A Greener Production Process of Acetylene and Calcium

Letter Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Greener Production Process of Acetylene and Calcium Diglyceroxide via Mechanochemical Reaction of CaC2 and Glycerol Ao Li,†,‡,§ Hongyan Song,†,§ Xuebing Xu,†,‡ Hong Meng,‡ Yingzhou Lu,‡ and Chunxi Li*,†,‡,∥ †

State Key Laboratory of Chemical Resource Engineering, ‡College of Chemical Engineering, §Faculty of Science, ∥Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China

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S Supporting Information *

ABSTRACT: Calcium carbide (CaC2) is widely used for the production of various acetylene derivatives, accompanying with a huge amount of carbide slag waste. To develop a clean production process, we explored the reaction of CaC2 and glycerol at varying conditions for the first time. The products were characterized by various techniques. It is observed that CaC2 can react with glycerol at ambient temperature in a stirred mill, with 96% of glycerol conversion after 1 h of milling at rotating speed of 450 rpm. Meanwhile, a quantitative amount of anhydrous acetylene free of PH3, AsH3, and H2S was obtained directly due to the lower reactivity of glycerol that suppresses its side reactions with the concomitant Ca3P2, Ca3As2, and CaS impurities. The mechanochemical reaction of CaC2 with glycerol is more efficient than the corresponding thermochemical reaction at high temperature, and CaC2 shows much higher reactivity than CaO with glycerol. The present process achieves direct production of high purity acetylene along with efficient conversion of glycerol to calcium diglyceroxide, a green plasticizer and thermal stabilizer of plastics, realizing high value utilization of both glycerol and CaC2 with full atom economy. This process may aid the sustainable development of the downstream industry of calcium carbide. KEYWORDS: Acetylene production, Clean production, Reaction selectivity, Calcium carbide, High value utilization of glycerol, Ball mill, Mechanochemical activation, Atomic economy

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INTRODUCTION Calcium carbide (CaC2) is an important product of the coal chemical industry.1 Its production capacity was 46 million tons in China with actual output of 20 million tons in 2016. As a commodity chemical, CaC2 has been widely used for the production of various acetylene derivatives, e.g., vinyl chloride, vinyl acetate, carbon black, and so on.2 In these processes, wet acetylene is first produced via hydrolysis of CaC2, accompanying with a huge amount of carbide slag, which has arisen serious environmental concerns for the downstream users of calcium carbide. The wet acetylene needs to be purified and dried through a complicated process. Therefore, it is important to develop a new process that can produce dry acetylene directly without concomitant carbide slag, Ca(OH)2. Acetylenic anion (C22−) of CaC2 has superbasicity and reactivity with many acidic molecules, e.g., water, acetone3 and alcohols.4 If CaC2 reacts with a high-boiling acid, we can directly get dry acetylene and valuable organic calcium products, e.g., calcium acetate as a deicing agent5,6 and calcium stearate as a plasticizer and thermal stabilizer of plastics.7−9 Herein, we studied the mechanochemical reaction of CaC2 with glycerol for the first time for the following reasons. First, as a byproduct of biodiesel,10,11 abundant © XXXX American Chemical Society

glycerol is available for high value utilization, and many high value derivatives of glycerol have been under investigation for the sustainable development of the biodiesel industry.12−15 Second, new glycerin derivatives are likely to be formed via deep dehydration of glycerol by the strong dehydrating agent of CaC 2 , which deserves exploration. Third, calcium diglyceroxide (Ca-DG) has been produced by a ball mill reaction of glycerol with CaO.16 Finally, Ca-DG is an important chemical with many potential uses, e.g., as a basic catalyst for some organic reactions,17−20 and as a plasticizer and thermal stabilizer of plastics.21,22 Mechanochemistry has attracted increasing attention in recent years for the heterogeneous reactions with solid reactants.23 It has been widely used in preparing functional materials,24,25 waste treatment,26−28 and deemed as a greener synthesis approach.29,30 Some excellent reviews on the development and applications of mechanochemistry are available elsewhere.31−36 Generally, calcium carbide is inactive to many chemicals due to its insolubility37 and low efficient Received: April 25, 2018 Revised: June 6, 2018 Published: July 11, 2018 A

DOI: 10.1021/acssuschemeng.8b01864 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Letter

