CN107442134A - A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application - Google Patents
A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application Download PDFInfo
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- CN107442134A CN107442134A CN201710760376.6A CN201710760376A CN107442134A CN 107442134 A CN107442134 A CN 107442134A CN 201710760376 A CN201710760376 A CN 201710760376A CN 107442134 A CN107442134 A CN 107442134A
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- rhodium
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- nickel alloy
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- 239000010948 rhodium Substances 0.000 title claims abstract description 98
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 65
- 229910000629 Rh alloy Inorganic materials 0.000 title claims abstract description 54
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 claims abstract description 50
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 235000019441 ethanol Nutrition 0.000 claims description 16
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- PWDGLIWNOMOQHM-UHFFFAOYSA-N ethanol;hydrazine;hydrate Chemical compound O.NN.CCO PWDGLIWNOMOQHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- -1 aminopropyl Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000011160 research Methods 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 19
- 238000006555 catalytic reaction Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 8
- 150000004056 anthraquinones Chemical class 0.000 description 7
- 238000007405 data analysis Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical class C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- JBDYKGMNMDIHFL-UHFFFAOYSA-N 1-nitroanthracene Chemical class C1=CC=C2C=C3C([N+](=O)[O-])=CC=CC3=CC2=C1 JBDYKGMNMDIHFL-UHFFFAOYSA-N 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/51—
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
Abstract
The present invention relates to a kind of rhodium/nickel alloy nanocatalyst and its preparation method and application, belong to nanocatalyst research field；The catalyst of the present invention be spherical, polyhedral rhodium/nickel alloy nanoparticles, and the Size Distributions of prepared rhodium/nickel alloy nano-catalyst particles is 12 58 nm, and rhodium, the mol ratio of nickel are 0.01 0.05 in catalyst:1；The present invention is using nickel acetate, rhodium chloride as raw material, it is prepared for varying particle size, rhodium/nickel nanometer alloy catalyst of microstructure, then using 1 nitroanthraquinone, hydrogen as raw material, reacted using the catalyst, reaction temperature is set to be warming up to 100 160 DEG C, and the h of insulation reaction 28, obtain the amino anthraquinones of high-purity 1；Catalyst amount prepared by the present invention is few, has higher catalytic activity and stability；Method technological requirement using the amino anthraquinones of catalyst preparation 1 is simple, green, suitable for industrial requirement.
Description
Technical field
The present invention relates to a kind of rhodium/nickel alloy nanocatalyst and its preparation method and application, belong to nanocatalyst and grind
Study carefully field.
Technical background
1- amino anthraquinones is one of important intermediate of anthraquinone based dye, and its purposes is wide, and dosage is big.With dye industry
Development is all very big to the demand of 1- amino anthraquinones both at home and abroad.At home, the industrial production technology of 1- amino anthraquinones is often with 1-
Nitroanthraquinone is raw material, is reduced through sodium hydrosulfite, akali sulphide etc., reoxidizes obtained 1- amino anthraquinones.Production through these technique productions
Quality is stable, and production cost is low, simple to operate, and technical difficulty is low, but can produce substantial amounts of environmental contaminants, " three wastes " processing
Pressure is very big；There is also same problem for sulfonation ammoniation process.Environmental contaminants are fewer caused by ammonolysis process, but need higher
Pressure under reacted, the ammonium nilrite generated in reaction can be decomposed drastically in water, at high temperature heating have explosion danger,
Production safety be present.In order to solve the above problems, it is badly in need of developing clean and effective, work on the basis of existing production method
The new technology that skill is simple, cost is low, product purity is high.
Catalytic hydrogenating reduction method is a kind of friendly process at present, compared with vulcanizing alkaline process, is not produced a large amount of intractable
Sulphur-bearing waste solution, and product yield is higher.In addition also have some friendly process, such as hydrazine hydrate method and electrochemical process technique, but
It is due to that these process costs are higher, also rests on the laboratory research stage, it is still no to embody industrial value,.Therefore, study
Rhodium/nickel alloy nanocatalyst catalysis 1- nitroanthraquinone selection hydrogenation synthesis 1- amino anthraquinones has important research meaning.
