CN107694568B - Au/ZnO catalyst, preparation and application in acetylene selective hydrogenation reaction - Google Patents
Au/ZnO catalyst, preparation and application in acetylene selective hydrogenation reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/66—Silver or gold
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
Au/ZnO catalyst and preparation and application thereof in acetylene selective hydrogenation reaction. The invention relates to an Au/ZnO catalyst for acetylene selective hydrogenation reaction. The catalyst takes ZnO with different shapes as a carrier, then Au is loaded on the carrier, and the gold/zinc oxide catalyst for acetylene selective hydrogenation reaction is obtained after drying and roasting at a certain temperature, wherein the theoretical content of gold is 0.5-20% of the mass of the zinc oxide carrier. Under the same conditions, when the rod-shaped zinc oxide is used as a carrier, the catalyst shows better catalytic performance.
Description
Technical Field
The invention relates to a preparation method of a catalyst and application of the catalyst in selective hydrogenation reaction of acetylene. In particular to the preparation of a gold catalyst (gold/zinc oxide Au/ZnO) taking ZnO with a specific morphology as a carrier and the performance research of the gold catalyst in acetylene selective hydrogenation reaction.
Background
In industry, the ethylene raw material used for producing polyethylene contains a small amount of acetylene gas, and the presence of acetylene gas can cause side reactions, leading to the deactivation of ethylene polymerization catalyst, thereby affecting the product quality of polyethylene resin. Thus, the conversion of acetylene to ethylene by selective hydrogenation is a very important reaction in industry. For the catalyst used for the selective hydrogenation of acetylene, not only high ethylene selectivity but also high stability of the catalyst are required. At present, Pd-based catalysts are used industrially to eliminate a small amount of acetylene in ethylene raw materials, the conversion rate is very high, but the selectivity is very low, so that acetylene and even ethylene are excessively hydrogenated to generate ethane and other oligomers, and carbon deposition causes catalyst deactivation and waste of raw materials.
Research shows that the supported nano gold catalyst has catalytic activity on the hydrogenation reaction of olefin and alkyne. Compared with palladium-based catalyst, the gold catalyst has lower activity, but because the gold catalyst has weaker adsorption to reactants, the product is easier to desorb, so that the gold catalyst has unique advantage in the aspect of improving hydrogenation selectivity. At present, various supported gold catalysts are applied to the reaction of acetylene selective hydrogenation. Document 1(j.jia, et.al., j.phys.c)hem.B,2000,104,11153-11156) reported Au/Al2O3The catalyst has good selectivity in the reaction of preparing ethylene by acetylene selective hydrogenation, the loading amount of Au is 10 wt%, and the particle size of gold is increased along with the rise of roasting temperature, so that the activity of the catalyst is influenced, and the reaction is carried out in a batch reaction kettle and is far different from industrial reaction conditions. Reference 2 (T.V.Choudhury, et. al., Catal.letters,2003,86,1-3) reports Au/TiO2The catalyst shows good activity and selectivity in acetylene selective hydrogenation reaction, but the Au particle size is 4.7nm and the distribution is not uniform, so that the problem of low Au utilization rate exists. Document 3(y.azizi, et.al., j.catal.,2008,256,338-2/C2H2For Au/CeO2The influence of the activity and ethylene selectivity in the selective hydrogenation of acetylene, with H2The proportion is increased, the acetylene conversion rate is obviously improved, but the ethylene selectivity is obviously reduced. Literature 4(X.Liu, et. al., Journal of Catalysis,2012,285,152-159) reports Au/SiO treated under different conditions2The catalytic performance in the reaction of preparing ethylene by selective hydrogenation of acetylene in the presence of a large amount of ethylene. In the above reports, the influence of different carriers, pretreatment conditions and reaction conditions on the activity and selectivity of the catalyst in the selective hydrogenation reaction of acetylene is studied, but no research on the influence of the morphology of the carrier on the performance of the catalyst in the reaction is available at present.
