CN113908849A - Ethanol and CO2Preparation method of catalyst for coupling carbonylation reaction, catalyst and application - Google Patents
Ethanol and CO2Preparation method of catalyst for coupling carbonylation reaction, catalyst and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 17
- 230000008878 coupling Effects 0.000 title abstract description 9
- 238000010168 coupling process Methods 0.000 title abstract description 9
- 238000005859 coupling reaction Methods 0.000 title abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012691 Cu precursor Substances 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 16
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
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- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- 235000019253 formic acid Nutrition 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 238000011068 loading method Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
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- 239000012266 salt solution Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910018883 Pt—Cu Inorganic materials 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
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- 239000000126 substance Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910002708 Au–Cu Inorganic materials 0.000 description 5
- 229910002668 Pd-Cu Inorganic materials 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000007083 alkoxycarbonylation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005910 aminocarbonylation reaction Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J23/8926—Copper and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses ethanol and CO2A preparation method of a catalyst for coupling carbonylation reaction, the catalyst and application. The method comprises the following steps: (1) soaking the carrier in the copper precursor solution and drying; obtaining a copper catalyst precursor; (2) introducing hydrogen into the copper catalyst precursor obtained in the step (1) for reduction to obtain a copper catalyst; (3) dropping M precursor solution into copper catalyst, in N2Carrying out displacement reduction reaction under the protection condition, washing and drying to obtain an M-Cu alloy catalyst precursor; (4) introducing N into the M-Cu alloy catalyst precursor obtained in the step (3)2O is oxidized to obtain M-Cu/Cu1+An alloy catalyst. The catalyst prepared by the method can realize ethanol and CO under relatively mild conditions2Preparation of formic acid by direct carbonylationEthyl ester, high reaction efficiency, low energy consumption, CO2Has the advantages of wide source, low price, easy obtainment and low cost.
Description
Technical Field
The invention relates to the technical field of catalysts, and further relates to ethanol and CO2A preparation method of a catalyst for coupling carbonylation reaction, the catalyst and application.
Background
The carbonylation reaction refers to a reaction in which a carbonyl group (CO) is introduced into an organic molecule, such as formylation, oxycarbonylation, hydroformylation, alkoxycarbonylation, aminocarbonylation, carbonyl-type Heck reaction, Suzuki-Miyaura coupling reaction, and Sonogashira coupling reaction. Carbonylation reactions are considered to be an effective route for converting bulk chemicals to high value-added chemicals such as ketones, aldehydes, amides, esters, other carboxylic acid derivatives and pharmaceutical intermediates. The carbonylation of alcohols involving the insertion of CO and the construction of C-O bonds provides a sustainable and economical process for the production of ester products
Much research is currently done on CO in O2The alcohol is carbonylated in the presence of a catalyst. And CO compared with CO2Has the advantages of wide source, low cost and easy obtaining, and can convert CO into CO2And the direct carbonylation of the alcohol and the alcohol has economic value and ecological significance. But CO2The molecules themselves are chemically stable and difficult to activate effectively using thermal energy, so that the thermocatalytic CO is2The conversion utilization of (2) has the problems of low conversion rate and energy consumption.
