CN113522275A - Palladium-carbon catalyst for preparing disproportionated rosin and preparation method and application thereof - Google Patents
Palladium-carbon catalyst for preparing disproportionated rosin and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 23
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 133
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 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 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 244000060011 Cocos nucifera Species 0.000 claims description 12
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 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
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000007323 disproportionation reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 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
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a palladium-carbon catalyst for preparing disproportionated rosin and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field, and particularly relates to a palladium-carbon catalyst for preparing disproportionated rosin, and a preparation method and application thereof.
Background
The palladium carbon catalyst is widely used in the field of petrochemical industry, such as the preparation of styrene butadiene rubber polymerized emulsifier-disproportionated rosin in the automobile tire industry, and a skeleton nickel catalyst, an iodine catalyst, a sulfide catalyst and the like which do not use a carrier can also be adopted. However, when the catalyst is used for the disproportionated rosin catalytic reaction, the catalyst has the problems of low activity, large using amount of transition metal, long reaction time, high reaction temperature and the like, so that the application development of the catalyst in the disproportionated rosin production process is limited.
At present, palladium-carbon catalyst is mainly adopted for preparing disproportionated rosin at home and abroad, and the catalyst is adopted in industrial production in large scale due to the advantages of high activity, good selectivity, short reaction time, low temperature, small dosage and the like in the catalytic reaction of disproportionated rosin. However, the methods for preparing palladium carbon catalysts are different, for example, the dispersibility of activated carbon is different, and the activity of activated carbon is also different, and the existing palladium carbon catalysts have the following problems: (1) the activated carbon has high ash content, contains heavy metals and is not easy to remove. (2) The dispersion degree of the active components is high, so that the number of active centers per unit surface area of the active carbon is reduced, and the catalytic activity of the active carbon is reduced. Therefore, how to prepare the palladium-carbon catalyst for preparing disproportionated rosin with good dispersibility, low ash content, low heavy metal content and high catalytic activity becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to improve the above technical problems, the present invention provides a palladium on carbon catalyst comprising an activated carbon support and a noble metal palladium supported on the support.
According to an embodiment of the present invention, the noble metal Pd may be present in the palladium on carbon catalyst in an amount of 1 to 5% by weight, for example 2 to 4% by weight, illustratively 1%, 2%, 3%, 4%, 5%.
According to an embodiment of the present invention, in the palladium on carbon catalyst, the noble metal Pd is uniformly distributed on the activated carbon support.
After the activated carbon is oxidized, the concentrations of phenolic hydroxyl, lactone group and carbonyl group on the surface of the activated carbon are changed, and the Pd catalyst taking the activated carbon as a carrier can show higher metal dispersion degree and higher catalytic activity.
The invention also provides a preparation method of the palladium-carbon catalyst, which comprises the following steps:
1) carrying out oxidation treatment on the activated carbon;
2) loading a solution containing a Pd compound on an activated carbon carrier after oxidation treatment to obtain a catalyst precursor;
3) reducing the catalyst precursor obtained in the step 2) in the presence of a reducing agent to obtain the palladium-carbon catalyst.
According to an embodiment of the present invention, the activated carbon may be a shell activated carbon, such as at least one of coconut shell activated carbon, peach shell activated carbon, walnut shell activated carbon, or date shell activated carbon; coconut shell activated carbon is preferred.
According to the embodiment of the invention, the activated carbon is subjected to screening and washing treatment before the oxidation treatment. For example, the washing solvent may be water. Preferably, the ratio of the amount of activated carbon to the amount of washing solvent is 1kg (5-15) L, illustratively 1kg: 10L.
According to an embodiment of the present invention, the oxidizing agent may be hydrogen peroxide (H)2O2) And/or sodium hypochlorite; preferably hydrogen peroxide and sodium hypochlorite. The impurities dispersed in the activated carbon can be boiled and washed clean through oxidation treatment, so that the activated carbon has fewer micropores and developed mesopores.