In the hydrogenation reaction, there are many reports related to catalysts using ZnO as a carrier, such as Au/ZnO catalyzed selective hydrogenation of cinnamaldehyde to prepare cinnamyl alcohol (c.hangning, et.al., j.phys.chem.c., 119,28885-28894), Pt/ZnO catalyzed selective hydrogenation of 3-nitrostyrene to prepare 3-vinylaniline (c.bergueran, et.al., ind.eng.chem.res.,2015,54,8659-8669), Ru-Cu/ZnO catalyzed selective hydrogenation of benzene to prepare cyclohexene (h.liu, et.al., j.mol.cal.a-chem., 2011,341,35-41), and the like. In the hydrogenation reactions, the ZnO supported catalyst shows good hydrogenation selectivity. However, Au/ZnO is relatively less useful in the selective hydrogenation of acetylene. The only relevant patents of using ZnO carrier in acetylene selective hydrogenation reaction are ZnO supported Pd-based bimetallic catalyst (CN1317367) and Pd monatomic catalyst (CN 104689816A).
Nano ZnO is a novel high-functional fine inorganic product, and exhibits many specific functions in the aspects of catalysis, optics, magnetism, mechanics, etc. due to its specific surface effect, volume effect, quantum effect, dielectric confinement effect, etc. compared with common ZnO. The ZnO has anisotropic morphology and contains nonpolar surfaces
Contains equal amount of Zn atoms and O atoms, belongs to neutral electricity and has better stability; polar surface: containing Zn only (0001) or O only
Has larger dipole moment and is less stable. Compared with other metal oxides, ZnO can form a plurality of different morphologies more easily by controlling synthesis conditions. In addition, compared with the rare earth oxide carrier, the ZnO carrier has the advantages of simple preparation process, low cost and the like.
Based on the background, Au is used as an active component, and ZnO is used as a carrier to have potential advantages in the selective hydrogenation reaction of acetylene. Therefore, the Au/ZnO catalyst with high acetylene conversion rate and high ethylene selectivity is prepared by utilizing the characteristic of controllable ZnO morphology, and has important application value. The invention aims to invent an Au catalyst which is applied to acetylene selective hydrogenation reaction and takes ZnO with different shapes as carriers.
Disclosure of Invention
The invention aims to provide an Au/ZnO catalyst for a reaction of preparing ethylene by selective hydrogenation of acetylene. The catalyst has the characteristics of high selectivity and simple preparation method. Wherein the ZnO carriers with different morphologies comprise rod-shaped zinc oxide (ZnO-N), disk-shaped zinc oxide (ZnO-P) and amorphous ZnO.
In order to achieve the purpose, the invention adopts the technical scheme that: firstly, ZnO carriers with different shapes are prepared in advance by adopting a solvothermal method, then an active Au component is dispersed on the carriers by adopting an impregnation method or a deposition precipitation method, and the active Au component is dried and roasted to obtain the catalyst which can be directly used for reaction.
The rod-shaped ZnO carrier adopts a second materialThe alcohol heating method is to prepare the zinc oxide with ethanol as a solvent, polyvinylpyrrolidone (PVP) as a structure directing agent and Zn (CH)3COO)2·2H2O is a zinc source, and NaOH is alkali. The preparation process comprises the following steps: first, PVP and Zn (CH) are mixed at room temperature3COO)2·2H2O, NaOH dissolved in ethanol solvent in round flask (PVP, NaOH and Zn (CH)3COO)2·2H2The mass ratio of O is 1-10 and 1-12), and stirring for 10-60 min to obtain a white emulsion; and secondly, transferring the round-bottom flask into a constant-temperature water bath kettle at 80 ℃, installing a condenser pipe, opening condensed water, stirring at constant temperature, reacting for 6-48 h, centrifugally washing the obtained white emulsion for more than 1 time by using ultrapure water and ethanol respectively, drying the obtained white sticky matter for 6-4 h at 60 ℃, grinding the dried sample into powder, and roasting at 200-600 ℃ to obtain the carrier which can be directly used for catalyst preparation.
