COPPER-ZINC ALLOY CATALYST, AND PREPARATION METHOD AND USE THEREOF

Abstract

Provided are a copper-zinc alloy catalyst, and a preparation method and use thereof. The method for preparing the copper-zinc alloy catalyst includes: subjecting copper-zinc alloy particles to pretreatment to obtain the copper-zinc alloy catalyst; alternatively, subjecting copper-zinc alloy particles to pretreatment and partial dezincification in sequence to obtain the copper-zinc alloy catalyst.

Claims

1. A method for preparing a copper-zinc alloy catalyst, comprising: subjecting copper-zinc alloy particles to pretreatment to obtain the copper-zinc alloy catalyst; alternatively, subjecting copper-zinc alloy particles to pretreatment and partial dezincification in sequence to obtain the copper-zinc alloy catalyst.

2. The method of claim 1, wherein the copper-zinc alloy particles are prepared from brass.

3. The method of claim 1, wherein the pretreatment is performed by a process comprising: subjecting the copper-zinc alloy particles to ultrasonic cleaning by using an organic solvent, ultrasonic cleaning by using heated deionized water, and drying in sequence.

4. The method of claim 3, wherein the ultrasonic cleaning by using the organic solvent is conducted at a frequency of 15 KHz to 25 KHz.

5. The method of claim 3, wherein the ultrasonic cleaning by using heated deionized water is conducted at a frequency of 20 KHz to 35 KHz; and the ultrasonic cleaning by using heated deionized water is conducted at a temperature of 50 C. to 80 C.

6. The method of claim 1, wherein the partial dezincification is conducted by a process comprising: mixing a resulting pretreated copper-zinc alloy with an acid solution to obtain a mixture; subjecting the mixture to replacement to obtain a reaction system; and subjecting the reaction system to washing with a weakly alkaline solution, washing with water, and drying in sequence.

7. The method of claim 6, wherein the acid solution is one selected from the group consisting of a nitric acid solution, a sulfuric acid solution, and a hydrochloric acid solution.

8. A copper-zinc alloy catalyst prepared by the method of claim 1.

9. A method for preparing a low-carbon alcohol from a synthesis gas by using the copper-zinc alloy catalyst of claim 8, comprising: subjecting the copper-zinc alloy catalyst to impurity removal to obtain a cleaned copper-zinc alloy, introducing the synthesis gas into the cleaned copper-zinc alloy, and subjecting the synthesis gas to reaction at a temperature of 240 C. to 340 C. to obtain the low-carbon alcohol; wherein the synthesis gas is introduced at a pressure of 3 MPa to 5 MPa.

10. The method of claim 9, wherein the synthesis gas is introduced at a flow rate of 80 mL/min to 120 mL/min and a volume space velocity of 9,600 h.sup.1 to 14,400 h.sup.1; the synthesis gas consists of H.sub.2 and CO; and a volume ratio of the H.sub.2 to the CO is in a range of (1-3):1.

11. The copper-zinc alloy catalyst of claim 8, wherein the copper-zinc alloy particles are prepared from brass.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1 shows a scanning electron microscopy (SEM) image magnified 100 times of the copper-zinc alloy catalyst prepared in Example 1 of the present disclosure;

[0023] FIG. 2 shows an SEM image magnified 100 times of the copper-zinc alloy catalyst prepared in Comparative Example 1 of the present disclosure;

[0024] FIG. 3 shows an SEM image magnified 100 times of the copper-zinc alloy catalyst prepared in Comparative Example 2 of the present disclosure;

[0025] FIG. 4 shows an X-ray diffraction (XRD) pattern of the copper-zinc alloy catalysts prepared in Example 1 and Comparative Examples 1 to 2 of the present disclosure;

[0026] FIG. 5 shows an SEM image magnified 5,000 times of the copper-zinc alloy catalyst prepared in Example 1 of the present disclosure;

[0027] FIG. 6 shows an SEM image magnified 5,000 times of the copper-zinc alloy catalyst prepared in Example 2 of the present disclosure;

