CN106824182A - The modified Ir/C catalyst of ruthenium, its preparation method and the application in citral hydrogenation - Google Patents
The modified Ir/C catalyst of ruthenium, its preparation method and the application in citral hydrogenation Download PDFInfo
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- CN106824182A CN106824182A CN201710056691.0A CN201710056691A CN106824182A CN 106824182 A CN106824182 A CN 106824182A CN 201710056691 A CN201710056691 A CN 201710056691A CN 106824182 A CN106824182 A CN 106824182A
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229940043350 citral Drugs 0.000 title claims abstract description 24
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims abstract description 16
- 239000005792 Geraniol Substances 0.000 claims abstract description 16
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229940113087 geraniol Drugs 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 61
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- GWZHWRVINLCSIC-UHFFFAOYSA-N [Ir].[N+](=O)(O)[O-] Chemical compound [Ir].[N+](=O)(O)[O-] GWZHWRVINLCSIC-UHFFFAOYSA-N 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002503 iridium Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- WSLMHVFKYRAUMK-UHFFFAOYSA-N acetic acid;iridium Chemical compound [Ir].CC(O)=O WSLMHVFKYRAUMK-UHFFFAOYSA-N 0.000 claims 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- DDGFRKCTCQKGEI-UHFFFAOYSA-N [C].[N+](=O)(O)[O-] Chemical class [C].[N+](=O)(O)[O-] DDGFRKCTCQKGEI-UHFFFAOYSA-N 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 238000010306 acid treatment Methods 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation of the Ir/C catalyst being modified the invention discloses ruthenium and its application in citral hydrogenation, described catalyst include that absorbent charcoal carrier, active component are Ir nano-particles and Ru nano-particles.Wherein the load capacity of Ir nano-particles is 1.0 5.0%, and the load capacity of the Ru nano-particles is 0 4.0%.The invention also discloses the preparation method of ruthenium iridium/C catalyst, first activated carbon nitric acid treatment, then load active component iridium and auxiliary agent ruthenium, obtain catalyst precursor, dry reduction.Catalyst of the invention can replace the use of part Ir with less expensive Ru, while there is catalysis activity higher, selectivity, and catalyst can be used with time, reduce production cost.Citral hydrogenation synthesis nerol is applied to using catalyst of the invention, feed stock conversion 100%, nerol/geraniol is selective up to 98.0%, and reaction process condition is gentle, fully achieves industrialization production requirements.
Description
Technical field
The invention belongs to catalyst preparation and technical field of catalytic hydrogenation, and in particular to a kind of modified Ir/C catalysis of ruthenium
Agent, its preparation method and its application in citral hydrogenation.
Background technology
Citral is a kind of typical α, and beta-unsaturated aldehyde has important in the industry such as spices and medicine intermediate
Application value, its selective hydrogenation product unsaturated alcohol (nerol and geraniol) is in the middle of two kinds of valuable spices and medicine
Body, is widely used in diet, food, the allotment of daily use chemicals top grade essence.
Citral molecule contains isolated C=C double bonds, C=O keys and the C=C double bonds with carbonyl conjugation that can be hydrogenated with, hydrogen
It is applied only to C=O double bonds and is not added to nerol or geraniol that C=C double bonds are generated, is less than from the bond energy of thermodynamically C=C keys
C=O keys, are unfavorable for the product of carbonyl selective hydrogenation.Therefore the hydrogenation catalyst of high selectivity is designed, dynamics is passed to
Selective hydrogenation of the approach to improve carbonyl is the key for solving the above problems.
The catalyst activity component for synthesizing nerol or geraniol for citral selective hydrogenation can be divided into two major classes：One
Class is base metal, such as Ni, Co, Fe；Another kind of is noble metal, such as Pd, Pt, Ru and Rh.Research shows that base metal is urged
Although agent selectivity is higher, activity is relatively low, and reaction-ure conversion-age is typically very low, and severe reaction conditions.Relative to non-noble
Metallic catalyst, noble metal catalyst load capacity it is not high, reaction condition is gentleer when can just show activity higher and not
The selectivity of saturated alcohols.