The content of the invention
It is an object of the invention to overcome defect present in prior art, there is provided a kind of rhodium/nickel alloy nanocatalyst,
And for catalyzing and synthesizing 1- amino anthraquinones.The preparation method of catalyst of the present invention is simple, and three wastes produce, green；Meanwhile
Catalyst amount is few when catalyzing and synthesizing 1- amino anthraquinones, and catalytic activity is high, selectivity is high, stable performance.
Technical scheme is as follows：
Present invention firstly provides a kind of rhodium/nickel alloy nanocatalyst, the catalyst is spherical, polyhedral rhodium/nickel
Alloy nanoparticle, the Size Distribution of prepared rhodium/nickel alloy nano-catalyst particles is 12-58nm.
A kind of preparation method of rhodium/nickel alloy nanocatalyst, methods described using rhodium chloride, nickel acetate as raw material, with
Hydrazine hydrate or sodium borohydride are reducing agent, in the presence of organic modifier, are prepared for rhodium/nickel alloy nanocatalyst.
Specific preparation process is as follows：
It is a certain amount of according to metal rhodium and different ratio of the metallic nickel in rhodium/nickel alloy nanocatalyst, precise
Rh and Ni metal precursor rhodium chloride, nickel acetate is dissolved in 40mL ethanol solutions respectively, is added after being stirred
The ethanol solution of 20mL organic modifiers, 20min is mixed at 30-60 DEG C, adjusted with certain density NaOH ethanol solutions
Reacting liquid pH value is saved, then after temperature rises to 70 DEG C, by the certain density hydrazine hydrate ethanol solutions of 100mL or sodium borohydride second
Alcoholic solution is added dropwise in above-mentioned reaction solution, after reacting 4-8h, is repeatedly washed through absolute ethyl alcohol, after vacuum drying, you can is made
Required catalyst.
Wherein, in above-mentioned preparation method, the ethanol solution of the organic modifier, NaOH ethanol solution, hydrazine hydrate second
Alcoholic solution or ethanol solution of sodium borohydride are the solution for being dissolved in and being obtained in absolute ethyl alcohol, described in addition to organic modifier
Concentration be also concentration of each material in absolute ethyl alcohol.
Wherein, described organic modifier is 3- (aminopropyl) triethoxysilane (APTS), and its quality is Rh's and Ni
The 10wt% of presoma gross mass.
Rhodium, the mol ratio of nickel are 0.01-0.05 in alloy nano catalyst prepared by the above method:1.
Wherein, it is described regulation reaction solution pH value use 0.5-1.5mol/L NaOH ethanol solution adjust pH value for
10-14。
The concentration of the ethanol solution of wherein described hydrazine hydrate or the ethanol solution of sodium borohydride is 0.5-0.9mol/L.
The rhodium prepared according to above-mentioned preparation method/nickel alloy metallic catalyst is applied to catalyze and synthesize 1- amino anthracenes
Quinone, synthesis step are as follows：
(1) take 1- nitroanthraquinones and DMF (DMF) to be placed in reactor, add rhodium/nickel alloy and receive
Rice catalyst, wherein, the ratio of 1- nitroanthraquinones, DMF, rhodium/nickel alloy nanocatalyst is：3g:150mL:0.03g-0.3g；
(2) reaction unit is installed, nitrogen is passed through and purges about 5 minutes, remove the air in reactor, then pass to high-purity
Hydrogen simultaneously makes pressure increase to 0.5-1.0MPa, is to slowly warm up to 100-160 DEG C, is incubated lower reaction 2-8h, stir speed (S.S.) 600r/
min；
(3) after reaction terminates, reaction mass is cooled to room temperature.Sample is analyzed with liquid chromatograph.
The advantage of the invention is that：
Rhodium involved in the present invention/nickel alloy nanocatalyst is made in the presence of organic modifier silane coupling A PTS
Standby, the functional group such as silane coupling A PTS space steric effect and electrostatic effect and its aminopropyl, ethyoxyl.So far not
Have been reported that influence of the dressing agent to rhodium/nickel alloy nanoparticles size, pattern and microstructure.Under this experiment condition, silicon
Alkane coupling agent APTS inductive formations spherical, polyhedral rhodium/nickel alloy nanoparticles, prepared rhodium/nickel alloy nanometer are urged
The Size Distribution of catalyst particles is 12-58nm, and has good dispersiveness, has preferably catalysis in catalytic reaction process
Activity and stability.