[0028] FIG. 7 shows an SEM image magnified 5,000 times of the copper-zinc alloy catalyst prepared in Example 3 of the present disclosure;

[0029] FIG. 8 shows an SEM image magnified 5,000 times of the copper-zinc alloy catalyst prepared in Example 4 of the present disclosure;

[0030] FIG. 9 shows an SEM image magnified 5,000 times of the copper-zinc alloy catalyst prepared in Example 5 of the present disclosure;

[0031] FIG. 10 shows an XRD pattern of the copper-zinc alloy catalysts prepared in Examples 1 to 5 of the present disclosure;

[0032] FIG. 11 shows a CO conversion rate of the copper-zinc alloy catalysts in Use Example 1 and Comparative Use Examples 1 to 2 of the present disclosure;

[0033] FIG. 12 shows a total alcohol selectivity of the copper-zinc alloy catalysts prepared in Use Example 1 and Comparative Use Examples 1 to 2 of the present disclosure; and

[0034] FIG. 13 shows a C.sub.2+ alcohol proportion of the copper-zinc alloy catalysts prepared in Use Example 1 and Comparative Use Examples 1 to 2 of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0035] The present disclosure provides a method for preparing a copper-zinc alloy catalyst, including: subjecting copper-zinc alloy particles to pretreatment to obtain the copper-zinc alloy catalyst; alternatively, [0036] subjecting copper-zinc alloy particles to pretreatment and partial dezincification in sequence to obtain the copper-zinc alloy catalyst.

[0037] In one embodiment of the present disclosure, the copper-zinc alloy particles are subjected to the pretreatment to obtain the copper-zinc alloy catalyst.

[0038] In another embodiment of the present disclosure, the copper-zinc alloy particles are subjected to the pretreatment and partial dezincification in sequence to obtain the copper-zinc alloy catalyst.

[0039] In some embodiments of the present disclosure, the copper-zinc alloy particles are prepared from brass.

[0040] In the present disclosure, the brass is an industrial brass powder with only two elements: Cu and Zn. In the present disclosure, the copper-zinc alloy particles are limited to the above material, which could benefit a catalytic activity of the catalyst.

[0041] In some embodiments of the present disclosure, the pretreatment is performed as follows: subjecting the copper-zinc alloy particles to ultrasonic cleaning by using an organic solvent, ultrasonic cleaning by using heated deionized water, and drying in sequence.

[0042] In some embodiments of the present disclosure, the ultrasonic cleaning by using the organic solvent is performed by acetone ultrasonic cleaning and ethanol ultrasonic cleaning conducted in sequence. In some embodiments, the acetone ultrasonic cleaning is conducted twice, and the ethanol ultrasonic cleaning is conducted twice. In some embodiments, the ultrasonic cleaning by using the organic solvent is conducted at a frequency of 15 KHz to 25 KHz, and preferably 20 KHz.

[0043] In some embodiments of the present disclosure, the ultrasonic cleaning by using heated deionized water is conducted three times at a frequency of 20 KHz to 35 KHz, and preferably 30 KHz. In some embodiments, the ultrasonic cleaning by using heated deionized water is conducted at a temperature of 50 C. to 80 C., and preferably 60 C. There are no special limitations on operations of the ultrasonic cleaning by using the organic solvent and the ultrasonic cleaning by using heated deionized water, and conventional ultrasonic operations conducted by those skilled in the art may be used. In the present disclosure, the times and frequency of the ultrasonic cleaning are limited to the above ranges, which could ensure more thorough cleaning and impurities removal in the copper-zinc alloy particles.

[0044] In some embodiments of the present disclosure, the drying is conducted at a temperature of 90 C. to 120 C., and preferably 110 C. In some embodiments, the drying is conducted for 10 hours to 15 hours, and preferably 12 hours. In the present disclosure, the temperature and time for drying are limited to the above ranges, which could ensure sufficient drying of the pretreated copper-zinc alloy particles.