In technical scheme disclosed in United States Patent (USP) US4100180, under being catalyst with PtO/Zn/Fe, unsaturated aldehyde hydrogenation
The discontinuous method of unsaturated alcohol is obtained, when citral conversion ratio reaches 70%, the overall selectivity of geraniol and nerol is
85.5%.Chinese patent CN101747152 is then catalyst with the platinum being supported on iron oxide, and citral selective hydrogenation is closed
Into nerol and geraniol, realize to geraniol and nerol selective regulation.It is fragrant when citral conversion ratio is 14.2%
The overall selectivity of leaf-alcohol and nerol is 58.9%.More than this several method to there is citral conversion ratio low, geraniol and orange
The problem for spending the overall selectivity of alcohol low.
The water soluble complex that Chinese patent CN103342627 is formed with water-soluble metal salt and water soluble ligand is to urge
Agent, when citral carries out selective hydrogenation, conversion ratio is 98.7%, and the overall selectivity of nerol and geraniol is
99.2%.But, the preparation method of the technical scheme has that preparation technology is complicated, and operating condition is more harsh, and product is difficult to point
From the problems such as, particularly its reactivity, selectivity and stability can not be taken into account simultaneously.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, a kind of be modified the invention provides ruthenium Ir/C catalyst,
Its preparation method and its application in citral hydrogenation, the wherein catalyst uses composite catalyst, by changing Ru and Ir
Ratio be prepared into different catalyst, with reactivity high, selectivity and stability, and catalyst can time use.
In addition, being applied to citral selective hydrogenation synthesis nerol or geraniol, the selectivity of unsaturated alcohol is greatly improved, it is former
Material conversion ratio 100%, the selectivity of target product can be more than 98.0%, and process conditions are gentle, and equipment is simple, easily realizes work
Industry.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of modified Ir/C catalyst of ruthenium, its feature
It is that the catalyst includes carrier, active component and auxiliary agent, wherein, the carrier is activated carbon, and the active component is iridium
(Ir) nano-particle, auxiliary agent is ruthenium (Ru) nano-particle；
Wherein, the load capacity of the iridium nano-particle is 1.0-5.0%, and the load capacity of the ruthenium nano particle is 0-
4.0%.
Used as present invention further optimization, described activated carbon specific surface area is 600-2000m2/ g, aperture is 0.5-
10nm。
Used as present invention further optimization, the load capacity of the ruthenium nano particle is 0, the load of the iridium nano-particle
It is 1.0-5.0% to measure.
It is another aspect of this invention to provide that a kind of preparation of the Ir/C catalyst being modified there is provided ruthenium of citric acid hydrogenation
Method, comprises the following steps that：
Step S1 is by activated carbon HNO3Solution stir process at a certain temperature, is then washed with deionized into
Property；
Walk poly- S2 and prepare soluble iridium salting liquid, or prepare soluble iridium salting liquid and ruthenium salting liquid；
Step S3 takes the activated carbon after step S1 treatment, and the solution for preparing is impregnated with equi-volume impregnating, after drying
To Ir/C catalyst precursors；
Walk poly- S4 and sodium hydroxide solution is added in the Ir/C catalyst precursors obtained through step S3 treatment, adjust slurries
It is aging to alkalescence；
Walk poly- S5 and the product after being processed through the poly- S4 of step is reduced using reducing agent, you can value is obtained the modified Ir/C catalysis of ruthenium
Agent.
As present invention further optimization, walk in poly- S2, described iridium salt is soluble iridium chloride, nitric acid iridium and vinegar
One or more in sour iridium.
As present invention further optimization, walk in poly- S2, described ruthenium salt is soluble ruthenic chloride, nitric acid ruthenium and vinegar
One or more in sour ruthenium.
As present invention further optimization, walk in poly- S2, dip time is 4-10h, and drying temperature is 80-130 DEG C, when
Between be 2-12h.
As present invention further optimization, walk in poly- S5, described reducing agent is sodium borohydride or hydrogen, and reducing agent is used
Amount is preferably more than the 100% of theoretical amount, and the recovery time is preferably on 1-6h.
