realizes higher activity, higher selectivity and longer life than present catalysts prepared through present methods in the synthesis process of methyl isobutyl ketone from acetone.
Description
Technical field
The present invention relates to a kind of preparation method of vulcanization type palladium/aluminium oxide catalyst, especially a kind of acetone synthesizing methyl
The preparation method of isobutyl ketone catalyst.
Background technology
Methyl iso-butyl ketone (MIBK)（Abbreviation MIBK）It is a kind of important organic solvent, be mainly used in paint, cold coating, the content of wax
Oil dewaxing, is also to produce one of raw material of rubber antioxidant 4020, of many uses.
Traditional production method is three-step approach, haves such problems as to pollute that environment, production cost be high, flow process is numerous and diverse, by by
Gradually eliminate.One-step method is the state-of-the-art technology of methylisobutanone synthesized from acetone, and this technical requirements catalyst must have double work(
Energy activated centre, i.e. condensation dehydration acid centre and hydrogenation sites.
Pd/ resin catalyst is to be used for acetone through one-step method earliest to synthesize MIBK commercial plant.Such catalyst is typically adopted
With carrying out what ion exchange obtained in the aqueous solution containing palladium for the storng-acid cation exchange resin immersion.So in ion exchange,
H on some sulfonate radical on resin+By Pd2+Exchange is got off, Pd2+As hydrogenating function center after hydrogen reducing, separately
H on a part of sulfonate radical+Condensation function center as catalyst.The advantage of such catalyst is that production technology is ripe, turns
Rate, selectivity are also preferable；Shortcoming is that sulfonate radical is easy to fall off, and palladium runs off therewith, and catalyst life is shorter.
Another kind of catalyst synthesizing MIBK for acetone through one-step method is mineral-type catalyst, such as Pd/Al2O3With Pd/ molecule
Sieve, such catalytic benefits is that palladium not easily runs off, not etching apparatus, such as CN1069674A, US3666816, CN1255404A,
CN1385241A.The conversion ratio of Pd/ molecular sieve catalyst, selectively relatively permissible, generation in acetone synthesis MIBK course of reaction
Water, water intensity met in the reaction by catalyst and activity decrease is very fast, and catalyst is relatively costly, causes methyl iso-butyl ketone (MIBK) to produce
Cost raises, because this deadly defect of such catalyst is not so as to have industrial application value.
Pd/Al2O3Catalyst is used for methylisobutanone synthesized from acetone, and catalyst initial stage hydrogenation activity is higher, causes double work(
Can mismatch, such as under same conversion ratio, this catalyst choice is less than Pd/ molecular sieve catalyst, and generally acetone turns
Rate>During 40mol%, product selectivity< 95mol %.
Pd/Al for methylisobutanone synthesized from acetone2O3The method that catalyst generally adopts in-situ presulfurization, will
Pd/Al using conventional method preparation2O3Catalyst loads in reactor, first after carrying out reduction, then carries out in-situ presulfurization, so that
The too high part palladium atom passivation of hydrogenation activity, to improve selectivity, method disclosed in such as CN99113289.0.This technique mistake
Cheng Fanfu, cure time is long, and operating cost is high, the operating efficiency of impact device.
Content of the invention
The problem existing for prior art, the invention provides a kind of vulcanization type Pd/ Al2O3The preparation side of catalyst
Method.When being used for by methylisobutanone synthesized from acetone course of reaction by the method gained catalyst, its activity, selectivity and life-span
All increase than existing method.
Vulcanization type Pd/ Al of the present invention2O3The preparation method of catalyst, including：
（1）Prepare alkyl xanthogenic acid sodium solution and the maceration extract containing palladium, the maceration extract containing palladium is acidity；
（2）Alumina support is immersed in dipping in alkyl xanthogenic acid sodium solution, carries out after terminating filtering, be dried, spray
Part contains the maceration extract of palladium, obtains catalyst intermediate after being dried；
（3）Catalyst intermediate is added to dipping in the remaining maceration extract containing palladium, dry, roasting, obtains vulcanization type
Pd/ Al2O3Catalyst；
Wherein, the concentration of alkyl xanthogenic acid sodium solution is 0.1wt% ~ 1.0wt%, preferably 0.3 wt% ~ 0.6 wt%,
Step（2）Spray maceration extract volume containing palladium used and step（3）The ratio of the maceration extract volume containing palladium used is 1.0:1.0~
1.0:3.0, preferably 1.0：1.5~1.0：2.5.