According to the literature reports, in CeO2-ZrO2Realizes the reaction of ethanol on CO on a mixed oxide catalyst2Carbonylation to DEC in an atmosphere using a water scavenger (2, 2-dimethoxypropane, DMP) to promote the reaction in the forward direction, at a mass DMP/C2H5OH/CO2At a reaction temperature of 383K of about 1/1/1, 0.4mmol of DEC are obtained after 18h, since ZrO2Has strong acidity, and generates ethylene (Applied Catalysis A: Gene) as a by-product in the reactionral,2002,237(1-2): 103-109). Reports on CeO prepared at different calcination temperatures2Effect on DEC production CeO calcined at 873K was found2423K when the amount of catalyst added is 100mg, ethanol and CO2When the feeding amount is 100 mmol, the yield of DEC is the highest and is 0.42mmol, and a proper acidic site is arranged on the catalyst, so that CO is activated2The capacity is stronger (Catalysis Today,2006,115(1-4): 95-101). CexZr1-xO2The influence of the crystal structure and the acid-base property on the catalytic performance is found to obtain 0.28mmol of DEC (Catalysis Today,2009, 148(3-4):323-328) in 2h of reaction when the catalyst calcination temperature is 1073K and the reaction temperature is 373K. ZrO loaded using molecular sieves2As a catalyst for the reaction, 0.5 g of a catalyst and a substrate C were added2H5OH 20mL, CO2The reaction pressure is 7.0MPa, after 2 hours of reaction, the reaction is carried out on ZrO20.355mmol DEC is obtained on the/3A composite catalyst, and the 3A molecular sieve is used as a cocatalyst to provide an L acid site, so that C in the system is increased2H5OH and CO2Activation of the molecule and carbonyl insertion ability (Catalysis Letters, 2014,144(12): 2144-.
However, the reaction process has high energy consumption and low reaction efficiency. Therefore, developing a new catalyst for the reaction of ethanol and carbon dioxide to prepare ethyl formate is a technical problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides ethanol and CO2A preparation method of a catalyst for coupling carbonylation reaction, the catalyst and application. The catalyst prepared by the method can realize ethanol and CO under relatively mild conditions2The direct carbonylation preparation of ethyl formate has high reaction efficiency, low energy consumption and CO2Has the advantages of wide source, low price, easy obtainment and low cost.
One of the purposes of the invention is to provide ethanol and CO2A preparation method of a catalyst for coupling carbonylation reaction.
The method comprises the following steps:
(1) soaking the carrier in the copper precursor solution and drying; obtaining a copper catalyst precursor;
(2) introducing hydrogen into the copper catalyst precursor obtained in the step (1) for reduction to obtain a copper catalyst;
(3) dropping M precursor solution into copper catalyst, in N2Carrying out displacement reduction reaction under the protection condition, washing and drying to obtain an M-Cu alloy catalyst precursor;
m is one or a combination of Pd, Pt, Ru and Au;
(4) introducing N into the M-Cu alloy catalyst precursor obtained in the step (3)2O is oxidized to obtain M-Cu/Cu1+An alloy catalyst.
In a preferred embodiment of the present invention,
the carrier is doped Ti3+Of TiO 22。
The carrier can be prepared according to the method in the prior art, and the carrier can be prepared according to the following steps:
titanium dioxide and sodium borohydride in N2Roasting and reducing under the condition to obtain Ti3+Of TiO 22;
The molar ratio of titanium dioxide to sodium borohydride is 1: (1-5);
the roasting temperature is 300-500 ℃; the roasting time is 0.5-2 h.
By reducing Ti4+Is Ti3+To obtain TiO rich in oxygen defects2A carrier and is self-doped with Ti3+Of TiO 22Has visible light response and better photocatalysis performance.
In a preferred embodiment of the present invention,
step (2), the reduction temperature is 300-500 ℃; the reduction time is 0.5-2 h.
Loading Cu salt in H2Reducing the alloy into 0-valent metal Cu in the atmosphere;
in a preferred embodiment of the present invention,
in the step (3), the replacement reduction temperature ranges from 30 ℃ to 120 ℃, and the reduction time is 0.5-5 h.
Using Cu0By replacement of the M saltMetal ions to obtain M-Cu alloy
In a preferred embodiment of the present invention,
step (4), the oxidation temperature is 100-300 ℃; the oxidation time is 0.5-2 h.
Using N2O oxidizes 0-valent Cu in M-Cu into Cu1+To obtain Cu1+Supported M-Cu catalysts, noted M-Cu/Cu1 +. Increase Cu in sample while ensuring that sample contains alloy structure1+The presence of Cu1+ improves the ability of CO2 and ethanol to be directly carbonylated to ethyl formate over the catalyst.