[0045] In some embodiments of the present disclosure, the partial dezincification is performed as follows: mixing a resulting pretreated copper-zinc alloy with an acid solution to obtain a mixture; subjecting the mixture to replacement to obtain a reaction system; and subjecting the reaction system to washing with a weakly alkaline solution, washing with water, and drying in sequence.

[0046] In some embodiments of the present disclosure, the acid solution is one selected from the group consisting of a nitric acid solution, a sulfuric acid solution, and a hydrochloric acid solution, and preferably the hydrochloric acid solution. In some embodiments, the hydrochloric acid solution is a concentrated hydrochloric acid with a mass fraction of 36% to 38%. In the present disclosure, the concentration of the acid solution is limited to the above ranges, which could facilitate the replacement of the copper-zinc alloy with the acid solution.

[0047] In some embodiments of the present disclosure, the replacement is conducted at ambient temperature for 1 hour to 36 hours, preferably 12 hours to 36 hours, and more preferably 20 hours to 28 hours. In the present disclosure, the temperature and time for replacement are limited to the above ranges, which could ensure that a part of the zinc in the alloy is removed, resulting in increased pores on a surface of the catalyst, thereby improving a catalytic performance of the catalyst.

[0048] In some embodiments of the present disclosure, shaking is conducted after a certain interval during the displacement, preferably 2 hours to 6 hours. In the present disclosure, air bubbles generated in the reaction could be quickly removed by shaking, such that the partial dezincification of the copper-zinc alloy could be achieved.

[0049] In some embodiments of the present disclosure, the weakly alkaline solution is a sodium carbonate solution or a potassium carbonate solution, and preferably the potassium carbonate solution. In some embodiments, the weakly alkaline solution has a molar concentration of 0.1 mol/L to 0.5 mol/L.

[0050] In the present disclosure, there are no special limitations on operations of the cleaning with a weakly alkaline solution and washing with water, and operations commonly used by those skilled in the art may be used. A resulting filtrate is titrated by using a silver nitrate solution to determine that there is no Cl.sup.. In the present disclosure, other impurity ions on the surface of the copper-zinc alloy particles could be removed by cleaning and neutralizing a residual acid on the surface of the catalyst with the weakly alkaline solution, and then washing with water.

[0051] In some embodiments of the present disclosure, the drying is conducted at a temperature of 90 C. to 120 C., and preferably 110 C. There is no special limitation on a drying time, as long as the washed copper-zinc alloy catalyst could be dried.

[0052] In the present disclosure, the copper-zinc alloy particles are used as a catalyst. A CuZn alloy phase in the copper-zinc alloy serves as a catalytic active site to improve a catalytic performance of the copper-zinc alloy catalyst. The copper-zinc alloy is subjected to partial dezincification, such that Zn is partially removed in the alloy, so as to expand a specific surface area of the copper-zinc alloy particles, thereby providing more active sites for catalyzing the synthesis of the low-carbon alcohol from the synthesis gas, and achieving a desirable catalytic effect without using a carrier or additive.

[0053] The present disclosure further provides a copper-zinc alloy catalyst prepared by the method described above.

[0054] The present disclosure further provides use of the copper-zinc alloy catalyst in preparation of a low-carbon alcohol from a synthesis gas, including the following steps: [0055] subjecting the copper-zinc alloy catalyst to impurity removal to obtain a cleaned copper-zinc alloy, introducing the synthesis gas into the cleaned copper-zinc alloy, and subjecting the synthesis gas to reaction at a temperature of 240 C. to 340 C. to obtain the low-carbon alcohol; wherein the synthesis gas is introduced at a pressure of 3 MPa to 5 MPa.

[0056] In some embodiments of the present disclosure, a device for producing the low-carbon alcohol from the synthesis gas is a fixed bed reactor. In some embodiments, the copper-zinc alloy catalyst is loaded at a content of 0.5 g to 1.5 g, and preferably 1 g. In the present disclosure, the loading content of the catalyst are set within the above ranges, which could facilitate the reaction of the synthesis gas to the low-carbon alcohol.