The carbon number of the alkyl in described alkyl xanthogenic acid sodium is 2 ~ 4.Described vulcanization type Pd/ Al2O3Catalysis
In agent, the weight content of palladium is calculated as 0.1wt% ~ 0.7wt%, preferably 0.2wt% ~ 0.6wt% with metal.
Described alumina support, generally gamma-aluminium oxide carrier, its property is preferably as follows：Specific surface area 140 ~
260m2/ g, preferably 180 ~ 200m2/g；Pore volume 0.3～0.8 mL/g, preferably 0.3～0.6mL/g；The shape of described alumina support
Shape can be spherical or strip or other any suitable shape.
The described maceration extract containing palladium can be using conventional method preparation, such as will be soluble in water for soluble palladium salt, preferably
Deionized water, then be acid with the pH value that inorganic acid adjusts maceration extract, best pH value is 2 ~ 4, and in maceration extract, the concentration of palladium is
0.1wt% ~ 1.0wt%, preferably 0.1 wt% ~ 0.6 wt%.Described inorganic acid can be nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid etc.
One or more of.Described soluble palladium salt is one or more of palladium nitrate, palladium bichloride etc..
The inventive method step（2）Detailed process is as follows：During dipping in alkyl xanthogenic acid sodium solution for the alumina support
Between be 2 ~ 4 hours, filter, after 95 ~ 105 DEG C of dryings 2 ~ 4 hours, by the alumina support spray portion containing alkyl xanthogenic acid sodium
Divide the maceration extract containing palladium, be dried 4～8 hours at 105～120 DEG C, obtain catalyst intermediate.
Step（3）The method of described dipping residual metallic palladium is using conventional dipping method, i.e. satiety and/or saturation leaching
Stain method.By step（2）The catalyst intermediate obtaining is put in remaining acidity maceration extract, impregnates 4 ~ 8 hours, after terminating,
It is dried 4～8 hours at 105～110 DEG C, sintering temperature is 350～480 DEG C, roasting time 4～8 hours obtains final catalyst
Product.
The vulcanization type Pd/ Al of the inventive method gained2O3Catalyst, before use will be through reduction treatment, this reduction side
Method can be using conventional method of reducing, it is preferred to use hydrogen reducing, reducing condition is as follows：Pressure 1.0～6.0MPa, temperature
100～120 DEG C, 4～8 hours time, gas agent volume ratio 300 ~ 500.
In acetone through one-step method synthesis MIBK reaction, condensation dehydration acid centre and hydrogenation sites are on a catalyst
Distribution situation directly affects the coupling of two functions in catalyst.Palladium catalyst too high levels, hydrogenation activity strengthens, and easily causes acetone
Directly it is hydrogenated generation isopropanol.The acid centre too high levels of catalyst, palladium content is too low, easily causes condensation on acid site
The isopropylidene acetone part that dehydration generates is not hydrogenated generation MIBK, thus affecting the activity and selectivity of catalyst, and with
The growth of catalyst runs time, carbon distribution can make partial hydrogenation activated centre be poisoned, and therefore palladium content is too low, also impact catalysis
The life-span of agent.