ACS Sustainable Chemistry & Engineering

Figure 1. Characterization of Ca-DG product made by 2 h of milling at 450 rpm in a planetary ball mill if not specified otherwise. (a) XRD of CaDG made by thermal reaction at 120 °C and ball mill at different milling speed; (b) FTIR of Ca-DG; (c) TG/DTA of Ca-DG; and (d,e) SEM of Ca-DG.

ical reaction. The results demonstrate that the present process is a greener and viable process for the coproduction of acetylene and Ca-DG with full atomic economy.

mass transfer between reactants. Therefore, its reaction usually needs complicated solvent and catalyst systems, and longer reaction time ranging from several to dozens of hours.38−40 Herein, we attempted to use a ball mill to break its crystal structure, increase its surface area, promote the interfacial mass transfer, and accordingly accelerate its reactivity. In fact, a series of alkynyl carbon materials (ACMs) have been synthesized through mechanochemical reaction of CaC2 with polyhalogenated hydrocarbons41,42 or transitional metal chlorides43 at ambient temperature, which manifests the viability of the mechanical activation for the enhanced reactivity of CaC2. The ACMs with rich acetylene groups show promising adsorption capacity for organic sulfurs in oil and mercury in wastewater.44,45 In addition, Lukić et al. studied the ball mill reaction of CaO with glycerol, and obtained Ca-DG after 5 h milling at 300 rpm.16 Until now, the mechanochemical reaction of CaC2 with glycerol has not been reported. For this, we studied this reaction in both planetary and stirred mills, and compared the results with thermochem-

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RESULTS AND DISCUSSION

The composition, structure and property of the resulting CaDG was analyzed by XRD, FTIR, TG/DSC, XPS, and SEM, respectively. Detailed characterization methods can be found in the Supporting Information. As seen from Figure 1a, typical diffraction peaks of Ca-DG occur at 8.3°, 10.3°, 21.4°, 24.8°, and 26.7°, which agree well with the reported results (JCPDS card PDF #21-1544).46,47 All Ca-DG products show similar XRD patterns irrespective of their preparation method and conditions, namely via thermal reaction at 120 °C or via mechanochemical reaction at different milling rates. This suggests that the reaction between CaC2 and glycerol follows the same mechanism in both reaction approaches. Specifically, they all arise from the strong interaction between basic C22− of B


Letter

ACS Sustainable Chemistry & Engineering CaC2 and acidic hydrogen of glycerol, forming C2H2 and CaDG, as shown below. CaC2 + 2HOCH 2CH(OH)CH 2OH = C2H 2 + Ca(OCH 2CH(OH)CH 2OH)2

The IR adsorption, shown in Figure 1b, at 2932, 2882, and 2846 cm−1 belong to the C−H stretching vibration. The adsorption at 1470, 1447, 1423, 1267, 1231, 1004, 951, and 919 cm−1 may be ascribed to various bending modes of C−H bonds.46,47 The characteristic peaks of the alcoholic C−O stretching mode of diglyceroxide units present at 1131 and 1075 cm−1. As shown in Figure 1c, the mass loss occurs between 160 and 300 °C with a strong exothermic effect, which corresponds to the decomposition of Ca-DG to calcite. The observed mass loss, 56.2%, is in good agreement with the calculated one, 55.0%. The second weight loss, between 650 and 750 °C, belongs to the decomposition of calcite to CaO. The total weight loss in decomposition period is 76.1%, being consistent with the calculated value of 74.8%. As shown in Figure 1d,e, the solid product is composed of loose and fluffy aggregates with their size ranging from a few micrometers to 50 μm and with irregular shapes. As shown in Figure 2a, the solid product is mainly composed of C, O, and Ca, as indicated by the characteristic peaks at 297.6 eV for C1s, 545.6 eV for O1s, and 349.9 eV for Ca2p. To have a better insight into the bonding types of Ca-DG, the C1s spectrum was deconvulated to three peaks (Figure 2b), which corresponds to three types of C-bonds, i.e., CC sp3 at 284.5 eV, CO at 285.9 eV, and CO at 288.9 eV with their area ratio being 10:15:1. Here the small amount of CO bond may be originated from CaCO3 due to the carbonation of the carbide in storage. Meanwhile, the O1s spectrum can be well deconvulated into two peaks (Figure 2c), which corresponds to two types of O-bonds, i.e., CO at 531.2 eV and CaO at 532.6 eV with their area ratio being 3:1. It is noteworthy that CO is absent here, indicating its negligible amount among all O-bonds. Further, the observed area ratio of CO and CaO (3:1) is consistent with the theoretical one in Ca-DG. Figure 3 presents the GC spectra of commercial acetylene regent and the gas product for GC-MS analysis. It is noted that the acetylene reagent is of high purity except the impurities of acetone and some alkyl siloxanes. Herein, acetone and siloxanes come from the solvent and stabilizing agent used in acetylene cylinder. In contrast, only two main peaks occur for the gas product, corresponding to acetylene and acetone, respectively, and amounting to 98.3% of the total area. Herein, acetone and other trace impurities are most likely from the sampling gasbag used. More importantly, PH3, AsH3, and H2S are absent or nondetectable in the gas product, which, however, is inevitable in conventional acetylene production process due to the hydrolysis of Ca3P2, Ca3As2, and CaS impurities in calcium carbide.2 These impurities must be removed to an allowable limit before use, because of their strong poison for catalysts. For example, the requirement in India for carbide-derived acetylene of quality A is 99.0 vol % acetylene, with allowable impurities of 0.15% H2S, 0.06% PH3, and 0.001% AsH3.48 Therefore, this feature is very attractive for the industrial production of acetylene because the purification process for such impurities may be simplified and even eliminated. The absence of PH3, AsH3, and H2S in the gas product may be ascribed to the much lower reactivity of

