CN107199033A - A kind of preparation method of phenol gas phase hydrogenation preparing cyclohexanone catalyst - Google Patents
A kind of preparation method of phenol gas phase hydrogenation preparing cyclohexanone catalyst Download PDFInfo
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- CN107199033A CN107199033A CN201610154939.2A CN201610154939A CN107199033A CN 107199033 A CN107199033 A CN 107199033A CN 201610154939 A CN201610154939 A CN 201610154939A CN 107199033 A CN107199033 A CN 107199033A
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- palladium
- activated carbon
- preparation
- catalyst
- oxidant
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 239000003610 charcoal Substances 0.000 claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000002250 absorbent Substances 0.000 abstract description 12
- 230000002745 absorbent Effects 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 238000002803 maceration Methods 0.000 abstract 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- OOJYPCDXFPWXFL-UHFFFAOYSA-N [C].OC1=CC=CC=C1 Chemical class [C].OC1=CC=CC=C1 OOJYPCDXFPWXFL-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/397—
-
- 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
- B01J37/12—Oxidising
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
Abstract
The present invention relates to a kind of preparation method of phenol hydrogenation preparing cyclohexanone catalyst.This method carries out activated carbon after acid treatment and oxidation processes, then carries out the steps such as palladium absorption, alkali precipitation, reduction, finally gives catalyst prod.It is characterized in by way of activated carbon is carried out into oxidant pretreatment and oxidant is added in adsorption liquid, Metal Palladium is evenly distributed on the outer surface of absorbent charcoal carrier, prevent direct-reduction of the reduction group of activated carbon surface to the palladium ion in maceration extract；By ultrasonic spray adsorption technology load active component, Metal Palladium can be goed deep into activated carbon surface hole, further increase Pd decentralization, be conducive to phenol hydrogenation preparing cyclohexanone to react.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyst for all kinds of organic compound hydrogenation processes, more particularly to one
Plant the preparation method for the catalyst that phenol can be converted into cyclohexanone.
Background technology
Activity, selectivity and the stability of phenol gas phase hydrogenation preparing cyclohexanone catalyst have larger shadow to its production cost
Ring, and property, structure and the quantity of catalyst surface metallic atom are the keys for determining reactivity and selectivity.Ordinary circumstance
Under, the hydrogenation activity of metallic catalyst is relevant with metallic area size, and metallic area size and the grain size or metal of metal
Decentralization it is relevant.It is reported that Supported Pd-Catalyst shown in phenol gas phase hydrogenation preparing cyclohexanone good activity and
Selectivity（GB1063357A）, because Pd is noble metal, consumption is typically less, therefore we are using the activity with high surface area
High-area carbon is by Pd high degree of dispersion, to obtain big Pd areas.Because phenol hydrogenation reaction is main by external diffusion control, activearm
Divide to try one's best and be distributed in the outside of carried by active carbon external surface, however, the heat endurance in order to improve catalyst, also requires that Pd exists
Certain depth is distributed with absorbent charcoal carrier surface.So, there is considerable part Pd to be distributed in activated carbon hole, can also enter
One step improves Pd decentralization, and enhancing absorbent charcoal carrier is acted on, simultaneously because active component is suitably deep, exotic is to catalyst
Murder by poisoning also relative be difficult so that activity is protected.
The preparation method of traditional palladium-carbon catalyst is dipping absorption method（US4394299）, this method prepare palladium carbon urge
During agent, need to significantly it be stirred with reference to agitating paddle, so that palladium solution uniform adsorption, but for benzene on the activated carbon
Phenol is hydrogenated with preparing cyclohexanone palladium-carbon catalyst, and Metal Palladium is distributed in carrier surface in eggshell, and significantly whipping process easily makes table
Face palladium comes off, and causes surface palladium content reduction, influences the activity of catalyst.And ultrasonic spray adsorption technology is used, on the one hand
Adsorption liquid can be dispersed as ultra micro molecule by ultrasonic wave, go deep into activated carbon surface hole, further increase Pd decentralization；It is another
Aspect, carrier is slowly rotated with reactor, uniform adsorption ultra micro molecule, and frictional impact is lighter between carrier, is difficult to form powder falling.