Therefore, the present invention is in catalyst preparation process, step（2）Using alumina support in alkyl xanthogenic acid sodium solution
Middle dipping certain time, spray the acid maceration extract containing palladium after filtration, drying again, make the palladium ion in spray maceration extract in acidity
Spray maceration extract in adsorptive in the alumina support duct containing alkyl xanthogenic acid sodium, make carrier in the hole palladium ion and
Alkyl xanthogenic acid sodium reacts in carrier in the hole, and the palladium sulfide precipitation thing uniform deposition of generation, in carrier duct, is so conducive to
The deposition of sulfuration palladium salt, thus prepare supported sulfided catalyst intermediate, step（3）Middle by step（2）The catalysis obtaining
Agent intermediate impregnates in acidic nitric palladium maceration extract, dry, roasting, the partial oxidation type palladium obtaining, and can make palladium crystal grain height
Dispersion is carried on alumina support surfaces externally and internally, and then makes oxidized form palladium and palladium salt sulfide be evenly distributed in the interior of carrier
On outer surface, i.e. uniformly type distribution, rather than eggshell type distribution.The catalyst so obtaining has good presulfurization effect, sulphur
Change type palladium has been passivated the hydrogenation activity of palladium at the catalyst initial stage, make catalyst difunctional coupling more preferable, thus improve urging
The activity and selectivity of agent.With the growth of the duration of runs, vulcanization type palladium progressively can be converted into active palladium in atmosphere of hydrogen,
And make catalyst life.The catalyst of the inventive method gained is applied to methylisobutanone synthesized from acetone process.This
Bright catalyst gama-alumina does carrier, cheap, has resistance to temp effect well, so that range of reaction temperature is widened, fortune
Turn cycle stretch-out, catalyst preparation process is easy, reduces the production cost of product.
Specific embodiment
With reference to embodiment, the present invention is further described in detail it is noted that following examples not
It is limiting the scope of the invention, those skilled in the art can do suitable expansion with reference to description of the invention and full text
Exhibition, these extensions should be all protection scope of the present invention.In the present invention, v% is volume fraction, and wt% is mass fraction.
Embodiment 1
（1）, the preparation of maceration extract
（a）Sodium ethylxanthate is put in 200 milliliters of beakers, adds deionized water dissolving, be configured to xanthan containing ethyl
The solution of sour sodium 0.5wt%；B () is by Pd (NO3)2·2H2O is put in 200 milliliters of beakers, adds deionized water dissolving, uses nitric acid
Adjust maceration extract pH value to 4, be configured to the dipping solution containing palladium 0.15wt%.
（2）11 milliliters of the solution that load vulcanization type active component measures containing sodium ethylxanthate 0.5wt% pours 100 milliliters into
In beaker, take 10g gama-alumina（Specific surface area 189m2/ g, pore volume 0.4mL/g）Pour into wherein, impregnate 3 hours, filter,
100 DEG C of dryings must be dried sample in 2 hours, measures the 14 milliliters of spray drying samples of dipping solution containing palladium 0.15wt%, in 115 DEG C of dryings
6 hours, obtain catalyst intermediate.
（3）Load oxidized form active component
Measure 23 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, by step（2）In the catalyst obtaining
Mesosome is poured into wherein, impregnates 6 hours, filters, in 105 DEG C of dryings 6 hours, in 400 DEG C of roastings 6 hours, obtains finished catalyst M-
1, carrying palladium amount in catalyst is 0.5wt%.
Embodiment 2
（1）（a）Xanthogen sodium is put in 200 milliliters of beakers, adds deionized water dissolving, be configured to yellow containing propyl group
The solution of ortho acid sodium 0.5wt%；Step（b）With embodiment 1 (b).
（2）, load vulcanization type active component
10 milliliters of solution measuring the 0.5wt% of sodium containing xanthogen is poured in 100 milliliters of beakers, takes 10g gamma oxidation
Aluminium（Specific surface area 189m2/ g, pore volume 0.4mL/g）Pour into wherein, impregnate 4 hours, filter, 3 hours must be dry in 105 DEG C of dryings
Sample, measures the 10 milliliters of spray drying samples of dipping solution containing palladium 0.15wt%, in 115 DEG C of dryings 6 hours, obtains in the middle of catalyst
Body.
