Method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material

Abstract

In a method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material, a nitrogen-modified activated carbon support is obtained by using 1,10-phenanthroline as a modifier. A trace amount of aurum is used as a main active component and an organic solvent with a low polarity and a low boiling point, isopropanol, is used as a solvent. An ultra-low content of aurum-based catalyst with the aurum loading amount of 0.01 wt % using the above nitrogen-modified activated carbon as a support is prepared by improving the synthesis procedure, and the efficiency of the catalyst is significantly improved. The catalyst has high activity and vinyl chloride selectivity for acetylene hydrochlorination to vinyl chloride, which is low cost, no mercury pollution, simple in preparation process and expansibility, and has great industrial application value.

Claims

1. A method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material, characterized in that: the ultra-low content aurum-based catalyst was used in acetylene hydrochlorination to vinyl chloride. And under the conditions of GHSV(C.sub.2H.sub.2)=170 h.sup.−1, V.sub.(C2H2)/V.sub.(HCl)=1:1.05 and reaction temperature of 180° C., vinyl chloride was synthesized, the reaction route was as follows:
C.sub.2H.sub.2+HCl.fwdarw.C.sub.2H.sub.3Cl wherein the method for preparing an ultra-low content aurum-based catalyst for acetylene hydrochlorination to vinyl chloride comprises the following steps of: (1) preparing a precursor solution: dissolving 0.1082 g of chloroauric acid (HAuCl.sub.4.Math.4H.sub.2O solids with Au≥47.5%) in an organic solvent, isopropanol (IPA), and preparing the IPA solution of HAuCl.sub.4.Math.4H.sub.2O by shaking and ultrasonic treatment; adjusting the ratio of isopropanol to chloroauric acid to prepare the IPA solution of HAuCl.sub.4.Math.4H.sub.2O as 0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA; (2) preparing a nitrogen-modified carbon support: weighing 3 g of 200 mesh activated carbon into a beaker containing 25 mL of deionized water, and adding 1.5 mL of glacial acetic acid under stirring at room temperature for 30 min; weighing 25 mL of deionized water, 1.0 g of nitrogen source 1,10-phenanthroline and 1.5 mL of 30% hydrogen peroxide, successively adding into the above beaker, and continuing stirring at room temperature in the dark for 24 h; The mixture was filtered and dried in an oven at 90° C. for 12-24 h; Under a nitrogen flow rate of 50 mL/min and a heating rate of 5° C./min in a tube furnace, increasing the calcination temperature to 900° C. and keeping for 1 h to obtain a nitrogen-modified carbon support; (3) preparing the catalyst by an impregnation method taking 2999.7 mg of the nitrogen-modified carbon support prepared in step (2), and laying it in a mortar; taking 292 uL of the HAuCl.sub.4.Math.4H.sub.2O solution prepared in step (1), adding isopropanol to prepare a 6 mL solution, and then uniformly dropwise adding it onto the above nitrogen-modified carbon support to finally obtain nitrogen-modified carbon support/g:solution/mL=0.5; the catalyst was thoroughly ground in the clockwise direction to have a smooth surface, and the mass ratio of the aurum to the support is (4) drying the ground catalyst in a blast drying oven for 12-24 h.

2. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material of claim 1, characterized in that: using isopropanol with low polarity and low boiling point as a solvent, 0.1082 g of chloroauric acid (HAuCl.sub.4.Math.4H.sub.2O solids with Au≥47.5%) are dissolved in 50 mL of isopropanol at room temperature, shaken with a homogenizer for 10 min, and then sonicated for 30 min to prepare an isopropanol solution of HAuCl.sub.4.Math.4H.sub.2O, 0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA, and stored in a sealed dark state at low temperature.

3. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material claim 1, characterized in that: the mass content of Au in chloroauric acid in step (1) is Au≥47.5%, and the ultrasonic frequency in step (1) is 40 KHz.

4. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material of claim 1, characterized in that: the activated carbon in step (2) is non-pretreated 200 mesh activated carbon.

5. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material of claim 1, characterized in that: the theoretical nitrogen loading of 1,10-phenanthroline in step (2) is 3.9%.

6. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material of claim 1, characterized in that: the catalyst after grinding in step (3) should ensure that the surface is smooth, and then put into a blast drying oven at 90° C. for drying.

7. The method for acetylene hydrochlorination to vinyl chloride catalyzed by ultra-low content aurum-based material of claim 6, characterized in that: the specific steps are as follows: (1) loading catalyst: padding a layer of quartz wool with a thickness of 10 mm on the middle position of a quartz reaction tube with a diameter of 10 mm, adding the catalyst into the reaction tube and ensuring that the catalyst is smooth, and then padding a layer of quartz wool with a thickness of 10 mm to cover the catalyst; (2) before the reaction: purging the whole pipeline with N.sub.2 at a flow rate of 20 mL min.sup.−1 for 60 min, so as to remove air and moisture in the system; at the same time, increasing the temperature by 5° C./min to 150° C. and keeping for 30 min, and then increasing the temperature by 5° C./min to 180° C.; after that, introducing hydrogen chloride at a flow rate of 20 mL/min and keeping for 30 min, subsequently introducing both reaction gas at a flow rate of V.sub.C2H2=16 mL/min and V.sub.HCl=16.8 mL/min and keeping for 10 min, so as to ensure that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, then reducing the flow rate of the reaction gas at a ratio of V.sub.C2H2/V.sub.HCl=1:1.05, and starting to detect after keeping for 10 min at the reaction flow rate; (3) after the reaction: first passing the gas phase product through an absorption flask containing NaOH solution to remove excess HCl and then analyzing online by gas chromatography GC-9790II to evaluate acetylene conversion and VCM selectivity.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] FIG. 1 acetylene conversion using catalysts of Examples 2 and 4 in acetylene hydrochlorination

[0035] FIG. 2 vinyl chloride selectivity using catalysts of Examples 2 and 4 in acetylene hydrochlorination

DETAILED DESCRIPTION OF THE INVENTION

Example 1 Catalyst Preparation

[0036] 2997 mg of 200 mesh activated carbon (AC*) was weighed and spread in a mortar. 2920 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above activated carbon, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0037] The catalyst was designated 0.1% Au/AC* (IPA).

Comparative Example 1-1 Catalyst Preparation

[0038] Preparing precursor solution: 0.1082 g of chloroauric acid (HAuCl.sub.4.Math.4H.sub.2O solids with Au≥47.5%) was dissolved in deionized water with high polarity and high boiling point and prepared the aqueous solution of HAuCl.sub.4.Math.4H.sub.2O by shaking and ultrasonic treatment.

[0039] 2997 mg of 200 mesh activated carbon (AC*) was weighed and spread in a mortar. 2920 uL of prepared aqueous solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL H.sub.2O) was taken, and added into deionized water to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted aquesous solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the activated carbon, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 100° C. for 12 h. At the end of drying, it is sealed and stored.

[0040] The catalyst was designated 0.1% Au/AC* (H.sub.2O).

Example 2 Catalyst Preparation

[0041] 2999.3 mg of 200 mesh activated carbon (AC*) was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the activated carbon, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0042] The catalyst was designated 0.01% Au/AC* (IPA).

Example 3 Catalyst Preparation

[0043] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 1.8 g of EDTA and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.1AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 3.1%.

[0044] 2999.3 mg of N.sub.1AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.1AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0045] The catalyst was designated 0.01% Au/N.sub.1AC* (IPA).

Example 4 Catalyst Preparation

[0046] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 1.0 g of 1,10-phenanthroline and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.2AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 3.9%.

[0047] 2999.7 mg of N.sub.2AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.2AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0048] The catalyst was designated 0.01% Au/N.sub.2AC* (IPA).

Comparative Example 4-1 Catalyst Preparation

[0049] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 1.0 g of 1,10-phenanthroline and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.2AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 650° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 3.9%.

[0050] 2999.7 mg of N.sub.2AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.2AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0051] The catalyst was designated 0.01% Au/N.sub.2AC*-650.