The content of the invention
It is evenly distributed it is an object of the invention to provide a kind of active component in carrier surface and there is the height of certain depth
The preparation method of performance phenol hydrogenation preparing cyclohexanone catalyst.
The present invention's is mainly characterized by：By the way that activated carbon is carried out oxidant pretreatment and added in adsorption liquid to aoxidize
The mode of agent, makes Metal Palladium be evenly distributed on the outer surface of absorbent charcoal carrier, prevents the reduction group of activated carbon surface to dipping
The direct-reduction of palladium ion in liquid；By ultrasonic spray adsorption technology load active component, Metal Palladium can go deep into activated carbon
In surface holes, Pd decentralization is further increased, is conducive to phenol hydrogenation preparing cyclohexanone to react.
The preparation method that the present invention is provided, it comprises the following steps：
Carrier active carbon is carried out pickling by step 1., and the concentration of acid solution is 0.1N-2.0N, and temperature is 30 DEG C -100 DEG C, and the time is
1h-4h, is washed to neutrality；
Activated carbon after step 2. pickling carries out oxidation processes again, and oxidant is 1 with activated carbon mol ratio:8-1:20, the time is
1h-6h, is filtered, and is washed, and is dried；
Treated activated carbon is carried out palladium absorption by step 3. by ultrasonic spray adsorption technology, and adsorption liquid is aerobic to add
The palladium salt solution of agent, oxidant is 1 with activated carbon mol ratio:8-1:20, palladium load capacity is the 0.05%-3% of activated carbon, time
For 1h-12h；
Step 4. alkaline chemical precipitation Metal Palladium, regulation pH value is 8.0-10.0, and the sedimentation time is 4h-48h, precipitation temperature is 30 DEG C-
90℃；
Step 5. adds the palladium compound of reducing agent reduction adsorption on the activated carbon, and reducing agent consumption is palladium ion molal quantity
50-200 times, reduction temperature is 30 DEG C -90 DEG C, and the time is 1h-8h, is filtered, and is washed, and is dried.
Activated carbon of the present invention is selected from irregular particle charcoal, regular spherical carbon or cylindricality charcoal.
Acid solution of the present invention is selected from hydrochloric acid, nitric acid or phosphoric acid.
One or more of the oxidant of the present invention in hydrogen peroxide, sodium hypochlorite or perchloric acid are in any proportion
Combination.
Palladium salt of the present invention is selected from palladium bichloride or palladium.
Ultrasonic spray adsorption technology of the present invention, adsorption liquid consumption is equal to the 40%- of activated carbon saturated extent of adsorption
90%。
One or more of the alkali of the present invention in subcarbonate, bicarbonate or alkaline earth oxide are pressed
Arbitrary proportion is combined.
The one kind of reducing agent of the present invention in formaldehyde, hydrazine hydrate, sodium borohydride, hydrogen or sodium formate.
Catalyst prepared by the present invention reacts available for phenol gas phase hydrogenation preparing cyclohexanone, and its method is：Catalyst is filled
Fill out in the reactor, first rise to 180 DEG C -240 DEG C from room temperature in atmosphere of hydrogen, then constant temperature reduction 6h-24h is down to 140
DEG C of -180 DEG C progress phenol gas phase hydrogenation reactions, reaction pressure is 0.05 MPa -0.3MPa, and hydrogen phenol ratio is 4/1-10/1, phenol
Mass space velocity is 0.1 h-1-0.6h-1, produce hydrogenation products cyclohexanone.
Beneficial effects of the present invention are：
1. the palladium-carbon catalyst of the acid treated preparation of activated carbon, impurity content is low, content of ashes is small.
2. after oxidized dose of processing of activated carbon after acid treatment, palladium metal being uniformly distributed on carrier can be improved.
3. adding oxidant in palladium salt solution, palladium salt can be prevented to be reduced directly, form the uniform eggshell shape of Metal Palladium
Distribution.
4. the palladium-carbon catalyst prepared using ultrasonic spray adsorption technology, resulting catalyst metals palladium distribution is equal
Even, palladium load capacity is the 0.05%-3% of activated carbon, and Metal Palladium is goed deep into depth for 50-200 μm on absorbent charcoal carrier, is conducive to
Phenol hydrogenation preparing cyclohexanone reacts.