（3）Load oxidized form active component
Measure 17 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, by step（2）Obtain in catalyst
Mesosome is poured into wherein, conventional dipping 3 hours, filters, and in 105 DEG C of dryings 6 hours, in 400 DEG C of roastings 7 hours, obtains finished product catalysis
Agent M-2, it is 0.40wt% that catalyst carries palladium amount.
Embodiment 3
（1）With embodiment 1
（2）Load vulcanization type active component
Measure 6 milliliters of the solution containing sodium ethylxanthate 0.5wt% to pour in 100 milliliters of beakers, take 10g gama-alumina
（Specific surface area 189m2/ g, pore volume 0.4mL/g）Pour into wherein, impregnate 4 hours, filter, 2 hours must be dry in 105 DEG C of dryings
Sample, measures the 6 milliliters of spray drying samples of dipping solution containing palladium 0.15wt%, in 115 DEG C of dryings 6 hours, obtains catalyst intermediate；
（3）Load oxidized form active component
Measure 14 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, by step（2）Obtain in catalyst
Mesosome is poured into wherein, conventional dipping 5 hours, filters, and in 105 DEG C of dryings 6 hours, in 450 DEG C of roastings 6 hours, obtains finished product catalysis
Agent M-3, it is 0.30wt% that catalyst carries palladium amount.
Embodiment 4
（1）（a）Sodium n-butyl-xanthate is put in 200 milliliters of beakers, adds deionized water dissolving, be configured to yellow containing butyl
The solution of ortho acid sodium 0.5wt%；Step（b）With embodiment 1 (b).
（2）, load vulcanization type active component
Measure 6 milliliters of the solution containing sodium n-butyl-xanthate 0.5wt% to pour in 100 milliliters of beakers, take 10g gama-alumina
（Specific surface area 189m2/ g, pore volume 0.4mL/g）Pour into wherein, impregnate 4 hours, filter, 3 hours must be dry in 105 DEG C of dryings
Sample, measures the 6 milliliters of spray drying samples of dipping solution containing palladium 0.15wt%, in 115 DEG C of dryings 8 hours, obtains catalyst intermediate.
（3）Load oxidized form active component
Measure 11 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, by step（2）Obtain in catalyst
Mesosome is poured into wherein, conventional dipping 5 hours, filters, and in 105 DEG C of dryings 6 hours, in 450 DEG C of roastings 7 hours, obtains finished product catalysis
Agent M-4, it is 0.25wt% that catalyst carries palladium amount.
Example applies 5
（1）With embodiment 4
（2）Load vulcanization type active component
Measure 14 milliliters of the solution containing sodium n-butyl-xanthate 0.5wt% to pour in 100 milliliters of beakers, take 10g gamma oxidation
Aluminium（Specific surface area 189m2/ g, pore volume 0.4mL/g）Pour into wherein, impregnate 4 hours, filter, 4 hours must be dry in 105 DEG C of dryings
Sample, measures the 14 milliliters of spray drying samples of dipping solution containing palladium 0.15wt%, in 115 DEG C of dryings 8 hours, obtains in the middle of catalyst
Body.
（3）Load oxidized form active component
Measure 26 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, by step（2）Obtain in catalyst
Mesosome is poured into wherein, conventional dipping 7 hours, filters, and in 105 DEG C of dryings 6 hours, in 450 DEG C of roastings 7 hours, obtains finished product catalysis
Agent M-5, it is 0.6wt% that catalyst carries palladium amount.
Comparative example 1
（1）By Pd (NO3)2·2H2O is put in 200 milliliters of beakers, adds deionized water dissolving, adjusts maceration extract with nitric acid
PH value, to 4, is configured to the dipping solution containing palladium 0.15wt%.
（2）Load oxidized form active component
Measure 34 milliliters of dipping solution containing palladium 0.15wt% in 200 milliliters of beakers, take 10g gama-alumina（Property is with real
Apply example 1）Pour into wherein, be gently mixed 5 hours, be filtered to remove residual solution, in 105 DEG C of dryings 7 hours, little in 400 DEG C of roastings 6
When, obtain finished catalyst DM-1, it is 0.5wt% that catalyst carries palladium amount.
