Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof
阅读说明：本技术 一种用于乙炔氢氯化反应的非金属催化剂及其制备方法 (Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof ) 是由 朱明远 卢雨生 张海洋 代斌 于 2021-01-14 设计创作，主要内容包括：本发明为一种用于乙炔氢氯化反应的非金属催化剂及其制备方法。一种用于乙炔氢氯化反应的非金属催化剂的制备方法,所述的制备方法为：将葡萄糖、胺、过硫酸铵加入到盐酸溶液中后,搅拌,进行水热处理后,过滤、洗涤、干燥、煅烧,得所述的非金属催化剂。本发明所述的一种用于乙炔氢氯化反应的非金属催化剂及其制备方法,由胺与葡萄糖聚合而成,聚合过程中抑制了葡萄糖的自聚反应,从而得到结构调控的非金属碳氮材料,该催化剂具有较高的催化剂活性,制备条件温和,工艺简单,制备周期短,成本低,适用于乙炔氢氯化反应。(The invention relates to a non-metal catalyst for acetylene hydrochlorination and a preparation method thereof. A preparation method of a non-metallic catalyst for acetylene hydrochlorination comprises the following steps: adding glucose, amine and ammonium persulfate into a hydrochloric acid solution, stirring, carrying out hydrothermal treatment, filtering, washing, drying and calcining to obtain the non-metal catalyst. The non-metal catalyst for acetylene hydrochlorination and the preparation method thereof provided by the invention are prepared by polymerizing amine and glucose, the self-polymerization reaction of the glucose is inhibited in the polymerization process, and the non-metal carbon nitrogen material with a regulated structure is obtained.)
1. A preparation method of a non-metal catalyst for acetylene hydrochlorination is characterized by comprising the following steps: adding glucose, amine and ammonium persulfate into a hydrochloric acid solution, stirring, carrying out hydrothermal treatment, filtering, washing, drying and calcining to obtain the non-metal catalyst.
2. The production method according to claim 1,
the amine is one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
the molar concentration of the hydrochloric acid solution is 1 mol/L.
3. The production method according to claim 2,
the amine is m-phenylenediamine.
4. The production method according to claim 1,
the temperature in the stirring process is 0-60 ℃, and the time is 0-5 h;
the temperature of the hydrothermal treatment is 120-200 ℃, and the time is 5-20 h;
the drying temperature is 80 ℃, and the drying time is 24 hours;
the calcination temperature is 600-1000 ℃, and the calcination time is 2 h.
5. The production method according to claim 4,
the calcination temperature is 800 ℃.
6. The production method according to claim 1,
the molar ratio of the amine to the glucose is 0.1-0.7: 1;
the molar ratio of the amine to the ammonium persulfate is 1: 0.5-2;
the mass volume ratio of the glucose to the hydrochloric acid solution is 10 g: 25 mL.
7. The production method according to claim 6,
the molar ratio of the amine to the glucose is 0.3: 1;
the molar ratio of the amine to the ammonium persulfate is 1:1.
8. The production method according to claim 1,
the washing process sequentially adopts water and ethanol for washing.
9. A non-metallic catalyst for hydrochlorination of acetylene, characterized in that the non-metallic catalyst is prepared by the method of any one of claims 1 to 8.
Technical Field
The invention belongs to the field of acetylene hydrochlorination, and particularly relates to a non-metal catalyst for acetylene hydrochlorination and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is the first and second synthetic resin material in china. The flame-retardant insulating material has electrical insulation, flame retardance and corrosion resistance, and is widely applied to various fields of buildings, capital construction, packaging, electrical and service industries and the like. China is the first major PVC consumer and producer countries in the world. The annual output of PVC in China is continuously rising, the annual total output accounts for more than half of the world's production of polyvinyl chloride, and likewise, the annual consumption of PVC in China accounts for one fifth of the world's total consumption.
Polyvinyl chloride is polymerized from Vinyl Chloride (VCM), which is produced mainly in two industrial processes, the calcium carbide acetylene process and the ethylene process. On one hand, VCM can be produced by a direct acetylene chlorination method, and acetylene is produced by coal-made calcium carbonate; on the other hand, ethylene is chlorinated or oxychlorinated to produce 1, 2-dichloroethane (EDC), and EDC is thermally dehydrochlorinated to produce VCM. As the petrochemical industry has developed in the western world, VCM production is primarily based on olefin technology. But China has the resource characteristics of poor oil, less gas and relatively rich coal, and the use of the calcium carbide acetylene method for producing polyvinyl chloride is more beneficial to relieving the shortage of petroleum resources in China, and has important effects on reducing the external dependence of petroleum and improving the energy safety. Therefore, the calcium carbide acetylene method has been developed as the mainstream process of the polyvinyl chloride industry in China.