Brief description of the drawings
Fig. 1 is palladium-carbon catalyst surface transmission electromicroscopic photograph prepared by the embodiment of the present invention 1（TEM）.
Fig. 2 is palladium-carbon catalyst Cross-section transmission electromicroscopic photograph prepared by the embodiment of the present invention 1（TEM）.
Fig. 3 is palladium-carbon catalyst surface transmission electromicroscopic photograph prepared by comparative example 7 of the present invention（TEM）.
Fig. 4 is palladium-carbon catalyst Cross-section transmission electromicroscopic photograph prepared by comparative example 7 of the present invention（TEM）.
Embodiment
Embodiment 1
Activated Carbon Pretreatment：
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 0.1N is added, 100 DEG C of washing 4h, filtering is washed to
It is neutral；400mL water is added, 20mL hydrogen peroxide, 3mL sodium hypochlorite is stored at room temperature 1h after being well mixed, filtered, washing, after drying
It is standby.
The preparation of palladium-carbon catalyst：
Weigh activated carbons of the 10g by pretreatment, ultrasonic spray absorption palladium bichloride containing 3mL20g/L and 2mL hydrogen peroxide it is mixed
Solution is closed, stands and 20mL water is added after 1h, is adjusted with sodium carbonate behind pH=8,10mLNaHCO is added3, 24h is precipitated at 30 DEG C, plus
Enter and reduce 8h at 3mL formaldehyde, 30 DEG C, filter, wash, dry, produce the palladium-carbon catalyst of the present embodiment.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 0.49% in catalyst, and palladium is brilliant
Spend for 26, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 100 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make phenol
Conversion ratio is 99%, cyclohexanone selectivity 90%.
Embodiment 2
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 0.5N is added, 100 DEG C of washing 4h, filtering is washed to
It is neutral；400mL water is added, 20mL hydrogen peroxide, 3mL sodium hypochlorite is stored at room temperature 1h after being well mixed, filtered, washing, after drying
It is standby.
The preparation of palladium-carbon catalyst：
Weigh 10g by pretreatment activated carbon, ultrasonic spray absorption palladium bichloride containing 2mL30g/L, 1.5mL hydrogen peroxide and
The mixed solution of 0.2mL sodium hypochlorite, stands and 20mL water is added after 4h, is adjusted with sodium carbonate behind flat pH=9, adds
10mLNaHCO3, 24h is precipitated at 50 DEG C, 60 DEG C are warming up to, and is added 8mL formaldehyde reduction 6h, is filtered, wash, dry, produce this reality
Apply the palladium-carbon catalyst of example.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 0.45% in catalyst, and palladium is brilliant
Spend for 46, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 60 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make turning for phenol
Rate is 99%, cyclohexanone selectivity 92%.
Embodiment 3
Activated Carbon Pretreatment：
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 1N, 80 DEG C of washing 3h, filtering, in being washed to is added
Property；400mL water is added, 30mL hydrogen peroxide, 3mL sodium hypochlorite is stored at room temperature 3h after being well mixed, filtered, and standby is dried in washing
With.
The preparation of palladium-carbon catalyst：
Weigh 10g by pretreatment activated carbon, ultrasonic spray absorption palladium bichloride containing 3mL40g/L, 1.5mL hydrogen peroxide and
The mixed solution of 0.2mL sodium hypochlorite, stands and 20mL water is added after 4h, is adjusted with sodium carbonate behind pH=9, adds 10mL
NaHCO3, 24h is precipitated at 50 DEG C, 60 DEG C are warming up to, and is added 8mlL formaldehyde reduction 6h, is filtered, wash, dry, produce this implementation
The palladium-carbon catalyst of example.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 1.12% in catalyst, and palladium is brilliant
Spend for 54, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 90 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make turning for phenol
Rate is 99%, cyclohexanone selectivity 89%.
Embodiment 4
Activated Carbon Pretreatment：
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 1N, 80 DEG C of washing 3h, filtering, in being washed to is added
Property；400mL water is added, 30mL hydrogen peroxide, 3mL sodium hypochlorite is stored at room temperature 3h after being well mixed, filtered, and standby is dried in washing
With.
