CN113908849B - Ethanol and CO 2 Preparation method of catalyst for coupling carbonylation reaction, catalyst and application - Google Patents
Ethanol and CO 2 Preparation 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 99
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 115
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
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- 239000012691 Cu precursor Substances 0.000 claims abstract description 3
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- 239000010936 titanium Substances 0.000 claims description 12
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- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
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- 239000004408 titanium dioxide Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 44
- 229910052751 metal Inorganic materials 0.000 description 19
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- 239000011521 glass Substances 0.000 description 14
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- 238000003756 stirring Methods 0.000 description 12
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- 238000006555 catalytic reaction Methods 0.000 description 11
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- 229910002708 Au–Cu Inorganic materials 0.000 description 5
- 229910002668 Pd-Cu Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect 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
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000002253 acid Substances 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
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- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging 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
- 238000006713 insertion reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses ethanol and CO 2 A preparation method of a catalyst for coupling carbonylation reaction, the catalyst and application. The method comprises the following steps: (1) immersing the carrier in a 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 the M precursor solution into the copper catalyst, adding N 2 Carrying 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) 2 O is oxidized to obtain M-Cu/Cu 1+ An alloy catalyst. The catalyst prepared by the method can realize ethanol and CO under relatively mild conditions 2 The direct carbonylation preparation of ethyl formate has high reaction efficiency, low energy consumption and CO 2 Has 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 CO 2 A 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 at O 2 The alcohol is carbonylated in the presence of a catalyst. And CO compared with CO 2 Has the advantages of wide source, low cost and easy obtaining, and can convert CO into CO 2 And the direct carbonylation of the alcohol and the alcohol has economic value and ecological significance. But CO 2 The molecules themselves are chemically stable and difficult to activate effectively using thermal energy, so that the thermocatalytic CO is 2 The conversion utilization of (2) has the problems of low conversion rate and energy consumption.
According to literature reports on CeO 2 -ZrO 2 Realizes the reaction of ethanol on CO on a mixed oxide catalyst 2 Synthesis of DEC by carbonylation in an atmosphere, in which a water scavenger (2, 2-dimethoxypropane, DMP) is used to promote the reaction in the forward direction, in the amount of substance DMP/C 2 H 5 OH/CO 2 At about 1/1/1, a reaction temperature of 383K gives 0.4mmol DEC after 18h, since ZrO 2 Is strongly acidic, and ethylene (Applied catalysts A: general,2002,237 (1-2): 103-109) is produced as a by-product in the reaction. Report on CeO prepared at different calcination temperatures 2 Effect on DEC production CeO calcined at 873K was found 2 423K, when the amount of the catalyst added is 100mg, ethanol and CO 2 When 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 activated 2 The capacity is stronger (Catalysis Today,2006,115 (1-4): 95-101). Ce x Zr 1-x O 2 The influence of the crystal structure and the acid-base property on the catalytic performance is found, and when the roasting temperature of the catalyst is 1073K and the reaction temperature is 373K, 0.28mmol of DEC (Catalysis Today,2009, 14) can be obtained in 2 hours of reaction8 (3-4):323-328). ZrO loaded using molecular sieves 2 As a catalyst for the reaction, 0.5 g of a catalyst and a substrate C were added 2 H 5 OH is 20mL, CO 2 The reaction pressure is 7.0MPa, after 2 hours of reaction, the reaction is carried out on ZrO 2 0.355mmol 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 increased 2 H 5 OH and CO 2 Activation of the molecule and carbonyl insertion ability (Catalysis Letters, 2014,144 (12): 2144-2150).
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 CO 2 A 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 conditions 2 The direct carbonylation preparation of ethyl formate has high reaction efficiency, low energy consumption and CO 2 Has the advantages of wide source, low price, easy obtainment and low cost.
One of the purposes of the invention is to provide ethanol and CO 2 A 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 the M precursor solution into the copper catalyst, adding N 2 Carrying out displacement reduction reaction under a protection condition, washing and drying to obtain an M-Cu alloy catalyst precursor;
m is one or the combination of Pd, pt, ru and Au;
(4) Introducing N into the M-Cu alloy catalyst precursor obtained in the step (3) 2 O is oxidized to obtain M-Cu/Cu 1+ An alloy catalyst.
In a preferred embodiment of the present invention,
the carrier is doped Ti 3+ Of TiO 2 2 。
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 N 2 Roasting and reducing under the condition to obtain Ti 3+ Of TiO 2 2 ；
The molar ratio of titanium dioxide to sodium borohydride is 1: (1-5);
the roasting temperature is 300-500 ℃; the roasting time is 0.5-2h.