Example 5 Catalyst Preparation

[0052] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 0.46 g of 2-methylimidazole and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.3AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 4.5%.

[0053] 2999.7 mg of N.sub.3AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.3AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0054] The catalyst was designated 0.01% Au/N.sub.3AC* (IPA).

Example 6 Catalyst Preparation

[0055] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 1.44 g of quinoline and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.4AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 3.5%.

[0056] 2999.7 mg of N.sub.4AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.4AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0057] The catalyst was designated 0.01% Au/N.sub.4AC* (IPA).

Example 7 Catalyst Preparation

[0058] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 0.94 g of vitamin B1 and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.5AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 4.0%.

[0059] 2999.7 mg of N.sub.5AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.5AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0060] The catalyst was designated 0.01% Au/N.sub.5AC* (IPA).

Example 8 Catalyst Preparation

[0061] 3 g of 200 mesh activated carbon (AC*) was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 0.86 g of TCCA and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.6AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 4.0%.

[0062] 2999.7 mg of N.sub.6AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.6AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0063] The catalyst was designated 0.01% Au/N.sub.6AC* (IPA).

Example 9 Catalyst Preparation

[0064] 3 g of 200 mesh activated carbon was weighed and placed into a beaker containing 25 mL of deionized water, and 1.5 mL of glacial acetic acid was added under stirring at room temperature for 30 min; 25 mL of deionized water, 0.24 g of melamine and 1.5 mL of hydrogen peroxide (30%) were weighed, successively added into the above beaker, and continued to stir at room temperature in the dark for 24 h; Then, the mixture was filtered and dried in an oven at 90° C. for 12-24 h; N.sub.7AC* was obtained by calcining the dried solid in a tube furnace at a heating rate of 5° C./min to 900° C. and keeping for 1 h under a nitrogen flow rate of 25-50 mL/min. The theoretical nitrogen loading was 4.9%.

[0065] 2999.7 mg of N.sub.7AC* was weighed and spread in a mortar. 292 uL of prepared IPA solution of HAuCl.sub.4.Math.4H.sub.2O (0.2164 mg HAuCl.sub.4.Math.4H.sub.2O/100 uL IPA) was taken, and added into isopropanol to prepare 6 mL solution, shaken for 10 min, and then sonicated at room temperature for 30 min with an ultrasonic frequency of 40 KHz to rapidly dissolve and mix it; Then, the resulted IPA solution of HAuCl.sub.4.Math.4H.sub.2O was added dropwise and uniformly to the above N.sub.7AC*, which is rapidly ground in a clockwise direction after the addition until the catalyst surface is smooth. It was then transferred to a watch glass and dried in a blast drying oven at 90° C. for 12 h. At the end of drying, it is sealed and stored.

[0066] The catalyst was designated 0.01% Au/N.sub.7AC* (IPA).

[0067] The evaluation process and conditions for all catalysts were: [0068] (1) loading catalyst: padding a layer of quartz wool with a thickness of 10 mm on the middle position of a quartz reaction tube with a diameter of 10 mm, adding the catalyst into the reaction tube and ensuring that the catalyst is smooth, and then padding a layer of quartz wool with a thickness of 10 mm to cover the catalyst. [0069] (2) before reaction: purging the whole pipeline with N.sub.2 at a flow rate of 20 mL min.sup.−1 for 60 min, so as to remove air and moisture in the system; at the same time, increasing the temperature by 5° C./min to 150° C. and keeping for 30 min, and then increasing the temperature by 5° C./min to 180° C. After that, introducing hydrogen chloride at a flow rate of 20 mL/min and keeping for 30 min, subsequently introducing both reaction gas at a flow rate of V(C.sub.2H.sub.2)=16 mL/min and V(HCl)=16.8 mL/min and keeping for 10 min, so as to ensure that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride; then reducing the flow rate of the reaction gas at a ratio of V(C.sub.2H.sub.2)/V(HCl)=1:1.05, and starting to detect after keeping for 10 min at the reaction flow rate. [0070] (3) after reaction: first passing the gas phase product through an absorption flask containing NaOH solution to remove excess HCl and then analyzing online by gas chromatography (GC-9790II) to evaluate acetylene conversion and VCM selectivity.