The disc-shaped ZnO carrier is prepared by a hydrothermal method, water is used as a solvent, gelatin is used as a structure directing agent, and Zn (NO) is added3)2·6H2O is a zinc source and Hexamethylenetetramine (HMT) is a base. The preparation process comprises the following steps: mixing gelatin and Zn (NO) at 80 deg.C3)2·6H2O, HMT are sequentially dissolved in water in a beaker (wherein Zn (NO)3)2·6H2The mass ratio of O to gelatin to HMT is 3-12 and 1-4 respectively) to obtain a white emulsion, stirring at a constant temperature and reacting for 6-48 h, respectively centrifugally washing the obtained white emulsion with ultrapure water and ethanol for more than 1 time, drying the obtained white sticky matter at 60 ℃ for 6-48 h, grinding the dried sample into powder, and roasting at 200-600 ℃ to obtain the carrier which can be directly used for catalyst preparation.
The specific process for preparing Au/ZnO by the dipping method comprises the following steps: dissolving a certain amount of Au cluster precursor in ultrapure water (or dichloromethane), adding a carrier under the condition of light-shielding stirring, stirring at room temperature, reacting for 1-12 h, centrifugally washing the obtained suspension for more than 1 time by using the ultrapure water, drying the obtained precipitate for 4-48 h under freeze drying, and roasting the dried powder at 100-600 ℃ to obtain the catalyst which can be directly used for the selective hydrogenation reaction of acetylene.
The specific process for preparing Au/ZnO by the deposition-precipitation method comprises the following steps: dispersing a carrier in ultrapure water, dropwise adding the neutral Au precursor solution into the carrier dispersion liquid, then adjusting the pH of the solution to 9.5, and stirring and reacting at room temperature for 12-48 h; the obtained mixed solution is centrifuged, washed, dried and roasted to finally obtain the catalyst which can be directly used for reaction.
The catalyst can be used for the reaction of preparing ethylene by selective hydrogenation of acetylene. The reaction adopts a fixed bed reactor, and the feed gas ratio is 0.1-2% C2H2，1～50％H2And the rest is one or more than two of inert gases. The reaction temperature interval is 60-300 ℃, one reaction temperature point is arranged at intervals of 40 ℃, each temperature point is subjected to constant temperature reaction for more than 15min, and the temperature rise speed between the two temperature points is 8 ℃/min.
The invention is characterized in that: the ZnO-loaded gold catalyst with a specific morphology is applied to the selective hydrogenation reaction of acetylene for the first time, and the selectivity of ethylene is 85%; the prepared catalyst can be directly used for reaction after being roasted without activation pretreatment; the ZnO carrier used in the invention has simple synthesis process, easy control and low cost.
Drawings
Fig. 1 is an XRD pattern of ZnO prepared in examples 1 and 2 of the present invention.
Fig. 2 is SEM images of ZnO prepared in examples 1 and 2 of the present invention. The ZnO carriers are respectively as follows: ZnO needle; ZnO plate.
FIG. 3 is a TEM photograph of Au/ZnO catalysts prepared in examples 3 and 4 of the present invention. The Au/ZnO catalyst is respectively as follows: a.1% Au/ZnO-N; 0.85% Au/ZnO-P.
FIG. 4 is a graph showing the activity and selectivity of the catalyst with different ZnO morphologies as the carrier.
Detailed Description
Example 1
Preparation of rod-shaped ZnO Carrier (ZnO needle)
A500 mL round-bottom flask is cleaned and dried, magnetons are placed, 6g of PVP and 360mL of absolute ethyl alcohol are sequentially added, and the normal temperature is 400 rpm. Stirring the mixtureThen, 1.5g of Zn (CH) was added3COO)2·2H2O, after ultrasonic dissolution, 9g of NaOH was added to turn the solution into a white turbid solution. After stirring the mixed solution for 30min, the NaOH is dissolved, and the solution becomes a uniform white emulsion. Fixing the round-bottom flask in a constant-temperature water bath kettle at 80 ℃, starting stirring, installing a condenser pipe, starting condensed water, stirring at constant temperature, and reacting for 24 hours to obtain white emulsion. Washing the product with ultrapure water, centrifuging for 2 times, washing with absolute ethanol, centrifuging for 2 times, and drying the obtained white precipitate in an oven at 60 deg.C for 12 h. And grinding the dried sample into powder, placing the powder in a sample tube, storing the sample tube in a dryer and using the sample tube as a catalyst carrier for later use. It was about 15nm in diameter and about 150nm in length as measured by SEM electron microscopy.