It is another object of the present invention to provide a catalyst prepared by the process.
Based on the total weight of the catalyst as 100 percent,
the content of M is 0.5-5 wt.%; preferably 0.5 to 1 wt.%;
the Cu content is 5-10 wt.%, preferably 5-8 wt.%.
In a preferred embodiment of the present invention,
the mass ratio of M to Cu in the catalyst is 1:5-1: 10.
It is another object of the present invention to provide a process for producing ethanol and CO using the catalyst2A method for preparing ethyl formate by coupling carbonylation.
Reacting ethanol and carbon dioxide under the action of the catalyst and under the illumination condition to prepare ethyl formate;
ethanol and CO2The mass ratio of (A) to (B) is: 1:1-1:10
The mass ratio of the catalyst to the ethanol is as follows: 1:1000-1:1500
The reaction temperature is 30-100 ℃, the reaction pressure is 0.1-1MPa, and the reaction time is 0.5-6 h.
The invention can adopt the following technical scheme:
the invention adopts TiO2Supported Cu-based alloy catalyst for catalyzing ethanol and CO under illumination condition2The ethyl formate is prepared by direct carbonylation, and the performance evaluation is carried out through a visible window high-pressure reaction kettle. Reaction temperature of 35 ℃ and reaction pressure of 1MPaThe reaction time is 0.5-6 h.
TiO of the invention2The supported Cu-based alloy catalyst is expressed as M-Cu/TR-R (M ═ Pd, Pt, Ru, Au and other metals) catalyst, M is supported on the Cu/TR-R catalyst prepared by an incipient wetness impregnation method by a potential displacement method to form a metal nanoparticle catalyst with an alloy structure, and N is used2O oxidizes 0-valent Cu in M-Cu into Cu1+To obtain Cu1+Supported M-Cu catalyst to obtain M-Cu/Cu1+An alloy catalyst. The active center of the catalyst is M-Cu alloy and TiO2Oxygen vacancy, CO2In Cu1+Activation at sites, Cu1+Promotes the generation of carbonyl insertion reaction, and the carbonylation product ethyl formate is mainly obtained by coupling activated states on an intermetallic interface (M-Cu).
TiO2Preparation of supported Cu-based alloy catalyst: by self-doping Ti3+Anatase phase of TiO2The precursor H loaded with Cu/TR-R is obtained by using an incipient wetness impregnation method as a carrier2Roasting and reducing in the atmosphere to obtain Cu/TR-R catalyst, and utilizing Cu0+Mn+→Cu2++M0By replacement reaction of N with2O oxidizes 0-valent Cu in M-Cu into Cu1+To obtain Cu1+Supported M-Cu catalyst to obtain M-Cu/Cu1+An alloy catalyst wherein Cu is supported at 5 to 10% (wt%) and M is supported at 0.5 to 5% (wt%).
The invention has the following advantages:
1. the catalyst consists of uniformly dispersed metal nano-particle M-Cu alloy and carrier TiO2And (4) forming. Utilizes the intermetallic synergy and the metal active center of the M-Cu alloy structure and TiO2Interfacial synergy of carrier oxygen defects, using N2Pt-Cu/Cu obtained after O treatment1+/TR-R catalysis of ethanol and CO2The co-activation coupling carbonylation is used for preparing the ethyl formate, so that the amount of the generated ethyl formate is effectively increased.
2. The catalyst is a heterogeneous photocatalyst, the reaction condition is mild, the treatment after the reaction is simple, the energy consumption is low, and the catalyst is favorable for being applied to the industrial production process and conforms to the scientific concept of environmental protection.
Drawings
FIG. 1 Synthesis of Cu/TR-R precursor by incipient wetness impregnation of (a) synthesized in example 2 of the present invention; (b) the Pt-Cu/TR-R catalyst spectrogram prepared by the displacement method.
