Production of Oxygen-containing Compounds Catalytic from Depolymerization of Calcium Lignosulphonate by Submicron-scale MgAl Solid Base †

doi:10.7503/cjcu20190318

Abstract

Abstract:

The MgAl layered hydrotalcites(MgAl-LDHs) precursors with submicron-scale were synthesized by introducing ethanol into hydrothermal synthesis method. The synthesis process parameters were optimized by orthogonal experiment, and then the composite metal oxide(MgAlO_x) was obtained after the calcination process. The crystal phase, morphology and alkalinity of both hydrotalcite precursors and solid base oxides were characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM) and the temperature-programmed desorption of CO₂(CO₂-TPD), respecitively. Finally, the catalytic performance of MgAlO_x was evaluated by the depolymerization test of calcium lignosulfonate. The products including solid, liquid, gas three phases, were analyzed by gel permeation chromatography(GPC), gas chromatography/mass spectrometry(GC-MS) and gas chromatography(GC). The results indicated that 140—230 nm of MgAl-LDHs were regulated by adding 15%(volume fraction) C₂H₅OH to the hydrothermal system, the optimal synthesis condition considered from relative crystallinity was n(Mg)/n(Al)=3, pH=12 and the temperature of 80 ℃ for 24 h. the MgAlO_x obtained after the calcination of MgAl-LDHs at 600 ℃ for 6 h under air atmosphere. The optimal depolymerization of calcium lignosulfonate was 270 ℃, 4 h, the addition of 65%(volume fraction) C₂H₅OH and m(MgAlO_x)/m(CLS)=1/2. The gas-liquid-solid three-phase yield distribution was 4.50%, 58.30% and 37.20% under the above condition, the liquid yields increased by 13.30% with the addition of MgAlO_x, the main components of liquid products were phenolics, aromatics, esters and others. Moreover, the selectivity of oxy-containing compounds was 79.05%(phenolics of 66.06%, esters of 12.99%). Fortunately, MgAlO_x would also keep high reactivity and stability even after four cycles of reactions.

Key words: Orthogonal test, MgAl hydrotalcite, Calcium lignosulfonate, Depolymerization, Oxygen-containing compound

CLC Number:

O643

TrendMD:

HAN Hongjing,WANG Yizhen,LI Jinxin,XUE Feng,WANG Haiying,ZHANG Yanan,GE Qin,LIU Yanli,ZHANG Mei,CHEN Yanguang. Production of Oxygen-containing Compounds Catalytic from Depolymerization of Calcium Lignosulphonate by Submicron-scale MgAl Solid Base ^†[J]. Chem. J. Chinese Universities, 2019, 40(11): 2322.

Figures/Tables 15

Level	n(Mg)/n(Al)	pH	Temperature/℃	Time/h
1	2	8	100	6
2	3	10	140	12
3	4	12	180	24

Fig.1 FTIR spectrum of CLS

Fig.2 SEM image of CLS

Fig.3 XRD spectra of MgAl-LDHs prepared under different conditions

Item	n(Mg)/n(Al)	pH	Crystallization temperature/℃	Crystallization time/h	RC(%)
Sample 1	2	10	100	6	51.45
Sample 2	2	11	140	12	59.44
Sample 3	2	12	180	24	83.19
Sample 4	3	10	140	24	67.52
Sample 5	3	11	180	6	89.53
Sample 6	3	12	100	12	91.26
Sample 7	4	10	180	12	62.74
Sample 8	4	11	100	24	74.28
Sample 9	4	12	140	6	78.91
k1	64.69	60.57	72.33	73.30
k2	82.77	74.41	68.62	71.15
k3	71.98	84.45	78.48	75.00
R	18.08	23.88	9.86	3.85

Fig.4 TG-DTG curve of MgAl-LDHs

Fig.5 XRD spectra(A) and SEM images of MgAl(absence of 15% C2H5OH)(B), MgAl-ET(presence of 15% C2H5OH)(C) and MgAlOx(D)

Fig.6 Optimization of process parameters for the depolymerization of CLS

Fig.7 Composition analyses of gas phase products (A) Yield; (B) selectivity.

Sample	$M ? Z$	$M ? w$	$M ? n$	Polydispersity
1	29391	7917	1300	6.08
2	1127	1051	944	1.11
3	756	886	724	1.22

Sample	$M ? Z$	$M ? w$	$M ? n$	Polydispersity
1	29391	7917	1300	6.08
2	1127	1051	944	1.11
3	756	886	724	1.22

Fig.8 Yields of various liquid products

Retention time/min	Liquid product	Relative peak area(%)
Retention time/min	Liquid product	Absence of MgAlO_x	Presence of MgAlO_x
10.62	Phenol(H)	20.04	16.95
13.82	Guaiacol(G)	19.40	16.38
14.14	4-Methyltetrahydro-2H-pyran-2-one(O)	4.57	1.97
15.30	Glutaric acid dimethyl ester(E)	1.19	——
16.26	4-Ethylphenol(H)	4.16	2.99
16.62	Butanedioic acid,1-ethyl ester(E)	——	2.08
16.91	Phenol, 2-methoxy-4-methyl-(G)	4.63	4.14
18.87	Toluene, 2,5-dimethoxy-(A)	1.02	0.64
19.36	Phenol, 4-ethyl-2-methoxy-(G)	10.67	8.99
20.90	Cyclopentanecarboxylic acid, pentyl ester(E)	——	2.99
21.30	Phenol, 2,6-dimethoxy-(S)	12.26	11.85
21.73	Phenol, 2-methoxy-4-propyl-(G)	1.03	0.79
22.21	Succinoic acid, 2-hydroxy-3-methyl-, diethyl ester(E)	——	5.28
22.62	Ethylene glycol di-n-butyrate(E)	——	2.64
23.76	Benzene,1,2,3-trimethoxy-(A)	3.11	2.96
24.73	Ethanone, 1-(4-hydroxy-3-methoxyphenyl)-(E)	3.89	3.97
25.71	Toluene, 3,4,5-trimethoxy-(A)	6.21	5.09
28.44	Homovanillyl alcohol(O)	0	0.71
30.39	Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl)-(A)	7.77	9.42

Fig.9 Catalytic performance for the cycling use of MgAlOx

Fig.10 SEM images of the spent MgAlOx(A) and the regenerated MgAlOx(B)

Fig.11 XRD spectra(A) and CO2-TPD curve(B) of different MgAlOx a. Fresh MgAlOx; b. regenerated MgAlOx; c. spent MgAlOx.

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