By reducing Ti 4+ Is Ti 3+ To obtain TiO rich in oxygen defects 2 A carrier and is self-doped with Ti 3+ Of TiO (2) 2 Has 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 0.5-2h.
Loading Cu salt in H 2 Reducing 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 0.5-5h.
Using Cu 0 Replacing metal ions of the M salt to obtain the M-Cu alloy
In a preferred embodiment of the present invention,
step (4), the oxidation temperature is 100-300 ℃; the oxidation time is 0.5-2h.
Using N 2 O oxidizes 0-valent Cu in M-Cu into Cu 1+ To obtain Cu 1+ Supported M-Cu catalysts, noted M-Cu/Cu 1 + . Increase Cu in sample while ensuring that sample contains alloy structure 1+ 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 1wt.%;
the content of Cu is 5 to 10wt.%, preferably 5 to 8wt.%.
In a preferred embodiment of the present invention,
the mass ratio of M to Cu in the catalyst is 1.
The invention also aims to provide a method for preparing the catalyst by using the ethanol and the CO 2 A 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 CO 2 The 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 0.5-6h.
The invention can adopt the following technical scheme:
the invention adopts TiO 2 Supported Cu-based alloy catalyst for catalyzing ethanol and CO under illumination condition 2 The ethyl formate is prepared by direct carbonylation, and the performance evaluation is carried out through a visible window high-pressure reaction kettle. The reaction temperature is 35 ℃, the reaction pressure is 1MPa, and the reaction time is 0.5-6h.
TiO of the invention 2 A supported Cu-based alloy catalyst, expressed as M-Cu/TR-R (M = Pd, pt, ru, au, etc.) catalyst, is prepared by supporting M on Cu/TR-R catalyst prepared by incipient wetness impregnation by a potential displacement method to form a metal nanoparticle catalyst of an alloy structure, and then using N 2 O oxidizes 0-valent Cu in M-Cu into Cu 1+ To obtain Cu 1+ Supported M-Cu catalyst to obtain M-Cu/Cu 1+ An alloy catalyst. The active center of the catalyst is M-Cu alloy and TiO 2 Oxygen vacancy, CO 2 In Cu 1+ On-site activation, cu 1+ Promote the occurrence of carbonyl insertion reaction, carbonylationThe product ethyl formate is mainly obtained by coupling the activated states at the intermetallic interface (M-Cu).
TiO 2 Preparation of supported Cu-based alloy catalyst: by self-doping of Ti 3+ Anatase phase TiO 2 The precursor H loaded with Cu/TR-R is obtained by using an incipient wetness impregnation method as a carrier 2 Roasting and reducing in atmosphere to obtain Cu/TR-R catalyst, and utilizing Cu 0 +M n+ →Cu 2+ +M 0 By replacement reaction of N with 2 O oxidizes 0-valent Cu in M-Cu into Cu 1+ To obtain Cu 1+ Supported M-Cu catalyst to obtain M-Cu/Cu 1+ An alloy catalyst wherein the loading of Cu is 5-10% (wt%) and the loading of M is 0.5-5% (wt%).
The invention has the following advantages:
1. the catalyst consists of uniformly dispersed metal nano-particle M-Cu alloy and carrier TiO 2 And (4) forming. Utilizes the intermetallic synergy and the metal active center of the M-Cu alloy structure and TiO 2 Interfacial synergy of carrier oxygen defects, using N 2 Pt-Cu/Cu obtained after O treatment 1+ /TR-R catalysis of ethanol and CO 2 The 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 provided by the invention 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) a spectrum of the Pt-Cu/TR-R catalyst prepared by a displacement method.
Where the abscissa is 2 θ, the unit: degree; intensity on the ordinate
The ab curves in the first graph all show good anatase TiO 2 And 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 invention 1+ catalyst/TR-RXPS spectrum of reagent (Cu LMM spectrum)
Wherein the abscissa is Kinect energy, unit: an electron volt; the ordinate is intensity;
the curves in FIG. 2 clearly demonstrate Pt-Cu/Cu 1+ the/TR-R catalyst contains Cu 1+ 。
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. 8mL of deionized water and 2mL of HNO 3 (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. The mixture was left to stand for 24 hours for aging, 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 TiO 2 A nanoparticle powder.