[0057] In some embodiments of the present disclosure, the copper-zinc alloy catalyst is placed in a quartz reaction tube and then placed in the fixed bed reactor to conduct the reaction. In the present disclosure, the copper-zinc alloy catalyst is placed in the quartz reaction tube first, which could avoid an influence caused by direct contact of the catalyst with the inner wall of a stainless steel tube of the fixed bed reactor.

[0058] In some embodiments of the present disclosure, the impurity removal is conducted as follows: feeding N.sub.2 into the quartz reaction tube and then heating the copper-zinc alloy catalyst to a temperature of 300 C. There are no special limitations on a N.sub.2 flow rate, a heating rate, and an impurity removal time, and parameters commonly used by those skilled in the art could be used.

[0059] In some embodiments of the present disclosure, the synthesis gas is introduced at a flow rate of 80 mL/min to 120 mL/min, and preferably 100 mL/min. In some embodiments, the synthesis gas is introduced at a volume space velocity of 9,600 h.sup.1 to 14,400 h.sup.1, and preferably 12,000 h.sup.1. In some embodiments, the synthesis gas consists of H.sub.2 and CO with a volume ratio of (1-3):1, and preferably 2:1. In the present disclosure, the flow rate, components, and ratio of the synthesis gas are limited to the above described ranges, which could make it possible to better synthesize the low-carbon alcohol.

[0060] In some embodiments of the present disclosure, the synthesis gas is introduced at a pressure of 3 MPa to 5 MPa, and preferably 4 MPa. In the present disclosure, the reaction is performed at a temperature of 240 C. to 340 C., and preferably 300 C. In some embodiments, the synthesis gas is heated to the temperature for reaction at a heating rate of 2 C./min. In the present disclosure, the pressure and temperature for the reaction are limited to the above described ranges, which could ensure a better progress of the reaction and improve a conversion rate of the synthesis gas.

[0061] In some embodiments of the present disclosure, after the reaction, a resulting reaction product is divided into a gas phase and a liquid phase through cyclic condensation, and the gas phase and the liquid phase are quantitatively analyzed by chromatography separately.

[0062] The embodiments of the present disclosure will be clearly and completely described below with reference to the examples of the present disclosure. Apparently, the described examples are merely some rather than all of the embodiments of the present disclosure. All other embodiments obtained by those skilled in the art based on the embodiments of the present disclosure without creative efforts shall fall within the scope of the present disclosure.

Example 1

[0063] 5 g of brass particles were added into a beaker, subjected to ultrasonic cleaning by using 25 mL of acetone twice at ambient temperature for 30 min each time, and subjected to ultrasonic cleaning by using absolute ethanol twice at an ultrasonic frequency of 20 KHz for 30 min each time, and then subjected to ultrasonic cleaning by using deionized water 3 times at 30 KHz in sequence to obtain cleaned brass particles. The cleaned brass particles were dried in an oven at 110 C. for 12 hours to obtain a copper-zinc alloy catalyst, recorded as Cu-ye.

Comparative Example 1

[0064] Comparative Example 1 was performed according to Example 1 except that the brass particles were replaced with red copper particles to obtain a copper-zinc alloy catalyst, recorded as Cu-pu.

Comparative Example 2

[0065] Comparative Example 2 was performed according to Example 1 except that the brass particles were replaced with bronze particles to obtain a copper-zinc alloy catalyst, recorded as Cu-cy.

Example 2

[0066] The copper-zinc alloy catalyst obtained in Example 1 was placed into a small beaker containing 15 mL of concentrated hydrochloric acid (36% to 38%), and subjected to partial dezincification at room temperature for 12 hours, with shaking every 2 hours to remove air bubbles on a catalyst surface as soon as possible. After the reaction, the alloy was washed twice with prepared 0.2 mol/L sodium carbonate until neutral, and then washed with deionized water to remove excess impurity ions on the catalyst surface, and dried at 110 C. to obtain a copper-zinc alloy catalyst, recorded as Cu-ye-12 h.