The preparation of palladium-carbon catalyst：
Weigh 10g by pretreatment activated carbon, ultrasonic spray absorption palladium bichloride containing 3mL50g/L, 1mL hydrogen peroxide and
The mixed solution of 0.4mL perchloric acid, stands and 20mL water is added after 8h, is adjusted with sodium carbonate behind pH=9, adds 10mLNaHCO3, 70
24h is precipitated at DEG C, 80 DEG C are warming up to, 10mL formaldehyde reduction 6h is added, filters, wash, dry, the palladium carbon for producing the present embodiment is urged
Agent.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 1.45% in catalyst, and palladium is brilliant
Spend for 86, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 95 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make turning for phenol
Rate is 99%, cyclohexanone selectivity 92%.
Embodiment 5
Activated Carbon Pretreatment：
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 2N, 50 DEG C of washing 2h, filtering, in being washed to is added
Property；400mL water is added, 40mL perchloric acid is stored at room temperature 4h after being well mixed, filtered, and washing is standby after drying.
The preparation of palladium-carbon catalyst：
Weigh 10g by pretreatment activated carbon, ultrasonic spray absorption palladium bichloride containing 3mL80g/L, 1mL hydrogen peroxide and
The mixed solution of 0.4mL perchloric acid, stands and 20mL water is added after 8h, is adjusted with sodium carbonate behind pH=9, adds 10mLNaHCO3, 70
24h is precipitated at DEG C, 80 DEG C are warming up to, 10mL formaldehyde reduction 6h is added, filters, wash, dry, the palladium carbon for producing the present embodiment is urged
Agent.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 2.35% in catalyst, and palladium is brilliant
Spend for 116, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 85 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make phenol
Conversion ratio is 99%, cyclohexanone selectivity 87%.
Embodiment 6
Activated Carbon Pretreatment：
100g4-8 mesh activated carbons are weighed, the hydrochloric acid solution that 500mL concentration is 2N, 30 DEG C of washing 4h, filtering, in being washed to is added
Property；400mL water is added, 40mL perchloric acid, 3mL sodium hypochlorite is stored at room temperature 4h after being well mixed, filtered, washing, after drying
It is standby.
The preparation of palladium-carbon catalyst：
Weigh 10g by pretreatment activated carbon, ultrasonic spray absorption palladium bichloride containing 3mL80g/L, 2mL hydrogen peroxide and
The mixed solution of 0.4mL sodium hypochlorite, stands and 20mL water is added after 12h, is adjusted with sodium carbonate behind pH=9, adds
10mLNaHCO3, 24h is precipitated at 90 DEG C, 90 DEG C are warming up to, and is added 10mL formaldehyde reduction 8h, is filtered, wash, dry, produce this
The palladium-carbon catalyst of embodiment.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 2.05% in catalyst, and palladium is brilliant
Spend for 136, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 125 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make phenol
Conversion ratio is 99%, cyclohexanone selectivity 82%.
Comparative example 7
This comparison example compared with Example 1 compared with, wherein, Activated Carbon Pretreatment method is identical, the preparation method of palladium-carbon catalyst
It is as follows：
The mixed solution of activated carbons of the 10g by pretreatment, spraying absorption palladium bichloride containing 3mL20g/L and 2mL hydrogen peroxide is weighed,
Stand and 20mL water is added after 1h, adjusted with sodium carbonate behind pH=8, add 10mLNaHCO3, 24h is precipitated at 30 DEG C, 3mL first is added
8h is reduced at 30 DEG C of aldehyde, is filtered, is washed, dries, produces the palladium-carbon catalyst of the present embodiment.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of Metal Palladium is 0.50% in catalyst, and palladium is brilliant
Spend for 76, go deep into depth of the Metal Palladium on absorbent charcoal carrier is 20 μm, and catalysis of phenol hydrogenation preparing cyclohexanone can make turning for phenol
Rate is 99%, cyclohexanone selectivity 76%.
Except the various embodiments described above, embodiment of the present invention also has a lot, all technical sides using equivalent or equivalence replacement
Case, in protection scope of the present invention.