Embodiment 6 ~ 10
The reaction unit evaluating catalyst is internal diameter 8mm, the continuous microreactor of stainless steel tubular type of long 300mm, reaction
Upper feeding, reaction mass flows out from reactor bottom, enters separator, gas phase circulation of tail gas or metering emptying, liquid after cooling
Phase timing sampling, uses gas chromatographic analysis.
In Example 1 ~ 5, (quartz sand being broken into 8 ~ 24 mesh with 5ml 24 ~ 40m mesh mixes each 5g of prepared catalyst
Close uniformly), be respectively charged in reactor, airtight qualified after, lead to hydrogen first（The electrolytic cleaning hydrogen of 99v%）Carry out catalyst
Reduce, reducing condition is：100 DEG C of reduction temperature；Pressure 4.0MPa；Gas agent volume ratio 500；4 hours time.
After reduction terminates, enter acetone raw material, be gradually heating to reaction temperature, reacted by reaction condition.Operating condition
And the results are shown in Table 1.
Comparative example 2
Reaction unit, Catalyst packing and the reducing condition of evaluating comparative example DM-1 oxidation catalyst, with embodiment 6, are gone back
After former end, enter the presulfurization stage.Detailed process：（1）Formulating vulcanization oil, accurately weighs dimethyl disulfide 0.0044g and is dissolved in
In 20ml acetone, mix, acetone consumption is 4 times of catalyst volume, wherein sulphur and the molar ratio of palladium are 0.4:1,（2）
Presulfurization, 120 DEG C of curing temperature；Pressure 3.5MPa；Sulfuration air speed 2.0h-1.After sulfurized oil has entered, switching raw material acetone just switchs to
The paradoxical reaction stage.Operating condition and the results are shown in Table 1.
Table 1
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 2 | |
| Catalyst is numbered | M-1 | M-2 | M-3 | M-4 | M-5 | DM-1 |
| Reaction temperature, DEG C | 160 | 170 | 160 | 180 | 150 | 160 |
| Reaction pressure, MPa | 6.0 | 5.0 | 5.0 | 6.0 | 6.0 | 6.0 |
| Air speed, h-1 | 2.0 | 1.5 | 1.5 | 1.0 | 1.0 | 2.0 |
| The duration of runs, h | 500 | 500 | 500 | 500 | 500 | 500 |
| H2/ AC, (v) | 500 | 600 | 700 | 800 | 800 | 500 |
| Conversion ratio, mol% | 47.98 | 46.52 | 44.65 | 45.81 | 47.91 | 43.14 |
| MIBK is selective, mol% | 97.77 | 97.59 | 97.79 | 97.86 | 97.66 | 96.57 |
Claims (12)
1. a kind of vulcanization type Pd/ Al2O3The preparation method of catalyst is it is characterised in that include：
（1）Prepare alkyl xanthogenic acid sodium solution and the maceration extract containing palladium, the maceration extract containing palladium is acidity；
（2）Alumina support is immersed in alkyl xanthogenic acid sodium solution, carries out after terminating filtering, be dried, shower portion contains palladium
Maceration extract, be dried after obtain catalyst intermediate；
（3）Catalyst intermediate is added to dipping in the remaining maceration extract containing palladium, dry, roasting, obtains vulcanization type Pd/
Al2O3Catalyst；
Wherein, the concentration of alkyl xanthogenic acid sodium solution is 0.1wt% ~ 1.0wt%, step（2）Spray maceration extract containing palladium used
Volume and step（3）The ratio of the maceration extract volume containing palladium used is 1.0:1.0~1.0:3.0.
2. method according to claim 1 it is characterised in that：The concentration of alkyl xanthogenic acid sodium solution is 0.3 wt% ~ 0.6
Wt%, step（2）Spray maceration extract volume containing palladium used and step（3）The ratio of the maceration extract volume containing palladium used is 1.0：
1.5~1.0：2.5.