Preferably, when the oxidizing agent is hydrogen peroxide and sodium hypochlorite, the dosage ratio of the activated carbon to the hydrogen peroxide and the sodium hypochlorite is 1kg (0.1-0.5) L, and the dosage ratio is 1kg:0.25L: 0.125L.
Preferably, the concentration of hydrogen peroxide is 5-20%, exemplary 10%, 15%, 20%.
Preferably, the concentration of sodium hypochlorite is 30-40%, exemplary 30%, 35%, 40%.
Preferably, the temperature of the oxidation treatment is 60-80 ℃, exemplary 60 ℃, 70 ℃, 75 ℃, 80 ℃. Further, the reaction time is 2-5h, exemplary 2h, 3h, 4h, 5 h.
According to an embodiment of the present invention, the palladium-containing compound may be at least one of a halide of Pd, an acetate of Pd, a nitrate of Pd, chloropalladic acid, a basic salt of chloropalladic acid, or a complex of palladium ammonia, and is preferably chloropalladic acid.
According to an embodiment of the present invention, in step 2), the supporting may be dipping or spraying, preferably dipping.
According to an embodiment of the present invention, in the step 3), the reducing agent is a mixed solution of aqueous ammonia and hydrazine hydrate.
Preferably, the volume ratio of the aqueous ammonia to hydrazine hydrate is (3-5):1, illustratively 3:1, 4:1, 5: 1.
Preferably, the ratio of the amount of activated carbon to the amount of reducing agent is (4-5) kg:1L, illustratively 4kg:1L, 4.5kg:1L, 5kg: 1L.
According to an embodiment of the invention, in step 3), the temperature of the reduction is 40 to 80 ℃, exemplary 60 ℃, 70 ℃, 75 ℃, 80 ℃.
According to an embodiment of the invention, in step 3), the reduction time is 0.5-2 h, and is exemplified by 0.5h, 1h and 2 h.
According to the embodiment of the invention, the preparation method further comprises the steps of carrying out solid-liquid separation on the reaction product obtained in the step 3) to obtain the palladium-carbon catalyst and recovering ammonia water and hydrazine hydrate. For example, the solid-liquid separation may be filtration.
According to an embodiment of the present invention, the preparation method further comprises the steps of washing and drying the separated palladium-carbon catalyst.
For example, the solvent for washing may be water. In another example, wash to pH 9.
For example, the temperature of the drying may be 80 to 100 ℃, illustratively 80 ℃, 90 ℃, 100 ℃.
According to an embodiment of the present invention, the method for preparing the palladium on carbon catalyst comprises the steps of:
s1, sieving the activated carbon, repeatedly boiling and washing the activated carbon with deionized water, and filtering to obtain clean activated carbon;
s2, adding H into the activated carbon prepared in the step S12O2Carrying out oxidation treatment on the solution and the sodium chlorate solution;
s3, mixing PdCl2Dissolved in H2Dissolving in O and HCl solution to obtain PdCl2Dissolving and converting into a chloropalladate solution;
s4, mixing the activated carbon subjected to the oxidation treatment of S2 with the chloropalladate solution prepared in the step S3, and reacting;
s5, adding the mixed solution of ammonia water and hydrazine hydrate into the reaction mixed solution prepared in the step S4, and reducing (until the solution is colorless;
s6, carrying out solid-liquid separation on the product obtained in the step S5, washing and drying to obtain the palladium-carbon catalyst, and recovering ammonia water and hydrazine hydrate.
The invention also provides the palladium-carbon catalyst prepared by the preparation method.
The invention also provides application of the palladium-carbon catalyst in catalytic disproportionation reaction, such as application in catalytic rosin disproportionation.
The invention has the beneficial effects that:
(1) the method comprises the steps of firstly, selectively and strongly oxidizing impurities in the activated carbon by oxidation treatment to convert the impurities into soluble salts so as to increase oxygen-containing groups on the surface of the activated carbon, thereby inhibiting the increase of the grain size of Pd. And after the strong oxidation treatment of the activated carbon, the concentration of acidic oxygen-containing groups on the surface of the activated carbon can be increased, so that active sites for nucleation are provided for subsequent noble metal loading.