Example 3

[0067] Example 3 was performed according to Example 2 except that the partial dezincification was conducted for 20 hours, with shaking every 4 hours to obtain a copper-zinc alloy catalyst, recorded as Cu-ye-20 h.

Example 4

[0068] Example 4 was performed according to Example 2 except that the partial dezincification was conducted for 28 hours, with shaking every 6 hours to obtain a copper-zinc alloy catalyst, recorded as Cu-ye-28 h.

Example 5

[0069] Example 5 was performed according to Example 2 except that the partial dezincification was conducted for 36 hours, with shaking every 6 hours to obtain a copper-zinc alloy catalyst, recorded as Cu-ye-36 h.

Use Example 1 and Comparative Use Examples 1 to 2

[0070] The copper-zinc alloy catalysts prepared in Example 1 and Comparative Examples 1 to 2 were used to produce a low-carbon alcohol from a synthesis gas by a fixed-bed reactor: the copper-zinc alloy catalyst was loaded into a quartz reaction tube at a loading content of 1 g, and heated at 2 C./min to 300 C. for 3 hours in a N.sub.2 (100 mL/min) atmosphere to remove impurities. After cooling the copper-zinc alloy catalyst to ambient temperature, the synthesis gas was introduced instead of N.sub.2 until the synthesis gas had a pressure of 4 MPa, and then subjected to a reaction at a temperature of 240 C. to 340 C. for 2 hours. The synthesis gas was heated to the reaction temperature at a heating rate of 2 C./min. The synthesis gas was consisted of H.sub.2 and CO at a volume ratio of 2:1. The synthesis gas was introduced at a total gas flow of 100 mL/min, and a volume space velocity of 12,000 h.sup.1. A resulting reaction product was divided into a gas phase and a liquid phase by using cyclic condensation, and the gas phase and the liquid phase were quantitatively analyzed by chromatography separately.

Use Examples 2 to 5

[0071] The copper-zinc alloy catalysts prepared in Examples 2 and 5 were used to produce a low-carbon alcohol from a synthesis gas by a fixed-bed reactor: the copper-zinc alloy catalyst was loaded into a quartz reaction tube at a loading content of 1 g, and heated at 2 C./min to 300 C. for 3 hours in a N.sub.2 (100 mL/min) atmosphere to remove impurities. After cooling the copper-zinc alloy catalyst to ambient temperature, the synthesis gas was introduced instead of N.sub.2 until the synthesis gas had a pressure of 4 MPa, and subjected to a reaction at a temperature of 300 C. for 2 hours. The synthesis gas was heated to the reaction temperature at a heating rate of 2 C./min. The synthesis gas was consisted of H.sub.2 and CO at a volume ratio of 2:1. The synthesis gas was introduced at a total gas flow of 100 mL/min, and a volume space velocity of 12,000 h.sup.1. A resulting reaction product was divided into a gas phase and a liquid phase by using cyclic condensation, and the gas phase and the liquid phase were quantitatively analyzed by chromatography separately.

Comparative Use Example 3

[0072] Comparative Use Example 3 was performed according to Use Example 2 except that the catalyst in Comparative Use Example 3 is prepared according to Chinese patent 201711158742.7, specifically, an electrolytic brass product disclosed in example 4 of the US201711158742.7 was used as a catalyst (i.e., Cat-4) to catalyze the synthesis gas to produce alcohol. The amount of the Cat-4 is 0.5 g. Before the reaction, the catalyst was reduced with a H.sub.2/N.sub.2 gas mixture at a volume ratio of 6:1 at 470 C. for 6 hours, and then the reaction was performed at a lowered temperature of 450 C.

[0073] In the present disclosure, an appearance of the copper-zinc alloy catalysts was observed by an electron microscope.