5g of TiO 2 The powder was mixed with 70mL NaOH (10 mol/L) (national reagent) solution and stirred well, pretreated in an oven at 130 ℃ for 20h, and hydrothermally treated in an oven at 175 ℃ for 48h. Obtaining white solid, drying and fully grinding to obtain TiO 2 And (4) the nanorod, and is marked as TR.
Mixing TR powder with NaBH 4 Physical mixing, calcining in a tube furnace, N 2 Heating 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.
Example 1
Step (1): the Cu/TR-R is accurately synthesized by the incipient wetness impregnation method1g of TR-R powder was weighed into a 10mL load vial for use, and 0.2445g of Cu (NO) was weighed 3 ) 2 ·6H 2 O (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 precursor 2 Heating 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 N 2 Pouring 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 500 r/min) 2 PdCl 4 (Damas-beta) solution (8 mg 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 B 2 O is oxidized at the temperature of 350 ℃ for 2 hours to obtain Pd-Cu/Cu 1+ A catalyst;
in the catalyst, the supported amount of Cu is 5%, the supported amount of Pd is 1%, and the ratio of the amounts of Pd and Cu is 1.
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 weighed 1+ A metal catalyst.
The catalyst is put into a reaction kettle, 20mL of ethanol is added, and CO is charged and discharged 2 Filling with CO ten times 2 To 0.1MPa, ethanol and CO 2 Of the amount of the substanceThe ratio is as follows: 1, and the mass ratio of the catalyst to the ethanol is as follows: 1, 1200, and recharging N 2 When 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 hours cat 。
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 weighed 3+ Of TiO 2 2 Nanorods) powder was placed in a 10mL load vial for use, and 0.2445g of Cu (NO) was weighed 3 ) 2 ·6H 2 And O, preparing 1.5mL of metal salt solution, dropwise adding the prepared metal salt solution into a load small bottle 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 load vial by using filter paper, placing the load vial into a shaker, oscillating for 8 hours at the temperature of 25 +/-3 ℃, placing the load vial into a 60 ℃ oven to dry for 12 hours after oscillation is finished to obtain dry solid, and grinding to obtain a Cu/TR-R catalyst precursor;
step (2), introducing H into the Cu/TR-R catalyst precursor 2 Heating 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 N 2 Pouring 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 500 r/min) 2 PtCl 6 Solution (8 mg drug in 10mL saline solution) (Damas-beta) at 25 deg.C, after the addition was completed, the oil bath was heated to 120 deg.C and stirred for 0.5h, 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 Pt-Cu/TR-R catalyst precursor.
And (4): introducing N into the obtained Pt-Cu/TR-R catalyst precursor 2 Oxidizing O at 300 ℃; the time is 0.5h, and Pt-Cu/Cu is obtained 1+ A catalyst.
In the catalyst, the supported amount of Cu was 5%, the supported amount of Pt was 1%, and the ratio of the amounts of Pt and Cu was 1.
Experiment: the catalytic performance evaluation is carried out in a visible window high-pressure reaction kettle. 0.02g of Pt-Cu/Cu was weighed 1 Loading metal catalyst into reactor, adding ethanol 15mL, charging and discharging CO 2 Ten times, charging CO 2 To 0.1MPa, ethanol and CO 2 The ratio of the amounts of the substances is: 1:1 2 When the pressure is up to 1MPa, after stirring for half an hour in a shading mode, 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/g cat 。
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 weighed 3+ Of TiO 2 2 Nanorod) powder was placed in a 10mL load vial for use, and 0.3912g of Cu (NO) was weighed 3 ) 2 ·6H 2 And 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 precursor 2 Heating 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 N 2 Pouring 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 500 r/min) 2 RuO 4 Solution (26 mg 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. Deionizing the solid in the glass tube after the replacement reactionAnd (3) repeatedly washing with 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 with deionized water, washing for one time with 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 precursor 2 Oxidizing O at 250 ℃; the time is 1h, ru-Cu/Cu is obtained 1+ A catalyst.
The loading amount of Cu in the catalyst is 8%, the loading amount of Ru is 1%, and the ratio of the amounts of Ru and Cu is 1.