Figure 2. XPS of the Ca-DG products made by 2 h of milling at 450 rpm in a planetary ball mill. (a) Full scan XPS; (b) narrow scans of C1s; (c) narrow scans of O1s.

Figure 3. GC spectra of the gas product. Experimental conditions: CaC2:glycerol = 1:2(mole ratio), stirred ball mill, 450 rpm, 2 h.

glycerol with Ca3P2, Ca3As2, and CaS. This may be inferred from the much lower reactivity of glycerol than water with CaC2 and weaker basicity of Ca3P2, Ca3As2, and CaS than CaC2. In short, it is the lower reactivity of glycerol than water that enhances its reaction selectivity with CaC2, and even suppresses its side reaction with Ca3P2, Ca3As2, and CaS for the resultant PH3, AsH3, and H2S impurities. Figure 4 shows the reaction behavior of CaC2 and CaO with glycerol in a planetary ball mill. The experimental details can C


Letter


Figure 4. Glycerol conversion against milling time. Experimental conditions: CaC2 (or CaO):glycerol = 1:2(mole ratio), room temperature, planetary ball mill.

Figure 5. Glycerol conversion in the stirred ball mill at varying speed. Experimental conditions: CaC2 (or CaO):glycerol = 1:2(mole ratio), room temperature.

be found in the Supporting Information. Obviously, the reaction rate increases greatly with the rising rotating speed. For instance, the glycerol conversion after 1 h milling with CaC2 at 300, 450, and 600 rpm is 32%, 58%, and 96%, respectively. The glycerol conversion at 600 rpm for 1 h is equivalent to that at 450 rpm for 4 h. This may be attributed to the drastically increased milling intensity with rotating speed. According to the mechanochemical theory, the reaction rate depends on both ball impact energy (E) and impact frequency (f), and accordingly the milling intensity, which is related to f· E and increased drastically with rotating speed.49 Moreover, the lattice structure of CaC2 is destroyed quickly by the milling balls, which decreases the particle sizes, increases the surface area and the availability of the C22− anions, and thus promotes its reaction with glycerol. This hypothesis may be supported by the fact that the structure of talc is changed from a crystalline state into an amorphous one after 1 h milling at rotating speed of 300 rpm in a planetary ball mill.50 Meanwhile, the particle size (r in radii) decreases exponentially with milling time, and accordingly the increased specific area (A = ∑in= 1ni × 4π × ri2, where ni is the number of particles with radii of ri). In comparison with CaO, CaC2 shows higher reactivity with glycerol due to its stronger Lewis basicity and affinity to the acidic hydrogen of glycerol. The much higher basicity of CaC2 than CaO can be inferred from the acidity of their conjugated acids, i.e., C2H2 and H2O, with their pKa1 values being about 25 and 15.8, respectively, at room temperature.51 The planetary ball mill is only an experimental setup, whereas the widely used industrial mills are stirred mill, drum mill, and vibration mill.52 For this, we also studied the mechnochemical reaction of CaC2 with glycerol in a stirred mill. As shown in Figure 5, the reaction takes place efficiently with 96% of glycerol conversion after 1 h of milling at rotating speed of 450 rpm. In contrast, CaO reacts slowly with glycerol, with 62% of glycerol conversion in 1 h and only 86% even after 5 h of continuous milling at fixed other conditions. As shown in Figure 6, the reaction behavior at different rotating speeds (300, 450, and 600 rpm) follows a similar pattern, and the gas volume increases drastically with the rising rotating speed. At 450 rpm, the acetylene volume increases drastically with time in the initial 10 min, and then increases steadily from 1300 to 1700 mL in the following 50 min, corresponding to 84% of CaC2 conversion. Such characteristic may be relative to the amorphization process of CaC2 in the ball mill, as inferred from the fact that the crystallinity of talc decreases exponentially with time, and its peak intensity at (002) decreases 80% after 10 min milling at 500 rpm.50 It is