Example 2
Preparation of a disk-shaped ZnO Carrier (ZnO plate)
The 1000mL beaker is cleaned and dried, the magneton is put into the beaker, and the beaker is put into a water bath kettle at 80 ℃ after 3g of gelatin and 600mL of ultrapure water are sequentially added. After dissolution with stirring, 17.8g of Zn (NO) was added3)2·6H2And O. After it had dissolved, 8.4g of HMT were added and the solution immediately turned into a white turbid liquid. Sealing the opening of the beaker by using a preservative film, stirring at constant temperature and reacting for 21 hours to obtain white turbid liquid. Washing and centrifuging the product for 3 times by using ultrapure water, washing and centrifuging the product for 1 time by using absolute ethyl alcohol, and drying the obtained white precipitate in an oven at the temperature of 60 ℃ for 12 hours. Grinding the dried sample into powder, roasting at 560 ℃ for 2h, placing the powder in a sample tube, storing the sample tube in a dryer, and using the sample tube as a catalyst carrier for later use. It has a diameter of about 500nm and a thickness of about 180nm as measured by SEM electron microscopy.
Example 3
Impregnation method for preparing rod-shaped ZnO supported gold catalyst (Au/ZnO-N)
Weighing 30mg of Au atom cluster precursor, dissolving in 10mL of ultrapure water, adding 2g of rod-shaped ZnO carrier under the condition of stirring and shading, and then reacting for 1h under the stirring of the rotation speed of 400 rpm. After the product was washed with ultrapure water and centrifuged 3 times, the precipitate was dried in a freeze-drying oven for 12 hours. Grinding the dried sample into powder, and roasting at 300 ℃ for 2h to obtain the catalyst which can be directly used for the selective hydrogenation reaction of acetylene. The theoretical loading of the Au/ZnO-N catalyst prepared by the method is equivalent to the actual value, and the ICP result shows that the loading of gold is about 1%.
Example 4
Immersion method for preparing disk-shaped ZnO supported gold catalyst (Au/ZnO-P)
Compared with example 3, the difference is that rod-shaped ZnO is changed into disc-shaped ZnO, the reaction time is changed from 1h to 12h, and the other materials are used in the same amount and the same operation conditions as example 3. ICP results indicate a gold loading of about 0.85%.
Example 5
Deposition-precipitation method for preparing rod-shaped ZnO supported gold catalyst (Au/ZnO-N-DP)
2g of the rod-shaped ZnO carrier was put into a 25mL beaker with magnetons, and then 15mL of ultrapure water was added thereto, and stirred at room temperature at 600rpm to uniformly disperse the carrier in water. Take 4.36mL of HAuCl4As for a 25mL beaker with magnetons, 0.1M Na was used2CO3The solution was adjusted to neutral pH. Then, the mixed solution containing Au is added into the carrier dispersion liquid drop by drop, and the reaction is carried out for 12 hours under the condition of shading and stirring. The product was washed with ultrapure water and centrifuged 3 times, and the resulting precipitate was dried in a freeze-drying oven for 12 h. Grinding the dried sample into powder, and roasting at 300 ℃ for 2h to obtain the catalyst which can be directly used for the selective hydrogenation reaction of acetylene. The ICP results indicate a gold loading of about 2.5%.
Example 6
Preparation of disk-shaped ZnO-loaded gold catalyst (Au/ZnO-P-DP) by deposition-precipitation method
Compared with example 5, the difference is that rod-shaped ZnO is replaced by disc-shaped ZnO, and the other materials and operation conditions are the same as example 5. ICP results indicate a gold loading of about 3%.