(2) The coconut shell activated carbon adopted by the invention has high hardness, and the activated carbon with different pore diameter structures and the chloropalladate solution can be loaded after treatment.
(3) The invention adopts a novel environment-friendly process to prepare the disproportionated rosin palladium-carbon catalyst, and the method does not need nitric acid to acidify the active carbon, thereby reducing NO2And (4) discharging. The preparation method is simple and easy to operate, reduces environmental pollution, has high speed, has high catalytic activity and high selectivity in the rosin disproportionation reaction, and has about 50 percent less catalyst dosage than the conventional disproportionation reaction.
(4) After the reducing agent is used up, the reducing agent can be repeatedly used through distillation instead of being reduced by formaldehyde, thereby reducing the environmental pollution.
(5) The invention has high recovery rate and reduces the loss of Pd, and the analysis shows that: the metal content in the waste liquid is less than 0.001 percent, thereby reaching the discharge standard.
(6) The palladium-carbon catalyst prepared by the method has high dispersity, excellent catalyst activity and reusability for 3-4 times.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The source of the activated carbon is as follows: the particle size of the coconut shell activated carbon (inner Mongolian red peak gem activated carbon) is 250-300 meshes. PdCl2(Jinrunhong, Lanzhou, New Material science and technology Co., Ltd.). Raw material gum rosin (Yunnan Cistus Co.), the equipment is 500L vertical enamel reaction kettle, box filter.
Example 1
The preparation method of the palladium-carbon catalyst for producing disproportionated rosin comprises the following steps:
s1, placing the coconut shell activated carbon into a frame type vibrating screen (250-300 meshes) for screening;
s2, adding 40kg of coconut shell activated carbon sieved in the step S1 into a reaction kettle, then adding 400L of deionized water for repeatedly boiling and washing, removing supernatant after cleaning, and then adding 10L of 10% H2O2And when the temperature is raised to 60 ℃, 5L of sodium chlorate solution with the concentration of 30 percent is dripped for 5 hours. Stopping the reaction after the dropwise addition is finished, and washing the mixture to be neutral by using deionized water;
s3, mixing 2kg of PdCl2Adding into a reaction kettle, adding 50L deionized water and 5L HCl solution with concentration of 36% for dissolving, and reacting at 90 deg.C for 3h to obtain PdCl2Dissolving and converting into a chloropalladate solution;
s4, adding deionized water into the chloropalladate solution prepared in the step S3 until the volume is 400L, adding the activated carbon prepared in the step S2, and reacting at 80 ℃ for 24 hours;
s5, adding 300L of deionized water into the reaction mixed solution prepared in the step S4, stirring, heating to 60 ℃, slowly dripping 10L of mixed solution of ammonia water and hydrazine hydrate (8L of ammonia water and 2L of hydrazine hydrate) into a reaction kettle, and carrying out reduction reaction for 30min until a supernatant is colorless;
s6, cooling the reaction liquid reduced in the step S5 to room temperature, filtering and separating, transferring the supernatant into a distillation kettle, and distilling at 90 ℃ to recover ammonia water and hydrazine hydrate; and washing the solid product palladium-carbon catalyst and drying in a 90 ℃ oven.