However, the problems of mercury consumption and mercury pollution become bottleneck problems restricting the development of the calcium carbide method polyvinyl chloride industry. The industry of calcium carbide method polyvinyl chloride is urgent without mercurization. The reduction is a process and the mercury-free is a direction. The development and the use of the mercury-free catalyst are important ways of fundamentally solving the problem of mercury pollution in the production of polyvinyl chloride by the calcium carbide acetylene method and realizing green manufacture in the polyvinyl chloride industry.
In view of the above, the present invention provides a non-metallic catalyst for hydrochlorination of acetylene and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a preparation method of a nonmetal catalyst for acetylene hydrochlorination, which is simple in process.
In order to realize the purpose, the adopted technical scheme is as follows:
a preparation method of a non-metallic catalyst for acetylene hydrochlorination comprises the following steps: adding glucose, amine and ammonium persulfate into a hydrochloric acid solution, stirring, carrying out hydrothermal treatment, filtering, washing, drying and calcining to obtain the non-metal catalyst.
Further, the amine is one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
the molar concentration of the hydrochloric acid solution is 1 mol/L.
Still further, the amine is m-phenylenediamine.
Further, the temperature in the stirring process is 0-60 ℃, and the time is 0-5 h;
the temperature of the hydrothermal treatment is 120-200 ℃, and the time is 5-20 h;
the drying temperature is 80 ℃, and the drying time is 24 hours;
the calcination temperature is 600-1000 ℃, and the calcination time is 2 h.
Still further, the calcination temperature is 800 ℃.
Further, the molar ratio of the amine to the glucose is 0.1-0.7: 1;
the molar ratio of the amine to the ammonium persulfate is 1: 0.5-2;
the mass volume ratio of the glucose to the hydrochloric acid solution is 10 g: 25 mL.
Still further, the molar ratio of amine to glucose is 0.3: 1;
the molar ratio of the amine to the ammonium persulfate is 1:1.
Furthermore, the washing process adopts water and ethanol for washing in sequence.
The invention also aims to provide the nonmetal catalyst for the hydrochlorination of acetylene, which is prepared by the preparation method and has low cost and higher catalytic activity.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst has high catalytic activity and stability.
2. The catalyst is simple to prepare and convenient to operate.
3. The catalyst has low preparation cost.
Drawings
FIG. 1 is a TEM characterization of the C-800 and 0.3mPDA-C-800 catalysts prepared in example 1 and comparative example 1; in the figure, a and b are TEM characteristics of a C-800 catalyst, and C and d are TEM characteristics of 0.3 mPDA-C-800;
FIG. 2 is a long life characterization of the 0.3mPDA-C-800 catalyst prepared in example 1.
Detailed Description
In order to further illustrate the non-metallic catalyst for hydrochlorination of acetylene and the preparation method thereof according to the present invention, the following detailed description of the non-metallic catalyst for hydrochlorination of acetylene and the preparation method thereof according to the present invention will be made with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The non-metallic catalyst for hydrochlorination of acetylene and the preparation method thereof according to the present invention will be described in further detail with reference to the following specific examples:
the technical scheme of the invention is as follows:
a preparation method of a non-metallic catalyst for acetylene hydrochlorination comprises the following steps: adding glucose, amine and ammonium persulfate into a hydrochloric acid solution, stirring, carrying out hydrothermal treatment, filtering, washing, drying and calcining to obtain the non-metal catalyst.
The hydrochloric acid solution is acidic, and provides an acidic environment for amine and ammonium persulfate, so that the hydrochloric acid solution can also be an acidic solution which does not influence the polymerization reaction, such as a sulfuric acid solution.
Preferably, the amine is one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
the molar concentration of the hydrochloric acid solution is 1 mol/L.
Further preferably, the amine is m-phenylenediamine.