According to another aspect of the present invention, a kind of Ir/C catalyst that ruthenium is modified is also provided and is applied to citral selectivity
The method of hydrogenation synthesis nerol or geraniol, concretely comprises the following steps：
Above-mentioned catalyst, citral and isopropanol are added in autoclave；
Vacuumize, and be passed through H after being heated to target temperature2The pressure needed for；
Magnetic agitation is opened, reaction is down to room temperature, is separated by filtration product and catalyst after terminating.
It is described to be passed through H as present invention further optimization2The pressure needed for is preferably 0.5-5MPa, and reaction temperature is excellent
Elect 60-180 DEG C as, the reaction time is preferably 2-24h.
In general, by the contemplated above technical scheme of the present invention compared with prior art, with following beneficial effect
Really：
1) it is carrier that catalyst of the invention uses activated carbon, with iridium as active component, ruthenium is auxiliary agent, it is to avoid iridium it is big
Amount is used, while catalyst of the invention has reactivity high, selectivity and stability, and catalyst can time use,
Significantly reduce production cost；
2) it is applied to citral selective hydrogenation synthesis nerol using catalyst of the invention and preferred process conditions
Or geraniol, feed stock conversion 100%, the selectivity of target product can be more than 98.0%, and process conditions are gentle, and equipment is simple,
Easily realize industrialization；
3) the modified Ir/C catalyst of ruthenium of the invention and its application process in citral hydrogenation, solve conventional orange
Spend the selectivity of alcohol and geraniol too low and cause to be difficult to industrialized problem, while having reduction noble metal cost and high selection
The advantage of property.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.As long as additionally, technical characteristic involved in invention described below each implementation method that
Conflict is not constituted between this can be just mutually combined.
According to the preparation method of the modified Ir/C catalyst of the ruthenium of the embodiment of the present invention, the Ir/C that the ruthenium that it is prepared is modified is urged
Agent can be used for citric acid hydrogenation.
The catalyst of the embodiment of the present invention includes carrier, active component and auxiliary agent, wherein, the carrier is activated carbon, institute
Active component is stated for iridium (Ir) nano-particle, auxiliary agent is ruthenium (Ru) nano-particle；Wherein, the load capacity of the iridium nano-particle is not
Higher than 5.0%, the load capacity of the ruthenium nano particle is 1.0-4.0%.
In a preferred embodiment, described activated carbon specific surface area is 600-2000m2/ g, aperture is 0.5-10nm.
The preparation method of Ir/C catalyst of the invention is described in detail with reference to specific embodiment.
Embodiment 1
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 5.0%, prepare iridium solution；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution for preparing is impregnated using equi-volume impregnating.40℃
Water-bath stands 8h, and 100 DEG C dry 4h, you can obtain Ir/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), at 100 DEG C, in addition autoclave, under pressure 2MPa, reductase 12 h, cooling, filtering, deionized water
Be washed till without by after chlorion Ir/C catalyst.
Embodiment 2
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 4.0%, ruthenium load capacity 1.0%, iridium solution is prepared respectively and ruthenium is molten
Liquid；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution and ruthenium for preparing are impregnated using equi-volume impregnating
Solution.40 DEG C of water-baths stand 8h, and 100 DEG C dry 4h, you can obtain Ir-Ru/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), above-mentioned solution reduced with sodium borohydride solution, consumption is more than 100%, reductase 12 h of theoretical amount,
Cooling, filtering, deionized water be washed till without after chlorion can obtain 4%Ir-1%Ru/C catalyst.
Embodiment 3
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 3.0%, ruthenium load capacity 2.0%, prepare iridium solution, ruthenium solution；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution and ruthenium for preparing are impregnated using equi-volume impregnating
Solution.40 DEG C of water-baths stand 8h, and 100 DEG C dry 4h, you can obtain Ir-Ru/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), above-mentioned solution reduced with sodium borohydride solution, consumption is more than 100%, reductase 12 h of theoretical amount,
Cooling, filtering, deionized water be washed till without after chlorion can obtain 3%Ir-2%Ru/C catalyst.