Example 2
The preparation method of the palladium-carbon catalyst for producing disproportionated rosin comprises the following steps:
s1, placing the coconut shell activated carbon into a frame type vibrating screen (250-300 meshes) for screening;
s2, transferring 45kg of coconut shell activated carbon sieved in the step S1 into a reaction kettle, adding 450L of deionized water for repeatedly boiling and washing, removing supernatant after washing, and adding 11L of H with the concentration of 10%2O2And when the temperature is raised to 70 ℃, 5.6L of 35 percent sodium chlorate solution is dripped for 5 hours. Stopping the reaction after the dropwise addition is finished, and washing the mixture to be neutral by using deionized water;
s3, mixing 2.2kg of PdCl2Adding the mixture into a reaction kettle, adding 60L of deionized water and 5.5L of HCl solution with the concentration of 36% for dissolution, and reacting at 90 ℃ for 3 hours to dissolve and convert palladium chloride into palladium chloride acid solution;
s4, adding deionized water into the chloropalladate solution prepared in the step S3 until the volume is 420L, adding the activated carbon prepared in the step S2, and reacting at 80 ℃ for 24 hours;
s5, adding 320L of deionized water into the reaction mixed solution prepared in the step S4, stirring and heating to 60 ℃, slowly dripping 10L of mixed solution of ammonia water and hydrazine hydrate (8L of ammonia water and 2L of hydrazine hydrate) into a reaction kettle, and carrying out reduction reaction for 30min until a supernatant is colorless;
s6, cooling the reaction liquid reduced in the step S5 to room temperature, filtering and separating, transferring the supernatant into a distillation kettle, and distilling at 90 ℃ to recover ammonia water and hydrazine hydrate; and washing the solid product palladium-carbon catalyst, transferring the solid product palladium-carbon catalyst into a tray, putting the tray into an oven, drying and warehousing.
Example 3
The preparation method of the palladium-carbon catalyst for producing disproportionated rosin comprises the following steps:
s1, placing the coconut shell activated carbon into a frame type vibrating screen (250-300 meshes) for screening;
s2, transferring 50kg of sieved coconut shell activated carbon into a reaction kettle, adding 400L of deionized water for repeatedly boiling and washing, removing supernatant after cleaning, adding 400L of deionized water and 15L of H with the concentration of 15%2O2When the temperature is raised to 75 ℃, 12.5L of 40 percent sodium chlorate solution is dripped for 5 hours. Stopping the reaction after the dropwise addition is finished, and washing the mixture to be neutral by using deionized water;
s3, mixing 2.4kg of PdCl2Transferring the solution to a reaction kettle, adding 70L of deionized water and 7L of HCl solution with the concentration of 36% for dissolution, and reacting at 90 ℃ for 4 hours to dissolve palladium chloride and convert the palladium chloride into palladium chloride acid solution;
s4, adding deionized water into the chloropalladate solution prepared in the step S3 until the volume is 400L, adding the activated carbon prepared in the step S2, and reacting at 80 ℃ for 24 hours;
s5, adding 350L of deionized water into the reaction mixed solution prepared in the step S4, stirring and heating to 60 ℃, slowly dripping 10L of mixed solution of ammonia water and hydrazine hydrate (8L of ammonia water and 2L of hydrazine hydrate) into a reaction kettle, and carrying out reduction reaction for 30min until a supernatant is colorless;
s6, cooling the reaction liquid reduced in the step S5 to room temperature, filtering and separating, transferring the supernatant into a distillation kettle, and distilling at 90 ℃ to recover ammonia water and hydrazine hydrate; and washing the solid product palladium-carbon catalyst, transferring the solid product into a tray, putting the tray into an oven, and drying. And (7) warehousing.
The palladium-carbon catalyst prepared in the embodiments 1 to 3 of the present invention is applied to the production of disproportionated rosin, and each index is shown in the following table 1.
TABLE 1
In Table 1, lots 1 to 3 are product performance indexes obtained when the palladium-carbon catalyst prepared in examples 1 to 3 of the present invention is applied to disproportionated rosin production.
Run Nos. 4 to 8 are product performance indexes obtained when the palladium-carbon catalyst prepared in examples 1 to 3 was applied to disproportionated rosin production when it was repeatedly used 3 times. The results in the table show that: the palladium-carbon catalyst prepared by the method and the palladium-carbon catalyst can be used repeatedly to prepare disproportionated rosin products meeting production indexes when the catalyst is applied to disproportionated rosin production.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A palladium-carbon catalyst is characterized by comprising an activated carbon carrier and noble metal palladium loaded on the carrier.