Preferably, the temperature in the stirring process is 0-60 ℃ and the time is 0-5 h. The stirring process is to ensure the uniform mixing of glucose and other substances and to limit the polymerization product of glucose and amine to a specific molecular weight.
The temperature of the hydrothermal treatment is 120-200 ℃, and the time is 5-20 h;
the drying temperature is 80 ℃, and the drying time is 24 hours;
the calcination temperature is 600-1000 ℃, and the calcination time is 2 h.
Further preferably, the calcination temperature is 800 ℃.
Preferably, the molar ratio of amine to glucose is 0.1-0.7: 1;
the molar ratio of the amine to the ammonium persulfate is 1: 0.5-2;
the mass volume ratio of the glucose to the hydrochloric acid solution is 10 g: 25 mL.
Further preferably, the molar ratio of amine to glucose is 0.3: 1;
the molar ratio of the amine to the ammonium persulfate is 1:1.
Preferably, the washing process sequentially adopts water and ethanol for washing.
Example 1:
the operation steps for preparing the catalyst are as follows:
10g of D- (+) -glucose was added to 25mL of 1M hydrochloric acid and stirred to form a transparent solution, and then M-phenylenediamine and ammonium persulfate were added to the clear solution in a molar ratio of 1:1 and the solution was stirred at 60 ℃ for 10 min. The molar ratio of (m-phenylenediamine to D- (+) -glucose) was 0.3: 1)
adding the solution into a stainless steel water heating kettle for hydrothermal treatment, keeping at 160 deg.C for 10 hr, and filtering to obtain sampleAnd (5) preparing the product. Washing the sample with water and ethanol for 10h, respectively, vacuum-filtering, placing the sample obtained by vacuum-filtering in a drying oven, and drying at 80 deg.C for 24 h. Controlling nitrogen and carbon. In an inert gas N2And (3) heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min in the atmosphere, and keeping the temperature for 2h to obtain the nonmetal catalyst. The obtained non-metal catalyst was named 0.3 mPDA-C-800.
2mL of the catalyst sample is taken to be placed in an acetylene hydrochlorination fixed bed reaction device for acetylene hydrochlorination reaction test. The reaction conditions are as follows: the reaction temperature is 220 ℃ and GHSV(C2H2)＝150h-1，HCl/C2H21.15/1. Under the reaction conditions, the conversion rate of vinyl chloride is as high as 96.41%. The product was analyzed by GC-2014C model gas chromatography, FID detector, GDX-301 packed column. At a reaction temperature of 240 ℃ and GHSV(C2H2)＝30h-1The catalyst is subjected to a life test, and the result is shown in fig. 2, the conversion rate of the catalyst is reduced by 12.6% after 260 hours, and the catalyst is proved to have good stability.
Comparative example 1:
the operation steps for preparing the catalyst are as follows:
10g of D- (+) -glucose was added to 25mL of 1M hydrochloric acid, and after stirring to form a clear solution, the solution was stirred at 60 ℃ for 10 min. And adding the solution into a stainless steel water heating kettle for hydro-thermal treatment, keeping the solution at 160 ℃ for 10 hours, and filtering to obtain a sample. Washing the sample with water and ethanol for 10h, respectively, vacuum-filtering, placing the sample obtained by vacuum-filtering in a drying oven, and drying at 80 deg.C for 24 h. In an inert gas N2And (3) heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min in the atmosphere, and keeping the temperature for 2 hours to obtain the non-metal catalyst named as C-800.
2mL of the catalyst sample is taken to be placed in an acetylene hydrochlorination fixed bed reaction device for acetylene hydrochlorination reaction test. The reaction conditions are as follows: the reaction temperature is 220 ℃ and GHSV(C2H2)＝150h-1，HCl/C2H21.15/1. Under the reaction conditions, the vinyl chloride conversion was 63.39%. The product was analyzed by GC-2014C model gas chromatography, FID detector, GDX-301 packed column.
TEM characterization was performed on the C-800 and 0.3mPDA-C-800 catalysts prepared in example 1 and comparative example 1, and the results are shown in FIG. 1. In FIG. 1, a and b are TEM characterization of C-800 catalyst, and C and d are TEM characterization of 0.3 mPDA-C-800. As can be seen from FIG. 1, the catalyst prepared by the technical scheme of the invention is blocky in microstructure, and compared with the catalyst prepared by a comparative example, the catalyst has more pore structures, is more beneficial to catalyzing the hydrochlorination of acetylene, and has better catalytic activity.