The method that 1- amino anthraquinones is prepared due to anthraquinone sulfonation ammonolysis process, nitrification-method of substitution, anthraquinone nitrification reducing process etc. is deposited
Largely polluting, 1- nitroanthraquinone catalytic hydrogenation methods are shown one's talent with its green advantage.It is usually used in the choosing of 1- nitroanthraquinones
The catalyst such as the unitary nano Pd particle for being hydrogenated to the reaction of 1- amino anthraquinones, Ni are selected to lack in the presence of easy reunion, easy in inactivation, stability difference etc.
Point, binary alloy nano metallic catalyst turn into new study hotspot due to its more preferable stability and higher catalytic performance.
It is applied to 1- nitroanthraquinones Hydrogenation using rhodium/nickel alloy nanocatalyst first in the present invention to react for 1- amino anthraquinones.
The alloying of metal not only increases the energy of the anti-sintering of particle in the rhodium prepared under this experiment condition/nickel alloy nanocatalyst
Power, while the Electronic Performance and geometry of catalyst activity component are changed, in nitro-aromatic selective hydrogenation reaction is catalyzed
Show more excellent catalytic activity and selectivity.The catalytic activity of rhodium/nickel alloy nanocatalyst is not only by its size, shape
The influence of looks, rhodium, the proportioning of nickel are also an important factor for influenceing the catalyst activity in catalyst.It is found through experiments that, rhodium, nickel
Match as 0.04:When 1, under this experiment condition, 1- nitroanthraquinones Hydrogenation for raw material in the reaction of 1- amino anthraquinones conversion
Rate and the selectivity of product are 100%.The catalyst activity is high, stability is good, and reaction condition is gentle, avoids high temperature high pressure reverse
Should, so as to avoid the generation of a large amount of accessory substances, improve the selectivity of catalyst so that product purity is high, is advantageous to downstream
The further exploitation of product.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1:
(1) preparation of catalyst：
Using rhodium chloride, nickel acetate as raw material, hydrazine hydrate is reducing agent, and rhodium/nickel is prepared in the presence of organic modifier and is closed
Gold nano catalyst.
When rhodium, nickel mol ratio are 0.04:When 1, rhodium/nickel alloy catalyst (Rh0.04Ni preparation)：Weigh respectively
0.2106g RhCl3·3H2O, 4.9768g C4H6NiO4.4H2O and 0.5187g 3- (aminopropyl) triethoxysilane
(APTS), it is dissolved separately in through excusing from death in 50mL, 90mL and 20mL absolute ethyl alcohol, the RhCl that will be obtained3·3H2O and
C4H6NiO4.4H2O ethanol solution mixing after again the ethanol solution with 3- (aminopropyl) triethoxysilane (APTS) at 50 DEG C
Under be stirred 20min.PH to 13 is adjusted with 0.8mol/L NaOH ethanol solution, by 100mL 0.75mol/L hydration
The ethanol solution of hydrazine is added dropwise in above-mentioned reaction solution, and 6h is reacted in 70 DEG C, and product is washed through multiple alcohol, vacuum drying
Afterwards, Rh is prepared0.04Ni alloy nano catalyst.
(2) 1- nitroanthraquinones selective catalysis Hydrogenation reacts for 1- amino anthraquinones：
Accurately weigh 3g 1- nitroanthraquinones and 0.24g Rh0.04Ni alloy nano catalyst, measures 150mL DMF, puts
In autoclave；High pure nitrogen displaced air 5min is passed through, it is 0.8MPa to then pass to hydrogen to pressure, confined reaction
Kettle, mixing speed 600rpm, react 6h at a temperature of 130 DEG C.After reaction terminates, product utilizes efficient liquid phase using external standard method
Chromatogram carries out sample composition analysis.Products therefrom selectivity is shown in Table 1 with feed stock conversion.