Where the abscissa is 2 θ, the unit: degree; intensity on the ordinate
The ab curves in FIG. 1 all show good anatase TiO2And no obvious diffraction peak of the metal particles is observed, which indicates that the metal particles are uniformly distributed on TR-R. The carrier did not change significantly before and after loading.
FIG. 2 Synthesis of Pt-Cu/Cu in example 3 of the invention1+XPS spectrum (Cu LMM spectrum) of/TR-R catalyst
Wherein the abscissa is Kinect energy, unit: electron volts; the ordinate is intensity;
the curves in FIG. 2 clearly demonstrate that Pt-Cu/Cu1+the/TR-R catalyst contains Cu1+。
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
Preparation of the carrier:
10mL of a solution of butyl titanate (TBOT) (national reagent) and dispersed with stirring in 20mL of absolute ethanol (Shanghai Aladdin reagent Co.) to form a mixed solution of TBOT and absolute ethanol, which is labeled as solution A. Taking 8mL of deionized water and 2mL of HNO3(national reagent) and 8mL of absolute ethanol, and mixing and continuously stirring to obtain a solution marked as B. Solution B was added dropwise to solution a, eventually forming a gel. Then, the mixture was aged for 24 hours and dried to obtain a dry gel. Roasting in a muffle furnace, heating to 500 ℃, keeping for 2h, naturally cooling to room temperature after the heat preservation procedure is finished to obtain white solid, and grinding the obtained white solid to obtain TiO2Nanoparticle powderAnd (3) grinding.
5g of TiO2The powder was mixed with 70mL of NaOH (10mol/L) (national reagent) solution and stirred well, pretreated in an oven at 130 ℃ for 20h, and hydrothermally treated in an oven at 175 ℃ for 48 h. Obtaining white solid, drying and fully grinding to obtain TiO2And (4) the nanorod, and is marked as TR.
Mixing TR powder with NaBH4Physical mixing, calcining in a tube furnace, N2Heating the atmosphere from room temperature to 400 ℃, and roasting and reducing for 1h to obtain TR-R, wherein the molar mass ratio of TR to NaBH4 is 1: 1.
Example 1
Step (1): synthesizing Cu/TR-R by incipient wetness impregnation, accurately weighing 1g of TR-R powder into a 10mL load vial for later use, and weighing 0.2445g of Cu (NO)3)2·6H2O (a Chinese medicine reagent) is prepared into 1.5mL of metal salt solution, the prepared metal salt solution is dropwise added into a load vial by a rubber head dropper, the metal salt solution is vibrated on a vortex oscillator while being dropwise added, and the metal salt solution is uniformly mixed into a molten paste after the dropwise addition is finished. Sealing the load vial with filter paper, placing into a shaking table, shaking at 25 + -3 deg.C for 8 hr, drying the load vial in a 60 deg.C oven for 12 hr to obtain dry solid, grinding to obtain Cu/TR-R catalyst precursor,
step (2) introducing H into the Cu/TR-R catalyst precursor2Heating to 300 ℃, keeping for 2h, and taking out to obtain the Cu/TR-R catalyst.
And (3): the Pd-Cu/TR-R is synthesized by a displacement method, 1.0g of Cu/TR-R catalyst is accurately weighed, and the catalyst is added into N2Pouring the mixture into a glass tube under protection, putting the mixture into an oil bath, and dropwise adding H while magnetically stirring (the rotating speed is 500r/min)2PdCl4(Damas-beta) solution (8mg drug in 10mL saline solution), the temperature of the dropping process is 25 ℃, after the dropping process, the oil bath is heated to 30 ℃ and stirred for 2h, and the amount of liquid in the glass tube is maintained by adding condensing reflux. And after the displacement reaction is finished, repeatedly washing the solid in the glass tube by using deionized water, centrifuging for 10min by using a centrifugal machine after washing, pouring the upper layer transparent liquid into a waste liquid barrel, washing for three times by using the deionized water, washing for one time by using alcohol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Pd-Cu/TR-R catalyst precursor.