Embodiment 4
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 2.0%, ruthenium load capacity 3.0%, prepare iridium solution, ruthenium solution；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution and ruthenium for preparing are impregnated using equi-volume impregnating
Solution.40 DEG C of water-baths stand 8h, and 100 DEG C dry 4h, you can obtain Ir-Ru/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), above-mentioned solution reduced with sodium borohydride solution, consumption is more than 100%, reductase 12 h of theoretical amount,
Cooling, filtering, deionized water be washed till without after chlorion can obtain 2%Ir-3%Ru/C catalyst.
Embodiment 5
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 1.0%, ruthenium load capacity 4.0%, prepare iridium solution, ruthenium solution；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution and ruthenium for preparing are impregnated using equi-volume impregnating
Solution.40 DEG C of water-baths stand 8h, and 100 DEG C dry 4h, you can obtain Ir-Ru/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), above-mentioned solution reduced with sodium borohydride solution, consumption is more than 100%, reductase 12 h of theoretical amount,
Cooling, filtering, deionized water be washed till without after chlorion can obtain 1%Ir-4%Ru/C catalyst.
Embodiment 6
Step (a), the treatment of activated carbon, by activated carbon 5%HNO3Solution stir process 4h at 80 DEG C, then spends
Ion water washing is to neutrality；
Walk poly- (b), by active component iridium load capacity 3.0%, ruthenium load capacity 2.0%, prepare iridium solution, ruthenium solution；
Walk poly- (c), take the activated carbon 5g of step (a), the iridium solution and ruthenium for preparing are impregnated using equi-volume impregnating
Solution.40 DEG C of water-baths stand 8h, and 100 DEG C dry 4h, you can obtain Ir-Ru/C catalyst precursors；
Walk poly- (d), with the sodium hydrate aqueous solution of 5wt%, the pH value for adjusting presoma is 10, stands aging 8h；
Walk poly- (f), at 100 DEG C, in addition autoclave, under pressure 2MPa, reductase 12 h, cooling, filtering, deionized water
Be washed till without by after chlorion 3%Ir-2%Ru/C catalyst.
Embodiment 7-12
Embodiment 7-12 is that catalyst obtained in above-described embodiment 1-6 preparation methods is applied into lemon aldehyde hydrogenation reaction
Example.Its operating process is as follows：Catalyst, citral and isopropanol are added in autoclave, is vacuumized, after being heated to 80 DEG C
It is passed through H2To 1.5MPa, magnetic agitation is opened, end is reacted after 2h and is down to room temperature, be separated by filtration product and catalyst, filtrate is produced
Thing passes through chromatographic.Its catalytic result is as shown in table 1
Embodiment 13
Embodiment 13 is that under the operating condition of embodiment 9, the catalyst prepared by embodiment 3 is in lemon aldehyde hydrogenation reaction
During apply mechanically experimental conditions, its result is as shown in table 2.
The catalytic performance result of the catalyst of table 1
| Embodiment | Catalyst | Conversion ratio/the % of citral | Selectivity/the % of nerol/geraniol |
| 7 | Embodiment 1 | 90.2 | 89.3 |
| 8 | Embodiment 2 | 95.3 | 95.7 |
| 9 | Embodiment 3 | 100.0 | 98.0 |
| 10 | Embodiment 4 | 93.6 | 93.2 |
| 11 | Embodiment 5 | 89.7 | 88.4 |
| 12 | Embodiment 6 | 85.4 | 83.9 |
The catalyst of 2 embodiment of table 3 applies mechanically result in embodiment 13
It should be noted that in the various embodiments described above, load capacity and ruthenium load capacity on iridium are not limited to above-mentioned number
Value scope, the load capacity of such as iridium can be arbitrary value in 1.0-5.0%, such as 1.0%, 1.5%, 2.0%, 2.5%,
3.0%th, 3.5%, 4.0%, 5.0% etc. or the scope other arbitrary values；The load capacity of ruthenium can be any in 0-4.0%
Value, such as 0,1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0% etc. or the scope other arbitrary values, two
Proportioning between person can arbitrarily arrange in pairs or groups proportioning according to respective value, however it is not limited to the concrete numerical value in above-described embodiment.