[0074] In the present disclosure, a physical phase of the copper-zinc alloy catalysts was characterized by an XRD diffractometer.

[0075] In the present disclosure, the resulting reaction products obtained from Use Examples of the catalyst to produce low-carbon alcohol from the synthesis gas were subjected to chromatographic quantitative analysis by a Haixin GC950 chromatography.

[0076] FIG. 1 to FIG. 3 show SEM images magnified 100 times of the copper-zinc alloy catalysts prepared in Example 1 and Comparative Examples 1 to 2. From FIG. 1 to FIG. 3, it can be seen that the Cu-ye catalyst has an irregular shape, and the Cu-pu and Cu-cy catalysts both have a relatively-smooth spherical shape.

[0077] FIG. 4 shows XRD patterns of the copper-zinc alloy catalysts prepared in Example 1 and Comparative Examples 1 to 2. From FIG. 4, it can be seen that the Cu-ye catalyst only contains a Cu.sub.5Zn.sub.8 alloy phase, the Cu-pu catalyst shows a Cu phase and a Zn phase, and the Cu-cy catalyst contains a Cu phase and a Cu.sub.41Sn.sub.11 alloy phase.

[0078] FIG. 5 to FIG. 9 show SEM images magnified 5,000 times of the copper-zinc alloy catalysts prepared in Examples 1 to 5. From FIG. 5 to FIG. 9, it can be seen that surface pores of the catalyst are increased after the dezincification.

[0079] FIG. 10 shows XRD patterns of the copper-zinc alloy catalysts prepared in Examples 1 to 5. From FIG. 10, it can be seen that the Cu-ye catalyst without the dezincification only has the Cu.sub.5Zn.sub.8 alloy phase. During the reaction with hydrochloric acid, Zn is partially removed. As a removal time increased, a peak of the Cu.sub.5Zn.sub.8 alloy phase gradually decreased, and a peak of the Cu phase became sharper. After part of the Zn is removed, the Cu.sub.5Zn.sub.8 alloy and Cu coexist in the catalyst.

[0080] The copper-zinc alloy catalysts prepared in Examples 1 to 5 are tested for a specific surface area, a pore volume, and a pore size, and the test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Specific surface area, pore volume, and pore size of the copper-zinc alloy catalysts prepared in Examples 1 to 5 Specific surface area/ Pore volume/ Average pore size/ Catalyst (m.sup.2 .Math. g.sup.1) (cm.sup.3 .Math. g.sup.1) nm Cu-ye 0.47 0.11 3.40 Cu-ye-12 h 0.79 0.18 15.29 Cu-ye-20 h 1.00 0.23 17.52 Cu-ye-28 h 1.21 0.28 21.12 Cu-ye-36 h 1.86 0.43 23.85

[0081] As shown in Table 1, after the partial dezincification of the copper-zinc alloy catalysts prepared in Examples 2 to 5, the specific surface area, pore volume, and pore size of the catalyst all increased.

[0082] FIG. 11 to FIG. 13 show a CO conversion rate, a total alcohol selectivity, and a C.sub.2+ alcohol proportion of the copper-zinc alloy catalysts prepared in Use Example 1 and Comparative Use Examples 1 to 2. From FIG. 11 to FIG. 13, it can be seen that with the reaction temperature increased, the copper-zinc alloy catalysts have increased CO conversion rate and decreased total alcohol selectivity, and the C.sub.2+ alcohol proportion in the total alcohol is increased and gradually stabilized at around 54%.

[0083] The results of reaction activity evaluation at 300 C. of the copper-zinc alloy catalysts prepared in Use Example 1 and Comparative Use Examples 1 to 2 are shown in Table 2.