Embodiment 2：
With embodiment 1, only changing catalyst amount is：0.03g, 0.09g, 0.15g, 0.24g, 0.3g, carry out 1- nitros
Anthraquinone selective hydrogenation reaction.Products therefrom selectivity is shown in Table 1 with feed stock conversion.
Table 1 is shown in 0.8MPa H2Under pressure, reaction temperature is 130 DEG C, is incubated lower reaction 6h, different catalysts
During dosage, the selectivity of rhodium/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinone hydrogenation reaction product 1- amino anthraquinones with
The conversion ratio of raw material；According to the data analysis of table 1, the dosage of rhodium/nickel alloy nanocatalyst is to its selective catalysis 1- nitroanthraquinones
Hydrogenation has a major impact for the catalytic activity that 1- amino anthraquinones reacts.When the dosage of rhodium/nickel alloy nanocatalyst is 0.24g
When, under this experiment condition, the conversion ratio of 1- nitroanthraquinones and the selectivity of 1- amino anthraquinones are 100%.
The different catalysts dosage of table 1. is to catalyzing and synthesizing the selectivity of 1- nitroanthraquinones and the influence of feed stock conversion
Embodiment 3：
With embodiment 1, the temperature for only changing reactor is：100 DEG C, 110 DEG C, 130 DEG C, 150 DEG C, 160 DEG C, carry out 1- nitre
Base anthraquinone selective hydrogenation reaction.Products therefrom selectivity is shown in Table 2 with feed stock conversion.
Table 2 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, at a temperature of differential responses, lower react is incubated
6h, the selectivity and raw material of rhodium/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinone hydrogenation reaction product 1- amino anthraquinones
Conversion ratio；According to the data analysis of table 2, under this experiment condition, reaction temperature is to rhodium/nickel alloy nanocatalyst selective catalysis
1- nitroanthraquinones Hydrogenation has a major impact for the catalytic activity that 1- amino anthraquinones reacts.When reaction temperature is 130 DEG C, 1- nitre
The conversion ratio of base anthraquinone and the selectivity of 1- amino anthraquinones are 100%.When reaction temperature is relatively low, the conversion ratio of 1- nitroanthraquinones
It is relatively low；And reaction temperature it is higher when, there are a large amount of by-products to generate, reduce the selectivity of target product 1- amino anthraquinones.
The different translation temperature of table 2. are to catalyzing and synthesizing 1- nitroanthraquinones selectivity and the influence of feed stock conversion
Embodiment 4：
With embodiment 1, the only change reaction time is：2h, 4h, 6h, 8h, carry out 1- nitroanthraquinone selective hydrogenation reactions.Institute
Obtain selectivity of product and be shown in Table 3 with feed stock conversion.
Table 3 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction temperature is 130 DEG C, during differential responses
Between under, the selectivity of rhodium/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinone hydrogenation reaction product 1- amino anthraquinones with it is former
The conversion ratio of material；According to the data analysis of table 3, under this experiment condition, the reaction time is urged rhodium/nickel alloy nanocatalyst selection
Change 1- nitroanthraquinones Hydrogenation to have a major impact for the catalytic activity that 1- amino anthraquinones reacts.When being 6h between when reacted, 1- nitre
The conversion ratio of base anthraquinone and the selectivity of 1- amino anthraquinones are 100%.When reaction time is shorter, insufficient, 1- nitros are reacted
The conversion ratio of anthraquinone is low；And the reaction time it is longer when, there is a small amount of by-product to generate, reduce the selection of target product 1- amino anthraquinones
Property.