In addition, the active carbon treatment process in step (a), nitric acid preferred concentration is 5-10%, such as 5% etc., its stirring
Shi Wendu can be for example 70-90 DEG C, and preferably 80 DEG C, mixing time is selected according to temperature and real needs, for example 2-
4h.If when the load of iridium measures 0 in step (b), it is only necessary to the load capacity requirement corresponding iridium solution of configuration according to iridium, such as
When the load capacity of fruit iridium is not 0, the load capacity according to both configures solution respectively.
In step (c), in dipping presoma operation, the quality of activated carbon is not limited to above-mentioned numerical value, can be according to specific
Demand is selected, and dipping temperature, time are also not necessarily limited to concrete numerical value in embodiment, for example, can be 30-60 DEG C, dip time
It is preferred that 4-10h, drying temperature and time are also not necessarily limited to concrete numerical value in embodiment, for example can be 80-130 DEG C of drying temperature,
Time is 2-12h.
In step (d), regulation pH value to the solution of alkalescence of addition is preferably sodium hydrate aqueous solution but it is also possible to be it
He will not produce the alkaline solution of extra reaction, its percentage by weight can be selected according to specific needs, such as 4-
10wt%, pH value is preferably adjusted to 9-11, more preferably 10 effects, and ageing time afterwards is not limited to specific in embodiment
Numerical value, can determine, such as 6-10h according to real needs.
In step (f), the reducing agent for carrying out reduction reaction can be hydrogen or sodium borohydride solution, and its reduction mode has
Body can be that hydrogen is passed through into autoclave to be reduced, and reduction pressure, temperature and time are not limited in embodiment
Concrete numerical value；Can also be using adding sodium borohydride solution to be reduced, the consumption preferably unnecessary theoretical amount of reducing agent, when
Between preferably 1-4h.
In a word, each group classifying type and parameter are only for preferably explaining technical scheme in above-described embodiment,
The more crucially preparation technology therein of the technical scheme being not intended to limit the present invention, actually technical solution of the present invention
And the application of key component, it is hereby achieved that the catalyst and application effect of function admirable.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (10)
1. the Ir/C catalyst that a kind of ruthenium is modified, it is characterised in that the catalyst includes carrier, active component and auxiliary agent, its
In, the carrier is activated carbon, and the active component is iridium (Ir) nano-particle, and auxiliary agent is ruthenium (Ru) nano-particle；
Wherein, the load capacity of the iridium nano-particle is 1.0-5.0%, and the load capacity of the ruthenium nano particle is 0-4.0%.
2. the Ir/C catalyst that ruthenium according to claim 1 is modified, wherein, described activated carbon specific surface area is 600-
2000m2/ g, aperture is 0.5-10nm.
3. the Ir/C catalyst that ruthenium according to claim 1 and 2 is modified, wherein, the load capacity of the ruthenium iridium nano-particle
It is 0, the load capacity of the iridium nano-particle is 1.0-5.0%.
4. a kind of citric acid hydrogenation with ruthenium be modified Ir/C catalyst preparation method, it is characterised in that the tool of the preparation method
Body step is as follows：
Step S1 is by activated carbon HNO3Solution stir process at a certain temperature, is then washed with deionized to neutrality；
Walk poly- S2 and prepare soluble iridium salting liquid, or prepare soluble iridium salting liquid and ruthenium salting liquid；
Step S3 takes the activated carbon after step S1 treatment, and the solution for preparing is impregnated with equi-volume impregnating, and Ir/ is obtained after drying
C catalyst presoma；
Walk poly- S4 and add sodium hydroxide solution in the Ir/C catalyst precursors obtained through step S3 treatment, regulation slurries pH to
Alkalescence is aging；
Walk poly- S5 and the product after being processed through the poly- S4 of step is reduced using reducing agent, you can value is obtained the modified Ir/C catalyst of ruthenium.