TABLE-US-00002 TABLE 2 Results of reaction activity evaluation at 300 C. of the copper-zinc alloy catalysts prepared in Use Example 1 and Comparative Use Examples 1 to 2 Alcohol product Con- distribution/ Alcohol version Product selectivity/mol % wt % yield/g .Math. mL.sup.1 .Math. h.sup.1 Catalyst rate/% CH.sub.x CO.sub.2 ROH DME CH.sub.3OH C.sub.2+OH ROH C.sub.2+OH Cu-ye 6.96 60.49 12.48 26.97 0.06 48.67 51.33 64.35 27.25 Cu-pu 0.85 40.79 10.76 47.97 0.48 65.43 34.57 1.60 0.45 Cu-cy 5.74 58.73 13.09 28.11 0.07 47.79 52.21 71.15 30.45

[0084] From Table 2, it can be seen that catalysts containing only CuZn alloy could also be used to synthesize the low-carbon alcohol. Compared with the Cu-ye catalyst, the Cu-pu catalyst does not have an alloy phase, and shows the worst catalytic effect, a low CO conversion rate, and a low C.sub.2+ alcohol proportion. Although the Cu-cy catalyst contains a CuSn alloy phase, the catalytic effect is also significantly reduced compared with the catalyst containing CuZn alloy phase. Therefore, the copper-zinc alloy catalyst containing the CuZn alloy phase shows a good catalytic effect.

[0085] The results of activity evaluation of Use Examples 1 to 5 and Comparative Use Example 3 are shown in Table 3.

TABLE-US-00003 TABLE 3 Results of activity evaluation of Use Examples 1 to 5 and Comparative Use Example 3 Con- Product Product Alcohol version selectivity/mol % distribution/wt % yield/g .Math. mL.sup.1 .Math. h.sup.1 Catalyst rate/% CH.sub.x CO.sub.2 ROH DME CH.sub.3OH C.sub.2+OH ROH C.sub.2+OH Cu-ye-12h 18.89 46.57 19.06 34.37 0.00 40.17 59.83 261.28 156.32 Cu-ye-20h 18.57 54.31 20.96 24.73 0.00 57.49 42.51 177.12 75.27 Cu-ye-28h 20.05 47.38 21.75 30.87 0.00 39.34 60.66 218.62 132.62 Cu-ye-36h 20.86 47.94 21.58 30.48 0.00 37.22 62.78 200.60 125.94 Cu-ye 6.96 60.49 12.48 26.97 0.06 48.67 51.33 64.35 27.25 Cat-4 41.20 42.80 15.60 41.60 0.00 74.30 25.70

[0086] Table 3 shows the results of activity evaluation of Use Examples 1 to 5 and Comparative Use Example 3. Compared with the catalyst (Cu-ye) in Use Example 1, the catalysts of Use Examples 2 to 5 show an increased conversion rate, an increased total alcohol selectivity, and an increased alcohol yield, indicating that the catalytic properties of the catalysts could be improved after the dezincification. In Comparative Use Example 3, the Cat-4 catalyst is used, where the Cat-4 catalyst is required to be reduced at a higher temperature for 6 hours (the Examples of the present disclosure are not required to be reduced, while Comparative Example 3 is reduced at 470 C.) and reacted at a higher temperature (the Examples of the present disclosure are reacted at 300 C., while Comparative Example 3 are reacted at 450 C.) to achieve a CO conversion rate of 41.2%. Moreover, the C.sub.2+ alcohol in the product of the Comparative Example 3 only accounts for 25.7%. Even if the reaction is conducted at 450 C., carbon chain growth effect is not desirable. On the contrary, the catalysts in the Examples of present disclosure have a better selectivity for C.sub.2+ alcohols when the reaction is conducted at 300 C., and the C.sub.2+ alcohol proportion is as high as 62.78%.

[0087] In the present disclosure, the copper-zinc alloy catalysts have a CO conversion rate of 20.86% and a C.sub.2+ alcohol selectivity of 62.78% when used alone, showing excellent catalytic effect and C.sub.2+ alcohol selectivity, which may have better industrialization prospects.

[0088] The above descriptions are merely preferred embodiments of the present disclosure. It should be noted that those skilled in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the scope of the present disclosure.