The differential responses time of table 3. is to catalyzing and synthesizing the selectivity of 1- nitroanthraquinones and the influence of feed stock conversion
Embodiment 5：
With embodiment 1, only changing rhodium, the proportioning of nickel in step 1 is：0:1、0.01:1、0.04:1、0.05:1、1:0, will
RhCl3·3H2O quality is changed to：0g, 0.0527g, 0.1053g, 0.1580g, 0.2106g, 0.2633g, 0.2633g, respectively
Prepare Ni, Rh0.01Ni、Rh0.02Ni、Rh0.03Ni、Rh0.04Ni、Rh0.05Ni, Rh nanometer alloy catalyst carry out 1- nitroanthraquinone choosings
Select hydrogenation reaction.In order to be contrasted with the catalytic performance of rhodium/nickel nanometer alloy catalyst, using rhodium, nickel mol ratio as 0.04:1
Rhodium, nickel composite catalyst (Rh0.04@Ni) carry out 1- nitroanthraquinone selective hydrogenation reactions.Products therefrom selectivity converts with raw material
Rate is shown in Table 4.
Table 4 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction temperature is 130 DEG C, is incubated lower react
6h, different rhodiums, rhodium/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinone hydrogenation reaction product 1- amino anthracenes of nickel mol ratio
The selectivity of quinone and the conversion ratio of raw material.
According to the data analysis of table 4, under this experiment condition, the composition of catalyst is selected rhodium/nickel alloy nanocatalyst
Catalysis 1- nitroanthraquinones Hydrogenation has a major impact for the catalytic activity that 1- amino anthraquinones reacts.When rhodium in catalyst, nickel rub
Your proportioning is 0.04:When 1, the conversion ratio of 1- nitroanthraquinones and the selectivity of 1- amino anthraquinones are 100%.As rhodium, nickel rub
The increase of your proportioning, the conversion ratio of 1- nitroanthraquinones also improve therewith, still, when rhodium, nickel mol ratio are higher than 0.04, there is pair
Produce into, reduce the selectivity of target product 1- amino anthraquinones.And contrast the Rh of core-shell type structure0.04@Ni bielement nanos gold
Metal catalyst, Rh/Ni alloy nanoparticles prepared by this experiment show more excellent catalytic activity, show pattern, microcosmic knot
Structure has a major impact to the catalytic activity of binary alloy nano metallic catalyst.
4. different rhodiums of table, rhodium/nickel alloy nanocatalyst of nickel mol ratio are to catalyzing and synthesizing the selectivity of 1- nitroanthraquinones
With the influence of feed stock conversion
Embodiment 6：
With embodiment 1, the pH value for only changing reaction solution in catalyst preparation process is：10th, 11,12,13,14, carry out 1-
Nitroanthraquinone selective hydrogenation reaction.Products therefrom selectivity is shown in Table 5 with feed stock conversion.
Table 5 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction temperature is 130 DEG C, is incubated lower react
6h, the rhodium prepared in the reaction solution of different pH value/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinones hydrogenation reaction production
The selectivity of thing 1- amino anthraquinones and the conversion ratio of raw material.
According to the data analysis of table 5, during this experiment condition prepares rhodium/nickel alloy nanocatalyst, pH value is to preparing
Size, pattern and the crystal structure of rhodium/nickel alloy nanoparticles have a major impact, and influence its and be catalyzed 1- nitroanthraquinones hydrogenation
Prepare the catalytic activity of 1- amino anthraquinones.When pH value is 13, the average grain diameter of rhodium/nickel alloy nanoparticles of preparation is
21nm, Spherical polycrystalline structure, particle surface have point defect.During from the alloy nanoparticle as catalyst, 1- nitroanthracenes
The conversion ratio of quinone and the selectivity of 1- amino anthraquinones are 100%.With the increase of pH value, grain diameter is gradually reduced, particle
Microstructure also change therewith.When pH value is 13, the average grain diameter of rhodium/nickel alloy nanoparticles is 12nm, still
Its surface does not have a point defect presence, and the conversion ratios of 1- nitroanthraquinones is that the selectivity of 97.6%, 1- amino anthraquinones is 96.7%.
The rhodium prepared under the different pH condition of table 5/nickel alloy nanocatalyst is to catalyzing and synthesizing 1- nitroanthraquinones selectivity
With the influence of feed stock conversion
Embodiment 7：
With embodiment 1, the concentration for only changing hydrazine hydrate ethanol solution in catalyst preparation process is：0.5mol/L、
0.65mol/L, 0.75mol/L, 0.9mol/L, carry out 1- nitroanthraquinone selective hydrogenation reactions.Products therefrom selectivity and raw material
Conversion ratio is shown in Table 6.