TABLE-US-00001 TABLE 1 Activity test of catalysts for acetylene hydrochlorination Vinyl Reaction Acetylene chloride temperature GHSV conversion selectivity Catalyst (° C.) (h.sup.−1) in 6 h (%) (%) 0.1% Au/AC* (IPA) 180 170 91.6% >99.0% (Example 1) 0.1% Au/AC* (H.sub.2O) 180 170 70.9% >99.0% (Comparative Example 1-1) 0.01% Au/AC* 180 170 40.8% >99.0% (IPA) (Example 2) 0.01% Au/N.sub.1AC* 180 170 51.0% >99.0% (IPA) (Example 3) 0.01% Au/N.sub.2AC* 180 170 58.8% >99.0% (IPA) (Example 4) 0.01% 180 170 52.2% >99.0% Au/N.sub.2AC*-650 (Comparative Example 4-1) 0.01% Au/N.sub.3AC* 180 170 48.9% >99.0% (IPA) (Example 5) 0.01% Au/N.sub.4AC* 180 170 55.4% >99.0% (IPA) (Example 6) 0.01% Au/N.sub.5AC* 180 170 53.8% >99.0% (IPA) (Example 7) 0.01% Au/N.sub.6AC* 180 170 46.8% >99.0% (IPA) (Example 8) 0.01% Au/N.sub.7AC* 180 170 54.5% >99.0% (IPA) (Example 9)

[0071] The ICP test results for Examples 2 and 4 are shown in Table 2.

TABLE-US-00002 TABLE 2 ICP Test Results Au content in Catalyst the catalyst (wt %) 0.01% Au/AC* (IPA) 0.0096% (Example 2) 0.01% Au/N.sub.2AC* (IPA) 0.0090% (Example 4)

[0072] The elemental analysis test results of Examples 2 and 4 are shown in Table 3.

TABLE-US-00003 TABLE 3 Elemental analysis test results Catalyst N (%) C (%) H (%) S (%) 0.01% 0.73% 83.13% 1.993% 0.097% Au/AC* (IPA) (Example 2) 0.01% 3.39% 87.87% 2.963% 0.008% Au/N.sub.2AC* (IPA) (Example 4)

[0073] As can be seen from Table 1, the catalytic activity of 0.1% Au/AC* (IPA) was better than that of 0.01% Au/AC* (H.sub.2O) under the condition of the reaction temperature of 180° C. and GHSV(C.sub.2H.sub.2)=170 h.sup.−1. Under the condition of the reaction temperature of 180° C. and GHSV(C.sub.2H.sub.2)=170 h.sup.−1, 0.01% Au/AC* (IPA) has an acetylene conversion of 40.8% and a vinyl chloride selectivity higher than 99%. Under the optimal synthesis conditions, 0.01% Au/N.sub.xAC* (IPA) was prepared by using nitrogen-modified carbon as support. Under the optimal synthesis conditions, the conversion of acetylene was improved obviously and the selectivity of vinyl chloride was higher than 99%, wherein the catalytic activity of synthesized 0.01% Au/N.sub.2AC* (IPA) with 1,10-phenanthroline as nitrogen modifier was the best, and under the condition of the reaction temperature of 180° C. and GHSV(C.sub.2H.sub.2)=170 h.sup.−1, the conversion of acetylene was 58.8% and the selectivity of vinyl chloride was higher than 99%, respectively. As can be seen from Example 4 and Comparative Example 4-1, the nitrogen-modified carbon support prepared by calcination at 900° C. had a more significant effect on catalytic performance. Combining the ICP analysis results in Table 2 and the elemental analysis results in Table 3, it can be seen that the catalysts prepared under this synthesis method can maintain high Au and N loadings, indicating that the method of the present invention has significant practical value.

[0074] The present invention is not limited to the specific embodiments described in the above embodiments, and all technical solutions formed by equivalent replacement are within the scope of protection required by the present invention.