3. method according to claim 1 it is characterised in that：The carbon number of the alkyl in described alkyl xanthogenic acid sodium
For 2 ~ 4.
4. method according to claim 1 it is characterised in that：Described vulcanization type Pd/ Al2O3The weight of palladium in catalyst
Content is calculated as 0.1wt% ~ 0.7wt% with metal.
5. method according to claim 1 it is characterised in that：Described alumina support is gamma-aluminium oxide carrier, its property
Matter is as follows：Specific surface area 140 ~ 260m2/g；Pore volume 0.3～0.8 mL/g；Described alumina support be shaped as spherical or bar
Shape.
6. method according to claim 1 it is characterised in that：The described maceration extract containing palladium is adopted and is prepared with the following method, will
Soluble palladium salt is soluble in water, then is acid with the pH value that inorganic acid adjusts maceration extract, and in maceration extract, the concentration of palladium is 0.1wt%
~ 1.0wt%.
7. method according to claim 6 it is characterised in that：The pH value that inorganic acid adjusts maceration extract is 2 ~ 4, in maceration extract
The concentration of palladium is 0.1 wt% ~ 0.6 wt%.
8. method according to claim 6 it is characterised in that：Described inorganic acid is nitric acid, hydrochloric acid, phosphoric acid, in sulfuric acid
One or more, described soluble palladium salt is one or more of palladium nitrate, palladium bichloride.
9. method according to claim 1 it is characterised in that：Step（2）Detailed process is as follows：Alumina support is in alkyl
Dip time in sodium xanthogenate solution be 2 ~ 4 hours, filter, after 95 ~ 105 DEG C of dryings 2 ~ 4 hours, will be containing alkyl xanthan
The alumina support shower portion of sour sodium contains the maceration extract of palladium, is dried 4～8 hours, obtains in catalyst at 105～120 DEG C
Mesosome.
10. method according to claim 1 it is characterised in that：Step（3）The described remaining maceration extract containing palladium of dipping
Method using satiety and/or saturation infusion process.
11. methods according to claim 1 it is characterised in that：By step（2）The catalyst intermediate obtaining puts into residue
Acid maceration extract in, impregnate 4 ~ 8 hours, after terminating, at 105～110 DEG C be dried 4～8 hours, sintering temperature be 350～
480 DEG C, roasting time 4～8 hours, obtain final catalyst prod.
12. methods according to claim 1 it is characterised in that：The vulcanization type Pd/ Al of gained2O3Catalyst, before use
Will be through reduction treatment, this method of reducing adopts hydrogen reducing, and reducing condition is as follows：Pressure 1.0～6.0MPa, temperature 100～
120 DEG C, 4～8 hours time, gas agent volume ratio 300 ~ 500.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069674A (en) * | 1991-08-29 | 1993-03-10 | 中国石油化工总公司抚顺石油化工研究院 | The molecular sieve catalyst of synthesize methyl-isobutyl ketone and method for making |
| CN1255404A (en) * | 1998-11-27 | 2000-06-07 | 吉林化学工业公司研究院 | One-step method for synthesizing methylisobutone acetone catalyst and preparing process for same |
| CN1273231A (en) * | 2000-06-09 | 2000-11-15 | 边俊民 | Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst |
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| FR2968002B1 (en) * | 2010-11-30 | 2012-11-23 | Rhodia Poliamida E Especialidades Ltda | PROCESS FOR THE PRODUCTION OF DIBK |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069674A (en) * | 1991-08-29 | 1993-03-10 | 中国石油化工总公司抚顺石油化工研究院 | The molecular sieve catalyst of synthesize methyl-isobutyl ketone and method for making |
| CN1255404A (en) * | 1998-11-27 | 2000-06-07 | 吉林化学工业公司研究院 | One-step method for synthesizing methylisobutone acetone catalyst and preparing process for same |
| CN1273231A (en) * | 2000-06-09 | 2000-11-15 | 边俊民 | Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst |
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