Table 6 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction temperature is 130 DEG C, is incubated lower react
6h, the rhodium prepared under the concentration of different hydrazine hydrates/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinones hydrogenation reaction production
The selectivity of thing 1- amino anthraquinones and the conversion ratio of raw material.
According to the data analysis of table 6, during this experiment condition prepares rhodium/nickel alloy nanocatalyst, reducing agent hydration
The concentration of hydrazine has a major impact to size, pattern and the crystal structure of rhodium/nickel alloy nanoparticles of preparation, and influences its catalysis
1- nitroanthraquinones Hydrogenation for 1- amino anthraquinones catalytic activity.When the concentration of hydrazine hydrate is 0.75mol/L, the rhodium of preparation/
The average grain diameter of nickel alloy nanoparticles is 21nm, Spherical polycrystalline structure, and particle surface has point defect.From the alloy nano
When particle is as catalyst, the conversion ratio of 1- nitroanthraquinones and the selectivity of 1- amino anthraquinones are 100%.As hydrazine hydrate is dense
Spend for 0.9mol/L when, spherical rhodium/nickel alloy nanoparticles of preparation, mean particle size 19nm, there is agglomeration hair
It is raw.
Catalyst prepared by the hydrazine hydrate ethanol solutions of the various concentrations of table 6. is to catalyzing and synthesizing the selectivity of 1- nitroanthraquinones
With the influence of feed stock conversion
Embodiment 8：
With embodiment 1, the ethanol solution concentration for only changing NaOH in catalyst preparation process is：0.5mol/L、0.8mol/
L, 1.0mol/L, 1.5mol/L, 1- nitroanthraquinone selective hydrogenation reactions are carried out.Products therefrom is selectively shown in Table with feed stock conversion
7。
Table 7 is in 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction temperature is 130 DEG C, is incubated lower react
The rhodium that 6h is prepared under different NaOH concentration/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinone hydrogenation reaction products 1-
The selectivity of amino anthraquinones and the conversion ratio of raw material.
According to the data analysis of table 7, during this experiment condition prepares rhodium/nickel alloy nanocatalyst, NaOH ethanol is molten
The concentration of liquid has a major impact to dispersiveness, the size of rhodium/nickel alloy nanoparticles of preparation, and influences it and be catalyzed 1- nitroanthracenes
Quinone Hydrogenation for 1- amino anthraquinones catalytic activity.When NaOH ethanol solution concentrations are 0.8mol/L, rhodium/nickel alloy of preparation
The average grain diameter of nano particle is 21nm, Spherical polycrystalline structure, and particle surface has point defect.Made from the alloy nanoparticle
For catalyst when, the conversion ratio of 1- nitroanthraquinones and the selectivity of 1- amino anthraquinones are 100%.As NaOH ethanol solutions are dense
The increase of degree, grain diameter unity phenomenon is obvious, reduces its catalytic activity.It is 1.5mol/L when selecting NaOH ethanol solution concentrations
Under the conditions of rhodium/nickel alloy nanoparticles for preparing as catalyst when, the conversion ratio of 1- nitroanthraquinones is 65.2%, 1- amino anthracenes
The selectivity of quinone is 68.1%.
Catalyst prepared by the NaOH ethanol solutions of the various concentrations of table 7. to catalyze and synthesize the selectivity of 1- nitroanthraquinones with
The influence of feed stock conversion
Embodiment 9：
With embodiment 1, in catalyst preparation process, 0.5mol/L ethanol solution of sodium borohydride is used as reducing agent, is selected
Solution ph is adjusted with 1.5mol/L NaOH ethanol solutions, prepared rhodium/nickel alloy nanoparticles particle diameter is 48nm.Use
State catalyst and carry out 1- nitroanthraquinone selective hydrogenation reactions.In 0.8MPa H2Under pressure, when catalyst amount is 0.24g, reaction
Temperature is 130 DEG C, is incubated lower reaction 6h, and prepared rhodium/nickel alloy nanocatalyst selective catalysis 1- nitroanthraquinones hydrogenation is anti-
The selectivity for answering product 1- amino anthraquinones is 63.9%, and the conversion ratio of raw material is 57.6%.Comparative example 1, different reducing agents
Under the conditions of, the particle size of rhodium/Raney nickel of preparation is different.Meanwhile further prove, particle size has to its catalytic activity
Material impact.