2. The palladium on carbon catalyst as claimed in claim 1, wherein the palladium on carbon catalyst has a metal Pd content of 1 to 5% by weight, for example 2 to 4% by weight.
3. The method for preparing a palladium on carbon catalyst according to claim 1 or 2, comprising the steps of:
1) carrying out oxidation treatment on the activated carbon;
2) loading a solution containing a Pd compound on an activated carbon carrier after oxidation treatment to obtain a catalyst precursor;
3) reducing the catalyst precursor obtained in the step 2) in the presence of a reducing agent to obtain the palladium-carbon catalyst.
4. The method according to claim 3, wherein the activated carbon is a shell activated carbon, such as at least one of coconut shell activated carbon, peach shell activated carbon, walnut shell activated carbon, or date shell activated carbon; coconut shell activated carbon is preferred.
Preferably, the activated carbon is subjected to screening and washing before the oxidation treatment. For example, the washing solvent may be water. Preferably, the dosage ratio of the activated carbon to the washing solvent is 1kg (5-15) L.
5. The method of claim 3 or 4, wherein the oxidizing agent is hydrogen peroxide (H)2O2) And/or sodium hypochlorite; preferably hydrogen peroxide and sodium hypochlorite.
Preferably, when the oxidant is hydrogen peroxide and sodium hypochlorite, the dosage ratio of the activated carbon to the hydrogen peroxide and the sodium hypochlorite is 1kg (0.1-0.5) L.
Preferably, the concentration of hydrogen peroxide is 5-20%.
Preferably, the concentration of sodium hypochlorite is 30-40%.
Preferably, the temperature of the oxidation treatment is 60-80 ℃, and the reaction time is 2-5 h.
6. The method according to any one of claims 3 to 5, wherein the palladium-containing compound is at least one of a halide of Pd, an acetate of Pd, a nitrate of Pd, chloropalladic acid, a basic salt of chloropalladic acid, or a complex of palladium and ammonia, and is preferably chloropalladic acid.
Preferably, in step 2), the loading may be dipping or spraying, preferably dipping.
7. The production method according to any one of claims 3 to 6, wherein in the step 3), the reducing agent is a mixed solution of aqueous ammonia and hydrazine hydrate.
Preferably, the volume ratio of the ammonia water to the hydrazine hydrate is (3-5): 1.
Preferably, the dosage ratio of the activated carbon to the reducing agent is (4-5) kg: 1L.
Preferably, in the step 3), the reduction temperature is 40-80 ℃, and the reduction time is 0.5-2 h.
8. The method according to any one of claims 3 to 7, wherein the method for preparing the palladium on carbon catalyst comprises the steps of:
s1, sieving the activated carbon, repeatedly boiling and washing the activated carbon with deionized water, and filtering to obtain clean activated carbon;
s2, adding H into the activated carbon prepared in the step S12O2Carrying out oxidation treatment on the solution and the sodium chlorate solution;
s3, mixing PdCl2Dissolved in H2Dissolving in O and HCl solution to obtain PdCl2Dissolving and converting into a chloropalladate solution;
s4, mixing the activated carbon subjected to the oxidation treatment of S2 with the chloropalladate solution prepared in the step S3, and reacting;
s5, adding the mixed solution of ammonia water and hydrazine hydrate into the reaction mixed solution prepared in the step S4, and reducing (until the solution is colorless;
s6, carrying out solid-liquid separation on the product obtained in the step S5 to obtain the palladium-carbon catalyst, and recovering ammonia water and hydrazine hydrate.
9. The palladium-carbon catalyst prepared by the preparation method according to any one of claims 3 to 8.
10. Use of a palladium on carbon catalyst according to any one of claims 1 to 2 and/or a palladium on carbon catalyst prepared by the preparation method according to any one of claims 3 to 8 in catalytic disproportionation reactions, for example in catalytic disproportionation of rosin.
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