And (4): introducing N into the Pd-Cu alloy catalyst precursor obtained in the step B2O is oxidized at the temperature of 350 ℃ for 2 hours to obtain Pd-Cu/Cu1+A catalyst;
in the catalyst, the loading amount of Cu is 5%, the loading amount of Pd is 1%, and the ratio of the Pd to the Cu is 1: 5.
And (3) testing: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. 0.01g of Pd-Cu/Cu was weighed1+A metal catalyst.
The catalyst is put into a reaction kettle, ethanol and 20mL are added, and CO is charged and discharged2Filling with CO ten times2To 0.1MPa, ethanol and CO2The ratio of the amounts of the substances is: 1:1, the mass ratio of the catalyst to the ethanol is as follows: 1:1200, recharge N2When the pressure is up to 1MPa, after stirring for half an hour in the shade, a 300W Xe lamp light source is turned on to evaluate the catalytic reaction, and the reaction temperature is 35 ℃. On-line gas chromatography was used. The yield of the generated ethyl formate reaches 322 mu mol/g after the catalysis is stable for 6 hourscat。
Example 2
Step (1): Cu/TR-R is synthesized by an incipient wetness impregnation method, and 1g of TR-R (self-doped Ti) is accurately weighed3+Of TiO 22Nanorods) powder was placed in a 10mL load vial for use, and 0.2445g of Cu (NO) was weighed3)2·6H2And O, preparing 1.5mL of metal salt solution, dropwise adding the prepared metal salt solution into a load vial by using a rubber head dropper, oscillating on a vortex oscillator while dropwise adding, and uniformly mixing to form a molten paste after dropwise adding. Sealing the loaded vial by using filter paper, placing the sealed loaded vial into a shaking table, shaking for 8 hours at the temperature of 25 +/-3 ℃, placing the loaded vial into a 60 ℃ drying oven after shaking is finished, drying for 12 hours to obtain a dried solid, and grinding to obtain a Cu/TR-R catalyst precursor;
step (2), introducing H into the Cu/TR-R catalyst precursor2Heating to 450 ℃, keeping for 0.5h, and taking out to obtain the Cu/TR-R catalyst.
And (3): synthesizing Pt-Cu/TR-R by a displacement method, accurately weighing 1.0g of Cu/TR-R catalyst in N2Pouring the mixture into a glass tube under protection, putting the mixture into an oil bath, and dropwise adding H while magnetically stirring (the rotating speed is 500r/min)2PtCl6Solution (8mg drug formulation)10mL of saline solution) (Damas-beta), the temperature of the dropping process was 25 ℃, the oil bath was heated to 120 ℃ after the dropping was completed and stirred for 0.5h, and the amount of liquid in the glass tube was maintained by adding reflux condensation. And after the displacement reaction is finished, repeatedly washing the solid in the glass tube by using deionized water, centrifuging for 10min by using a centrifugal machine after washing, pouring the upper layer transparent liquid into a waste liquid barrel, washing for three times by using the deionized water, washing for one time by using alcohol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Pt-Cu/TR-R catalyst precursor.
And (4): introducing N into the obtained Pt-Cu/TR-R catalyst precursor2Oxidizing O at 300 ℃; the time is 0.5h, and Pt-Cu/Cu is obtained1+A catalyst.
In the catalyst, the loading amount of Cu is 5%, the loading amount of Pt is 1%, and the ratio of the amounts of Pt and Cu is 1: 5.