Claims (10)
1. a kind of rhodium/nickel alloy nanocatalyst, it is characterised in that rhodium, the mol ratio of nickel are 0.01- in the catalyst
0.05:1；The catalyst is spherical, polyhedral rhodium/nickel alloy nanoparticles, described rhodium/nickel alloy nanocatalyst
The Size Distribution of grain is 12-58 nm.
2. the preparation method of a kind of rhodium/nickel alloy nanocatalyst, it is characterised in that specific preparation process is as follows：
Precise a certain amount of Rh and Ni metal precursor rhodium chloride, nickel acetate is dissolved in ethanol solution respectively,
The ethanol solution of organic modifier is added after being stirred, after being mixed at 30-60 DEG C, with certain density NaOH second
Alcoholic solution adjusts the pH value of reaction solution, then after temperature rises to 70 DEG C, by certain density hydrazine hydrate ethanol solution or boron hydrogen
Change sodium ethoxide solution to be added dropwise in above-mentioned reaction solution, after reaction 4-8 h, repeatedly washed through absolute ethyl alcohol, after vacuum drying, i.e.,
Required catalyst can be made.
3. preparation method according to claim 2, it is characterised in that the metal precursor rhodium chloride, nickel acetate
Dosage is calculated according to the different ratio of metal rhodium and metallic nickel in the rhodium obtained in advance/nickel alloy nanocatalyst and added, wherein institute
Rhodium, the mol ratio of nickel are 0.01-0.05 in the alloy nano catalyst stated:1.
4. preparation method according to claim 2, it is characterised in that described organic modifier is the second of 3- (aminopropyl) three
TMOS (APTS), the quality of described organic modifier are 10 wt% of Rh and Ni presoma gross masses.
5. preparation method according to claim 2, it is characterised in that the pH value of the regulation reaction solution uses 0.5-1.5
Mol/L NaOH ethanol solution regulation pH value is 10-14.
6. preparation method according to claim 2, it is characterised in that the ethanol solution or sodium borohydride of described hydrazine hydrate
The concentration of ethanol solution be 0.5-0.9 mol/L.
A kind of 7. method of catalyst synthesis 1- amino anthraquinones, it is characterised in that the catalyst is rhodium/nickel alloy nanometer
Catalyst, rhodium, the mol ratio of nickel are 0.01-0.05 in the catalyst:1.
8. the method according to claim 7 for catalyzing and synthesizing 1- amino anthraquinones, it is characterised in that specific synthesis step is such as
Under：
（1）Take 1- nitroanthraquinones and N,N-dimethylformamide（DMF）It is placed in reactor, adds rhodium/nickel alloy nanometer and urge
Agent, wherein, the ratio of 1- nitroanthraquinones, DMF, rhodium/nickel alloy nanocatalyst is：3 g:150 mL:0.03 g-0.3 g；
（2）Reaction unit is installed, nitrogen purging is passed through, removes the air in reactor, then pass to High Purity Hydrogen and make pressure
0.5-1.0 MPa are increased to, are to slowly warm up to 100-160 DEG C, are incubated lower reaction 2-8 h, stir speed (S.S.) is 600 r/min；
（3）After reaction terminates, reaction mass is cooled to room temperature；Sample is analyzed with liquid chromatograph.
9. the method according to claim 7 for catalyzing and synthesizing 1- amino anthraquinones, it is characterised in that step（1）Described in 1-
The ratio of nitroanthraquinone, DMF, rhodium/nickel alloy nanocatalyst is：3 g:150 mL:0.24 g-0.3 g.
10. the method according to claim 7 for catalyzing and synthesizing 1- amino anthraquinones, it is characterised in that step（2）Described in
The MPa of pressure 0.8,130 DEG C are to slowly warm up to, are incubated lower reaction 6h.
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