Although describing the present invention in the illustration more than, but it is to be understood that, described details is only used for
For example, those skilled in the art can make in the spirit and scope that the claim without departing substantially from the present invention is limited to it
Change.
Claims (8)
1. a kind of preparation method of phenol hydrogenation preparing cyclohexanone catalyst, it comprises the following steps：
Carrier active carbon is carried out pickling by step 1., and the concentration of acid solution is 0.1N-2.0N, and temperature is 30 DEG C -100 DEG C, and the time is
1h-4h, is washed to neutrality；
Activated carbon after step 2. pickling carries out oxidation processes again, and oxidant is 1 with activated carbon mol ratio:8-1:20, the time is
1h-6h, is filtered, and is washed, and is dried；
Treated activated carbon is carried out palladium absorption by step 3. by ultrasonic spray absorption, and adsorption liquid is added with oxidant
Palladium salt solution, oxidant and activated carbon mol ratio are 1:8-1:20, palladium load capacity is the 0.05%-3% of activated carbon, and the time is
1h-12h；
Step 4. alkaline chemical precipitation Metal Palladium, regulation pH value is 8.0-10.0, and the sedimentation time is 4h-48h, precipitation temperature is 30 DEG C-
90℃；
Step 5. adds the palladium compound of reducing agent reduction adsorption on the activated carbon, and reducing agent consumption is palladium ion molal quantity
50-200 times, reduction temperature is 30 DEG C -90 DEG C, and the time is 1h-8h, is filtered, and is washed, and is dried.
2. preparation method according to claim 1, it is characterised in that described activated carbon is selected from irregular particle charcoal, rule
Spherical carbon or cylindricality charcoal.
3. preparation method according to claim 1, it is characterised in that described acid solution is selected from hydrochloric acid, nitric acid or phosphoric acid.
4. preparation method according to claim 1, it is characterised in that described oxidant be selected from hydrogen peroxide, sodium hypochlorite or
One or more in perchloric acid are combined in any proportion.
5. preparation method according to claim 1, it is characterised in that described palladium salt is selected from palladium bichloride or palladium.
6. preparation method according to claim 1, it is characterised in that described ultrasonic spray absorption, adsorption liquid consumption etc.
In the 40%-90% of the saturated extent of adsorption of activated carbon.
7. preparation method according to claim 1, it is characterised in that described alkali be selected from subcarbonate, bicarbonate or
One or more in alkaline earth oxide are combined in any proportion.
8. preparation method according to claim 1, it is characterised in that described reducing agent is selected from formaldehyde, hydrazine hydrate, boron hydrogen
Change one kind in sodium, hydrogen or sodium formate.
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| CN109453767A (en) * | 2019-01-21 | 2019-03-12 | 郴州高鑫铂业有限公司 | A kind of Pd-Au/C bimetallic catalyst and its preparation method and application |
| CN110560048A (en) * | 2019-09-03 | 2019-12-13 | 昆明理工大学 | Preparation method of megalophyta biological carbon palladium-based catalyst with high specific surface area |
| CN111282567A (en) * | 2019-12-17 | 2020-06-16 | 江苏欣诺科催化剂有限公司 | Palladium-carbon catalyst and method and application thereof |
| CN114602524A (en) * | 2022-03-02 | 2022-06-10 | 武汉科技大学 | Preparation of nitrogen modified catalyst and application thereof in preparation of cyclohexanone by phenol hydrogenation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453767A (en) * | 2019-01-21 | 2019-03-12 | 郴州高鑫铂业有限公司 | A kind of Pd-Au/C bimetallic catalyst and its preparation method and application |
| CN110560048A (en) * | 2019-09-03 | 2019-12-13 | 昆明理工大学 | Preparation method of megalophyta biological carbon palladium-based catalyst with high specific surface area |
| CN111282567A (en) * | 2019-12-17 | 2020-06-16 | 江苏欣诺科催化剂有限公司 | Palladium-carbon catalyst and method and application thereof |
| CN114602524A (en) * | 2022-03-02 | 2022-06-10 | 武汉科技大学 | Preparation of nitrogen modified catalyst and application thereof in preparation of cyclohexanone by phenol hydrogenation |
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