Experiment: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. 0.02g of Pt-Cu/Cu was weighed1Loading metal catalyst into reactor, adding ethanol 15mL, charging and discharging CO2Filling with CO ten times2To 0.1MPa, ethanol and CO2The ratio of the amounts of the substances is: 1:5, the mass ratio of the catalyst to the ethanol is as follows: 1:1000 recharge N2When the pressure is up to 1MPa, after stirring for half an hour in the shade, a 300W Xe lamp light source is turned on to evaluate the catalytic reaction, and the reaction temperature is 35 ℃. On-line gas chromatography was used. The ethyl formate is generated after 6 hours of catalytic stabilization and the amount reaches 363 mu mol/gcat。
Example 3
Step (1): Cu/TR-R is synthesized by an incipient wetness impregnation method, and 1g of TR-R (self-doped Ti) is accurately weighed3+Of TiO 22Nanorod) powder was placed in a 10mL load vial and 0.3912g of Cu (NO) was weighed3)2·6H2And O, preparing 1.5mL of metal salt solution, dropwise adding the prepared metal salt solution into a load vial by using a rubber head dropper, oscillating on a vortex oscillator while dropwise adding, and uniformly mixing to form a molten paste after dropwise adding. Sealing the loaded vial with filter paper, placing in a shaking table, shaking at 25 + -3 deg.C for 8 hr, drying in a 60 deg.C oven for 12 hr to obtain dried solid, and grinding to obtain Cu/TR-R catalystAn agent precursor.
Step (2) introducing H into the Cu/TR-R catalyst precursor2Heating to 400 ℃, keeping for 1.5h, and taking out to obtain the Cu/TR-R catalyst.
And (3): synthesizing Ru-Cu/TR-R by a displacement method, accurately weighing 1.0g of Cu/TR-R catalyst in N2Pouring the mixture into a glass tube under protection, putting the mixture into an oil bath, and dropwise adding H while magnetically stirring (the rotating speed is 500r/min)2RuO4Solution (26mg drug in 10mL saline solution) (Damas-beta) at 25 deg.C, after the addition was completed, the oil bath was heated to 110 deg.C and stirred for 1h, and the amount of liquid in the glass tube was maintained by reflux condensation. And after the displacement reaction is finished, repeatedly washing the solid in the glass tube by using deionized water, centrifuging for 10min by using a centrifugal machine after washing, pouring the upper layer transparent liquid into a waste liquid barrel, washing for three times by using the deionized water, washing for one time by using alcohol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Ru-Cu/TR-R catalyst precursor.
And (4): introducing N into the obtained Ru-Cu/TR-R catalyst precursor2Oxidizing O at 250 ℃; the time is 1h, Ru-Cu/Cu is obtained1+A catalyst.
The loading of Cu in the catalyst was 8%, the loading of Ru was 1%, and the ratio of the amounts of Ru and Cu was 1: 8.
And (3) testing: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. 0.05g of Ru-Cu/Cu was weighed1+Loading metal catalyst into reactor, adding 10mL ethanol, charging and discharging CO2Filling with CO ten times2To 0.1MPa, ethanol and CO2The ratio of the amounts of the substances is: 1:8, and the mass ratio of the catalyst to the ethanol is as follows: 1:1500, recharge N2When the pressure is up to 1MPa, after stirring for half an hour in the shade, a 300W Xe lamp light source is turned on to evaluate the catalytic reaction, and the reaction temperature is 35 ℃. On-line gas chromatography was used. The amount of the generated ethyl formate reaches 299 mu mol/g when the catalyst is stable for 6 hourscat。
Example 4
Step (1): Cu/TR-R is synthesized by an incipient wetness impregnation method, and 1g of TR-R (self-doped Ti) is accurately weighed3+Of TiO 22Nanorod) powder was placed in a 10mL loading vial for use and weighed0.4890g of Cu (NO)3)2·6H2And O, preparing 1.5mL of metal salt solution, dropwise adding the prepared metal salt solution into a load vial by using a rubber head dropper, oscillating on a vortex oscillator while dropwise adding, and uniformly mixing to form a molten paste after dropwise adding. Sealing the loaded vial by using filter paper, placing the sealed loaded vial into a shaking table, shaking for 8 hours at the temperature of 25 +/-3 ℃, placing the loaded vial into a 60 ℃ drying oven after shaking is finished, drying for 12 hours to obtain a dried solid, and grinding to obtain a Cu/TR-R catalyst precursor;
step (2) introducing H into the Cu/TR-R catalyst precursor2Heating to 380 ℃, keeping for 1.5h, and taking out to obtain the Cu/TR-R catalyst.