Figure 6. Volume of acetylene released with time in the stirred mill at varying rotating speed. Experimental conditions: CaC2:glycerol = 1:2(mole ratio), room temperature.

also noted that the CaC2 conversion is about 10% less than glycerol conversion, which can be ascribed to the competitive consumption of glycerol by CaO as the main impurity of industrial CaC2. To contrast the superiority of mechanochemistry, we also conducted thermal chemical reaction of CaC2 with glycerol at varying conditions. As shown in Figure 7, the initial reaction rate is fast, with 60% of glycerol conversion in the initial 1 h, and then increases slowly to 70% in the following 4 h. This

Figure 7. Glycerol conversion for its thermochemical reaction with CaC2 at different times and temperatures. ●, reaction 2 h at different temperature; ○, reaction at 120 °C for different time (h). D



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ACKNOWLEDGMENTS The authors are grateful for the financial support from the National Natural Science Foundation of China (No. 21776015).

suggests that the intrinsic reaction rate between CaC2 and glycerol is quite high, and the overall reaction is a mass transfer controlled process. At the beginning, there are abundant exposed C22− anions on the surface of the tiny CaC2 crystals, which results in a rapid reaction. As the exposed C22− anions used up, glycerol has to react with the crystal CaC2, which shows much lower reactivity due to the least accessibility of C22− anions, and the increased diffusion resistance of glycerol by the increased coverage of Ca-DG, as well as the restricted reactivity of CaC2 crystals as stabilized by its high lattice energy. In addition, the reaction rate increases with the increasing temperature, since higher temperature favors a higher diffusivity and vapor pressure of glycerol, which facilitates both mass transfer and intrinsic reaction rate. In short, mechanochemistry is more suitable for such heterogeneous reaction of CaC2 and glycerol. This is because the ball mill with intensive impact energy can greatly increase the surface area of the solid reactants, improve the dynamic interfacial renewal, promote effective collision of reactants, and accordingly accelerate the heterogeneous reaction. The mechanochemical reaction in a planetary or stirred ball mill is much more efficient than the corresponding thermochemical reaction at high temperature, and the higher the mechanical energy (rotation speed), the faster the reaction rate.

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CONCLUSION In summary, the reaction of CaC2 and glycerol is studied toward developing a new production process of anhydrous acetylene without carbide slag. The glycerol conversion is above 96% after 1 h of milling in a stirred mill at room temperature under rotating speed of 450 rpm and stoichiometric ratio of CaC2/glycerol. A quantitative amount of high purity acetylene is obtained, and it is the lower reactivity of glycerol that suppresses its side reaction with Ca3P2, Ca3As2, and CaS for the resulting PH3, AsH3, and H2S impurities. The mechanochemical reaction rate of CaC2 with glycerol increases greatly with the rising rotating speed, and the reaction efficiency is superior to the corresponding thermal chemical reaction. In short, the present process is viable for the efficient production of high purity acetylene and Ca-DG, a novel basic catalyst as well as plasticizer and thermal stabilizer of plastics, realizing high value utilization of both glycerol and CaC2 with full atom economy. ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b01864. Experimental details on materials; reaction of CaC2 with glycerol at varying conditions; products treatment and characterization (PDF)

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REFERENCES

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Letter

AUTHOR INFORMATION

Corresponding Author

*C. Li. Tel/Fax: 86-10-64410308; E-mail: [email protected]. cn. ORCID

Chunxi Li: 0000-0003-4176-4480 Notes

The authors declare no competing financial interest. E


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A Greener Production Process of Acetylene and Calcium

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