Example 7
Au/ZnO-N catalyst for catalyzing selective hydrogenation reaction of acetylene
The selective hydrogenation reaction of acetylene is carried out in a quartz tube with the inner diameter of 8mm, firstly quartz wool with the thickness of about 7mm is filled, 40mg of Au/ZnO-N catalyst powder is added, and the catalyst is paved and then the quartz wool with the thickness of about 7mm is filled. The quartz tube was mounted in the apparatus, He was turned on, and gas at 20mL/minPurge with flow rate for 30 min. Then opening acetylene H2He three-way gas, the total gas flow rate is 20mL/min, acetylene and H2The volume ratio of (1: 20) and the acetylene content is 1%, the reaction temperature is from 60 ℃ to 300 ℃, a reaction temperature point is arranged at intervals of 40 ℃, each temperature point is subjected to constant temperature reaction for 25min, and the temperature rise speed between the two temperature points is 8 ℃/min. At 180 ℃, the conversion rate reaches 8 percent, and the selectivity is 76 percent. At 300 ℃, the conversion rate reaches 43 percent, and the selectivity is 16 percent.
Example 8
Au/ZnO-P catalyst for catalyzing selective hydrogenation reaction of acetylene
Compared with example 5, except that the Au/ZnO-N catalyst was changed to the Au/ZnO-P catalyst. The other material amounts and operating conditions were the same as in example 5. At 180 ℃ the conversion was 10% and the selectivity was 74%. At 300 ℃ the conversion was 4% and the selectivity 78%.
Example 9
Au/ZnO-N-DP catalyst for catalyzing selective hydrogenation reaction of acetylene
Compared with example 5, except that the Au/ZnO-N catalyst was changed to the Au/ZnO-N-DP catalyst. The other material amounts and operating conditions were the same as in example 5. At 180 ℃, the conversion is 15% and the selectivity is 85%. At 300 ℃, the conversion was 59% and the selectivity was 26%.
Example 10
Au/ZnO-P-DP catalyst for catalyzing acetylene selective hydrogenation reaction
Compared with example 5, except that the Au/ZnO-N catalyst was changed to the Au/ZnO-P-DP catalyst. The other material amounts and operating conditions were the same as in example 5. At 180 ℃ the conversion was 2.4% and the selectivity was 87%. At 300 ℃, the conversion was 8.8% and the selectivity was 73%.
Claims (10)
1. An application of Au/ZnO catalyst in acetylene selective hydrogenation reaction is characterized in that: the catalyst takes ZnO with a specific shape as a carrier, the shape of the ZnO carrier is one of a rod and a disc, and the catalyst takes gold atom cluster Aun(SR)mAs precursorsSR is a nontoxic and harmless biological agent containing sulfhydryl.
2. Use according to claim 1, characterized in that: the preparation process of the catalyst comprises the following steps:
gold atomic cluster Au with controllable atomic number and stable existence in solution for protecting protective agentn(SR)mDispersing the precursor in one of water, toluene and dichloromethane to ensure that the mass volume concentration of the precursor is 2-6 g/L, and then adding 20-60 g/L of ZnO carrieroStirring and reacting for 1-48 h at the temperature of C, centrifuging and washing the obtained mixed solution for 40-100 hoC, drying for 4-24 h, 200-400oAnd C, roasting for 1-6 h to finally obtain the catalyst directly used for reaction.
3. Use according to claim 1, characterized in that: gold cluster Aun(SR)mThe middle SR is a protective agent and comprises one or more than two of glutathione, cysteine and homocysteine, wherein m represents the number of ligands containing sulfydryl and is a positive integer of 1-100; wherein n represents the number of gold atoms and is a positive integer of 1-200.
4. Use according to claim 1, characterized in that: au coatingnIs Au15，Au18，Au21，Au22，Au23，Au24，Au25，Au28，Au32，Au36，Au38，Au55，Au99，Au102，Au144One or a mixture of two or more of them.
5. Use according to claim 1, characterized in that: au is used as an active component, and the weight percentage of Au in the carrier is 0.5-20% based on the total weight of the carrier.
6. Use according to claim 1, characterized in that: the morphology of the ZnO carrier is rod-shaped.
7. Use according to claim 1, characterized in that: the volume ratio of the reaction gas raw material is 0.1-2% C2H2，1~50% H2And the balance being inert gas.
8. Use according to claim 7, characterized in that: the inert gas is one or more of helium and argon.
9. Use according to claim 1, characterized in that: the reaction temperature is 60-300 deg.CoC。
10. Use according to claim 1, characterized in that: the acetylene conversion rate is 5-100%, and the ethylene selectivity is 1-95%.
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