And (3): the Au-Cu/TR-R is synthesized by a displacement method, 1.0g of Cu/TR-R catalyst is accurately weighed, and the catalyst is added into N2Pouring into a glass tube under protection, putting into an oil bath, and dropwise adding HAuCl while magnetically stirring (rotating speed of 500r/min)4Solution (40mg drug in 10mL saline solution) (Damas-beta) at 25 deg.C, after the addition was completed, the oil bath was heated to 100 deg.C and stirred for 2h, and the amount of liquid in the glass tube was maintained by reflux condensation. And after the displacement reaction is finished, repeatedly washing the solid in the glass tube by using deionized water, centrifuging for 10min by using a centrifugal machine after washing, pouring the upper layer transparent liquid into a waste liquid barrel, washing for three times by using the deionized water, washing for one time by using alcohol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Au-Cu/TR-R catalyst precursor.
And (4): introducing N into the obtained Au-Cu/TR-R catalyst precursor2Oxidizing O at 280 deg.c; the time is 1h, and Au-Cu/Cu is obtained1+A catalyst.
In the catalyst, the loading amount of Cu is 10%, the loading amount of Au is 5%, and the ratio of the amounts of Au and Cu is 1: 5.
And (3) testing: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. 0.05g of Au-Cu/Cu was weighed1+Loading metal catalyst into reactor, adding ethanol 20mL, charging and discharging CO2Filling with CO ten times2To 1MPa, ethanol and CO2The ratio of the amounts of the substances is: 1:10, the mass ratio of ethanol to catalyst is: 1:1500, recharge N2Stirring in shade at 1MPa for half an hour, and opening 30The catalytic reaction was evaluated by a 0W Xe lamp, and the reaction temperature was 35 ℃. On-line gas chromatography was used. The yield of the generated ethyl formate reaches 303 mu mol/g when the catalysis is stable for 6 hourscat。
Comparative example
Step (1): Cu/TR-R is synthesized by an incipient wetness impregnation method, and 1g of TR-R (self-doped Ti) is accurately weighed3+Of TiO 22Nanorods) powder was placed in a 10mL load vial for use, and 0.2445g of Cu (NO) was weighed3)2·6H2And O, preparing 1.5mL of metal salt solution, dropwise adding the prepared metal salt solution into a load vial by using a rubber head dropper, oscillating on a vortex oscillator while dropwise adding, and uniformly mixing to form a molten paste after dropwise adding. And sealing the load vial by using filter paper, placing the load vial into a shaking table, shaking for 8 hours at the temperature of 25 +/-3 ℃, placing the load vial into a 60 ℃ drying oven after shaking is finished, drying for 12 hours to obtain a dry solid, and grinding to obtain the Cu/TR-R catalyst precursor.
Step (2) introducing H into the Cu/TR-R catalyst precursor2Heating to 350 ℃, keeping for 1h, and taking out to obtain the Cu/TR-R catalyst.
And (3): synthesizing Pt-Cu/TR-R by a displacement method, accurately weighing 1.0g of Cu/TR-R catalyst, wherein the loading capacity of Cu is 5 percent, and adding N2Pouring the mixture into a glass tube under protection, putting the mixture into an oil bath, and dropwise adding H while magnetically stirring (the rotating speed is 500r/min)2PtCl6The solution (8mg of drug prepared into 10mL of salt solution) has the Pt loading of 1 percent and the mass ratio of Pt to Cu of 1:5, the temperature in the dropping process is 25 ℃, the oil bath is heated to 80 ℃ after the dropping is finished and stirred for 1h, and the amount of liquid in the glass tube is maintained by adding condensation reflux. And after the displacement reaction is finished, repeatedly washing the solid in the glass tube by using deionized water, centrifuging for 10min by using a centrifugal machine after washing, pouring the upper layer transparent liquid into a waste liquid barrel, washing for three times by using the deionized water, washing for one time by using alcohol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Pt-Cu/TR-R catalyst.