5. the preparation method of the Ir/C catalyst that citric acid hydrogenation according to claim 4 is modified with ruthenium, wherein, walk poly- S2
In, described iridium salt is one or more in soluble iridium chloride, nitric acid iridium and acetic acid iridium.
6. the citric acid hydrogenation according to claim 4 or 5 with ruthenium be modified Ir/C catalyst preparation method, wherein, step
In poly- S2, described ruthenium salt is one or more in soluble ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium.
7. the citric acid hydrogenation according to any one of claim 4 to 6 with ruthenium be modified Ir/C catalyst preparation method,
Wherein, walk in poly- S3, dip time is 4-10h, drying temperature is 80-130 DEG C, and the time is 2-12h.
8. the citric acid hydrogenation according to any one of claim 4 to 7 with ruthenium be modified Ir/C catalyst preparation method,
Wherein, in walking poly- S5, described reducing agent is sodium borohydride or hydrogen, reducing agent consumption be preferably the 100% of theoretical amount with
On, the recovery time is preferably on 1-6h.
9. a kind of modified Ir/C catalyst of ruthenium any one of claims 1 to 3 is applied to citral selective hydrogenation
The method of synthesis nerol or geraniol, it is characterised in that it is concretely comprised the following steps：
Above-mentioned catalyst, citral and isopropanol are added in autoclave；
Vacuumize, and be passed through H after being heated to target temperature2The pressure needed for；
Magnetic agitation is opened, reaction is down to room temperature, is separated by filtration product and catalyst after terminating.
10. the modified Ir/C catalyst of ruthenium according to claim 9 is applied to citral selective hydrogenation synthesis nerol
Or the method for geraniol, wherein, it is described to be passed through H2The pressure needed for is preferably 0.5-5MPa, and reaction temperature is preferably 60-180
DEG C, the reaction time is preferably 2-24h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107321387A (en) * | 2017-07-18 | 2017-11-07 | 万华化学集团股份有限公司 | A kind of catalyst, preparation method and its application in nerol and spiceleaf alcohol production of immobilized MPV reactions |
| CN107973705A (en) * | 2017-12-07 | 2018-05-01 | 万华化学集团股份有限公司 | A kind of citral hydrogenation prepares the production technology and production system of serial spices |
| CN111018666A (en) * | 2019-12-12 | 2020-04-17 | 万华化学集团股份有限公司 | Improved process for preparing nerol leaf alcohol and catalytic system therefor |
| CN111389395A (en) * | 2020-05-06 | 2020-07-10 | 云南大学 | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural |
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2017
- 2017-01-25 CN CN201710056691.0A patent/CN106824182B/en not_active Expired - Fee Related
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| 杨雪娇等: "Ir/C催化剂氯代硝基苯选择性催化加氢反应性能", 《工业催化》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321387A (en) * | 2017-07-18 | 2017-11-07 | 万华化学集团股份有限公司 | A kind of catalyst, preparation method and its application in nerol and spiceleaf alcohol production of immobilized MPV reactions |
| CN107321387B (en) * | 2017-07-18 | 2019-10-29 | 万华化学集团股份有限公司 | A kind of catalyst, preparation method and its application in nerol and spiceleaf alcohol production of immobilized MPV reaction |
| CN107973705A (en) * | 2017-12-07 | 2018-05-01 | 万华化学集团股份有限公司 | A kind of citral hydrogenation prepares the production technology and production system of serial spices |
| CN107973705B (en) * | 2017-12-07 | 2021-02-02 | 万华化学集团股份有限公司 | Production process and production system for preparing series of spices by hydrogenating citral |
| CN111018666A (en) * | 2019-12-12 | 2020-04-17 | 万华化学集团股份有限公司 | Improved process for preparing nerol leaf alcohol and catalytic system therefor |
| CN111018666B (en) * | 2019-12-12 | 2022-11-04 | 万华化学集团股份有限公司 | Improved process for preparing nerol leaf alcohol and catalytic system therefor |
| CN111389395A (en) * | 2020-05-06 | 2020-07-10 | 云南大学 | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural |
| CN111389395B (en) * | 2020-05-06 | 2022-09-30 | 云南大学 | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural |
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