And (3) testing: the catalytic performance evaluation was carried out in a sight-window high-pressure reaction vessel. 0.05g of Ru-Cu/Cu was weighed 1+ Loading metal catalyst into reactor, adding 10mL ethanol, charging and discharging CO 2 Filling with CO ten times 2 To 0.1MPa, ethanol and CO 2 The ratio of the amounts of the substances is: 1:1, 1500, and recharging N 2 When 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 hours cat 。
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 weighed 3+ Of TiO 2 2 Nanorod) powder was placed in a 10mL load vial and 0.4890g of Cu (NO) was weighed 3 ) 2 ·6H 2 And 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 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 precursor 2 Heating to 380 ℃, keeping for 1.5h, and taking out to obtain the Cu/TR-R catalyst.
And (3): substitution methodSynthesizing Au-Cu/TR-R, accurately weighing 1.0g of Cu/TR-R catalyst in N 2 Pouring into a glass tube under protection, putting into an oil bath, and dropwise adding HAuCl while magnetically stirring (rotating speed of 500 r/min) 4 Solution (40 mg 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 precursor 2 Oxidizing O at 280 deg.c; the time is 1h, and Au-Cu/Cu is obtained 1+ A catalyst.
In the catalyst, the supported amount of Cu was 10%, the supported amount of Au was 5%, and the ratio of the amounts of Au and Cu was 1.
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 weighed 1+ Putting a metal catalyst into a reaction kettle, adding 20mL of ethanol, charging and discharging CO 2 Ten times, charging CO 2 To 1MPa, ethanol and CO 2 The ratio of the amounts of the substances is: 1, ethanol and the catalyst in the following mass ratio: 1, 1500, and recharging N 2 When 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 303 mu mol/g when the catalysis is stable for 6 hours cat 。
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 weighed 3+ Of TiO 2 2 Nanorods) powder was placed in a 10mL load vial for use, and 0.2445g of Cu (NO) was weighed 3 ) 2 ·6H 2 Preparing 1.5mL of metal salt solution from O, dropwise adding the prepared metal salt solution into a load small bottle by using a rubber head dropper, oscillating on a vortex oscillator while dropwise adding, and uniformly mixing after dropwise addingForming a molten slurry. 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 precursor 2 Heating 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 load of Cu is 5 percent, and adding N 2 Pouring 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 500 r/min) 2 PtCl 6 Solution (8 mg drug made up into 10mL saline solution), pt loading 1%, pt and Cu mass ratio 1. 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 centrifuge 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 CO 2 Filling with CO ten times 2 To 0.1MPa, ethanol and CO 2 The ratio of the amounts of the substances is: 1:1, 1000, and recharging N 2 When the pressure is up to 1MPa, after stirring for half an hour in a shading mode, 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 hours cat 。
Claims (8)
1. Ethanol and CO 2 The preparation method of the catalyst for preparing the ethyl formate through the coupling carbonylation reaction is characterized by comprising the following steps:
(1) Soaking the carrier in a copper precursor solution, and drying to obtain 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 N 2 Carrying 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) 2 O is oxidized to obtain M-Cu/Cu 1+ An alloy catalyst;
the oxidation temperature is 100-300 ℃; the oxidation time is 0.5-2 h;
the carrier is doped Ti 3+ Of TiO (2) 2 。
2. The method of claim 1, wherein:
the carrier is prepared by a method comprising the following steps:
titanium dioxide and sodium borohydride in N 2 Roasting and reducing under the condition to obtain Ti 3+ Of TiO 2 2 ；
The molar ratio of titanium dioxide to sodium borohydride is 1: (1 to 5);
the roasting temperature is 300-500 ℃; the roasting time is 0.5-2h.
3. The method of claim 1, wherein:
step (2), the reduction temperature is 300-500 ℃; the reduction time is 0.5-2h.
4. The method of claim 1, wherein:
and (3) replacing and reducing at 30-120 deg.c for 0.5-5 hr.
5. A catalyst obtainable by the process according to any one of claims 1 to 4, 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.%.
6. The catalyst of claim 5, wherein:
based on the total weight of the catalyst as 100 percent,
the content of M is 0.5-1 wt.%;
the content of Cu is 5-8 wt.%.
7. The catalyst of claim 6, wherein:
the mass ratio of M to Cu in the catalyst is 1.
8. A process for preparing ethyl formate using the catalyst as claimed in any one of claims 5 to 7, characterized in that it comprises:
reacting ethanol and carbon dioxide under the action of the catalyst and under the illumination condition to prepare ethyl formate;
ethanol and CO 2 The mass ratio of (A) to (B) is: 1-1;
the mass ratio of the catalyst to the ethanol is as follows: 1;
the reaction temperature is 30-100 ℃, the reaction pressure is 0.1-1MPa, and the reaction time is 0.5-6h.
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