And (3) testing: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. Weighing 0.02g of Pt-Cu/TR-R metal catalyst, putting into a reaction kettle, adding 15mL of ethanol, charging and discharging CO2Filling with CO ten times2To 0.1MPa, ethanol and CO2The ratio of the amounts of the substances is: 1:5, the mass ratio of the catalyst to the ethanol is as follows: 1:1000, recharge N2When the pressure is up to 1MPa, after stirring for half an hour in the shade, a 300W Xe lamp light source is turned on to evaluate the catalytic reaction, and the reaction temperature is 35 ℃. On-line gas chromatography was used. The amount of the generated ethyl formate reaches 190 mu mol/g when the catalyst is stable for 6 hourscat。
Claims (10)
1. Ethanol and CO2A method of preparing a catalyst for a coupled carbonylation reaction, the method comprising:
(1) soaking the carrier in the copper precursor solution and drying; obtaining a copper catalyst precursor;
(2) introducing hydrogen into the copper catalyst precursor obtained in the step (1) for reduction to obtain a copper catalyst;
(3) dropping M precursor solution into copper catalyst, in N2Carrying out displacement reduction reaction under the protection condition, washing and drying to obtain an M-Cu alloy catalyst precursor;
m is one or a combination of Pd, Pt, Ru and Au;
(4) introducing N into the M-Cu alloy catalyst precursor obtained in the step (3)2O is oxidized to obtain M-Cu/Cu1+An alloy catalyst.
2. The method of preparing a catalyst according to claim 1, wherein:
the carrier is doped Ti3+Of TiO 22。
3. The method of preparing a catalyst according to claim 2, wherein:
the carrier is prepared by a method comprising the following steps:
titanium dioxide and sodium borohydride in N2Roasting and reducing under the condition to obtain Ti3+Of TiO 22;
The molar ratio of titanium dioxide to sodium borohydride is 1: (1-5);
the roasting temperature is 300-500 ℃; the roasting time is 0.5-2 h.
4. The method of preparing a catalyst according to claim 1, wherein:
step (2), the reduction temperature is 300-500 ℃; the reduction time is 0.5-2 h.
5. The method of preparing a catalyst according to claim 1, wherein:
and (3) replacing and reducing at 30-120 deg.c for 0.5-5 hr.
6. The method of preparing a catalyst according to claim 1, wherein:
step (4), the oxidation temperature is 100-300 ℃; the oxidation time is 0.5-2 h.
7. A catalyst obtainable by the process of any one of claims 1 to 6, wherein:
based on the total weight of the catalyst as 100 percent,
the content of M is 0.5-5 wt.%;
the Cu content is 5-10 wt.%.
8. The catalyst of claim 7, wherein:
based on the total weight of the catalyst as 100 percent,
the content of M is 0.5-1 wt.%;
the Cu content is 5-8 wt.%.
9. The catalyst of claim 8, wherein:
the mass ratio of M to Cu in the catalyst is 1:5-1: 10.
10. A process for producing ethyl formate using the catalyst as set forth in any one of claims 7 to 9, characterized in that the process comprises:
reacting ethanol and carbon dioxide under the action of the catalyst and under the illumination condition to prepare ethyl formate;
ethanol and CO2The mass ratio of (A) to (B) is: 1:1-1:10
The mass ratio of the catalyst to the mass of the ethanol is as follows: 1:1000-1: 1500;
the reaction temperature is 30-100 ℃, the reaction pressure is 0.1-1MPa, and the reaction time is 0.5-6 h.
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