Example 2:
the amines used in this example were o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, respectively. Other preparation and reaction conditions were the same as in example 1. The vinyl chloride conversion is shown in table 1.
TABLE 1 Effect of different amine species on acetylene hydrochlorination
O-phenylenediamine
M-phenylenediamine
P-phenylenediamine
Vinyl chloride conversion (%)
64.58
96.41
76.41
As can be seen from the data in table 1, the conversion of vinyl chloride exhibited different conversions with the addition of different amine species. Wherein, the addition of the m-phenylenediamine has the most obvious effect of promoting the hydrochlorination of the acetylene.
Example 3:
in this example, the molar ratio of m-phenylenediamine to ammonium persulfate was 1:0.5, 1:1, 1:1.5, and 1:2, respectively. Other preparation and reaction conditions were the same as in example 1. The vinyl chloride conversion is shown in table 2.
TABLE 2 influence of the molar ratio of m-phenylenediamine to ammonium persulfate on the hydrochlorination of acetylene
M-phenylenediamine and ammonium persulfate molar ratio
1:0.5
1:1
1:1.5
1:2
Vinyl chloride conversion (%)
95.87
96.41
85.38
83.68
As can be seen from the data in Table 2, the conversion of vinyl chloride showed a tendency to increase and then decrease as the amount of ammonium persulfate added was increased. Wherein, when the ratio of the m-phenylenediamine to the ammonium persulfate is 1:1, the promotion effect on the hydrochlorination reaction of acetylene is most obvious.
Example 4:
in this example, the hydrothermal temperature was 120 ℃, 160 ℃, 200 ℃. Other preparation and reaction conditions were the same as in example 1. The vinyl chloride conversion is shown in table 3.
TABLE 3 Effect of hydrothermal temperature on acetylene hydrochlorination
Hydrothermal temperature
120℃
160℃
200℃
Vinyl chloride conversion (%)
96.98
96.41
96.11
It can be seen from the data in table 2 that the conversion of vinyl chloride does not show large fluctuations with increasing hydrothermal temperature.
Example 5:
the hydrothermal time in this example was 5h, 10h, 15h, 20 h. Other preparation and reaction conditions were the same as in example 1. The vinyl chloride conversion is shown in table 4.
TABLE 4 Effect of hydrothermal time on acetylene hydrochlorination
Time of water heating
5h
10h
15h
20h
Vinyl chloride conversion (%)
95.73
96.92
96.53
95.72
It can be seen from the data in Table 4 that the conversion of vinyl chloride does not show large fluctuations as the hydrothermal time increases.
Example 6:
in this example, the inert gas N2Under the atmosphere, the temperature is raised from room temperature to different calcination temperatures (600 ℃, 800 ℃, 1000 ℃) at a temperature raising rate of 5 ℃/min. Other preparation and reaction conditions were the same as in example 1. The vinyl chloride conversion is shown in table 5.
TABLE 5 influence of calcination temperature on hydrochlorination of acetylene
Calcination temperature
600℃
800℃
1000℃
Vinyl chloride conversion (%)
91.91
96.41
94.82
As can be seen from the data in table 5, the conversion of vinyl chloride shows a tendency to increase and then decrease with increasing calcination temperature. Wherein, the accelerating effect on the hydrochlorination reaction of acetylene is most obvious when the calcining temperature is 800 ℃.
Example 7:
the nitrogen-carbon (m-phenylenediamine: D- (+) -glucose) molar ratios x in this example were controlled to be 0.1, 0.3, 0.5, and 0.7, respectively. Other preparation and reaction conditions were the same as in example 1. The conversions of vinyl chloride at different molar ratios are shown in table 6.
TABLE 6 influence of nitrogen-carbon molar ratio on acetylene hydrochlorination
Nitrogen to carbon molar ratio
0.1
0.3
0.5
0.7
Vinyl chloride conversion (%)
78.26
96.41
95.38
90.96
As can be seen from the data in Table 6, the conversion of vinyl chloride showed a tendency to increase first and then decrease as the molar ratio of nitrogen to carbon (m-phenylenediamine: D- (+) -glucose) was increased. Wherein, the most obvious accelerating effect on the hydrochlorination of acetylene is achieved when the nitrogen-carbon molar ratio is 0.3.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.