基于Aspen Plus的脱酸脱水热解液相产物高效分离及其综合利用模拟研究

doi:10.3969/j.issn.0253-2417.2019.02.003

摘要/Abstract

摘要：

对脱酸脱水热解液相产物沸点分布、分离工艺及高附加值酚类化学品的收益进行分析，提出了脱酸脱水热解液相产物分级精馏制备燃油粗品、富酚油和生物质沥青，以及对富酚油进一步分离制备精细化学品的工艺路线。Aspen Plus模拟结果表明：脱酸脱水热解液相产物经精馏塔T-1和T-2初步分离后，可得到燃油粗品、富酚油和生物质沥青；初步分离得到的富酚油经进一步精馏分离，可得到苯酚类(含苯酚91.13%)、邻甲苯酚类(含邻甲苯酚94.58%)、医药原料(主要含有愈创木酚53.44%、3-甲基苯酚34.85%、丙二酸二乙酯11.56%)、香料(2，4-二甲基苯酚32.78%、4-乙基苯酚26.03%、4-甲基愈创木酚31.85%以及其他少量酚类化合物)、染料(对烯丙基苯酚11.16%、3-甲基邻苯二酚35.84%、3-甲基环戊烷-1, 2-二酮41.56%以及少量其他有机物)等精细酚类化学品。按照每吨脱酸脱水热解液相产物成本2 000.00元计算，能耗为497.41元，产品总价5 362.20元，可得产品毛利润为2 864.79元，实现了脱酸脱水热解液相产物的高效综合利用。

关键词: 分级精馏, 化学品

Abstract:

The boiling point distribution of deacidified and dehydrated pyrolysis liquid phase product, separation process and the earnings of high value-added phenolic chemicals were analyzed. The process routes of graded distillation of the deacidified and dehydrated pyrolysis liquid phase product to prepare crude fuel oil, rich phenol oil and biological asphalt, as well as the process route for further separatmg rich phenol oil to prepare fine chemicals were put forward.Simulation results showed that the crude fuel oil, rich phenol oil and biological asphalt could be obtained by the initial separation for deacidified and dehydrated pyrolysis liquid phase product in distillation tower T-1 and T-2, and then by further distillation separation for the obtained rich phenol oil, 91.13% phenol, 94.58% o-cresol, medical raw materials (mainly including guaiacol 53.44%, 3-methylphenol 34.85%, diethyl malonate 11.56%), perfumery (2, 4-dimethylphenol 32.78%, 4-ethylphenol 26.03%, 4-methylguaiacol 31.85% and a small amount of other phenolic compounds), dye (allyl phenol 11.16%, 3-methylo-phenol 35.84%, 3-methylcyclopentane-1, 2- dione 41.56% and a small amount of other organics) and other fine phenolic chemicals are got. Calculation by the cost RMB 2 000 per ton of deacidified and dehydrated pyrolysis liquid phase product, energy consumption was RMB 497.41, total product price was RMB 5 362.20, gross profit of RMB 2 864.79 could got, which achieved the high efficient comprehensive utilization of deacidified and dehydrated pyrolysis liquid phase product.

Key words: fractional distillation, chemicals

中图分类号:

TQ35
TK6

操洪,戚婷婷,李瑞. 基于Aspen Plus的脱酸脱水热解液相产物高效分离及其综合利用模拟研究[J]. 林产化学与工业, 2019, 39(2): 16-24.

Hong CAO,Tingting QI,Rui LI. High-efficiency Separation and Comprehensive Utilization of Deacidification and Dehydration Pyrolysis Liquid Products by Aspen Plus[J]. Chemistry and Industry of Forest Products, 2019, 39(2): 16-24.

图/表 10

图1

表1

图2

表2

脱酸脱水热解液相产物主要化学组分表"

编号¹⁾ No.	保留时间/min retention time	分子式 molecular formula	化合物名称 compound name	沸点/℃ boiling point	GC含量/% GC content
1	1.702	C₃H₆O₂	乙酸甲酯 acetic acid, methyl ester	56.9	1.40
2	1.802	C₄H₈O₂	2-吡咯羧醛 1H-pyrrole-2-carbaldehyde	77.6	0.67
3	2.143	C₇H₁₀O₂	乙基环戊烯醇酮 ethylcyclopentenolone	78.0	0.95
4	4.466	C₄H₈O	2-丁酮 2-butanone	80.0	2.41
5	5.315	C₅H₈O	2, 3-二氢吡喃 2, 3-dihydropyran	85.5	3.04
6	2.372	C₅H₁₀O	3-甲基-2-丁酮 3-methyl-2-butanone	94.0	0.80
7	6.385	C₅H₄O₂	2H-吡喃-2-酮 2H-pyran-2-one	102.0	0.68
8	6.208	C₆H₁₂O	2-甲基-3-戊酮 2-methylpentan-3-one	113.0	0.74
9	2.222	C₅H₈O₂	2, 3-戊二酮 2, 3-pentadione	113.4	0.98
10	4.123	C₅H₁₀O₂	4-甲基-1, 3-二氧己烷 4-methyl-1, 3-dioxane	115.0	3.25
11	4.345	C₅H₈O	4-戊炔-2-醇 4-pentyne-2-ol	115.2	3.53
12	2.372	C₄H₈O₂	1-甲氧基-2-丙酮 1-methoxypropan-2-one	118.0	1.48
13	2.664	C₅H₈O	3-戊烯-2-酮 3-penten-2-one	122.0	1.27
14	2.867	C₅H₈O	2-戊烯醛trans-2-pentenal	123.9	1.52
15	3.346	C₅H₈O	环戊酮 cyclopentanone	130.6	0.72
16	5.950	C₆H₁₂O₂	4, 4-二甲基-1, 3-二氧己烷 4, 4-dimethyl-1, 3-dioxane	133.3	0.54
17	4.623	C₈H₁₀	1, 4-二甲苯 1, 4-dimethylbenzene	138.4	0.68
18	4.678	C₃H₆O₂	丙酸 propionic acid	141.0	0.49
19	4.136	C₆H₁₀O	2-甲基环戊酮 2-methylcyclopentanone	141.0	0.92
20	3.534	C₅H₁₀O₃	1-(二甲基缩醛)丙酮醛 1-(dimethyl acetal)pyruvaldehyde	142.4	3.05
21	3.814	C₆H₁₂O₃	2, 5-二甲氧基四氢呋喃 2, 5-dimethoxytetrahydrofuran	147.4	0.09
22	2.372	C₄H₈O₂	3-羟基-2-丁酮 3-hydroxybutan-2-one	148.0	2.44
23	3.271	C₄H₆O₃	丙酮酸甲酯 methyl pyruvate	148.3	1.82
24	3.417	C₆H₁₂O₃	乙二醇乙醚乙酸酯 ethylene glycol monoethyl ether acetate	156.6	0.48
25	6.290	C₆H₈O	3-甲基-2-环戊烯-1-酮 3-methyl-2-cyclopenten-1-one	157.5	0.94
26	5.221	C₆H₈O	甲基环戊烯酮 methylcyclopentenone	157.5	1.51
27	6.110	C₈H₁₈O	3-乙基-2-甲基-3-戊醇 3-ethyl-2-methylpentan-3-ol	159.8	0.57
28	7.978	C₄H₆O₂	2-甲基丙烯酸 methacrylic acid	161.0	2.06
29	3.686	C₅H₄O₂	糠醛 2-furancarboxaldehyde	161.7	0.45
30	6.900	C₇H₁₀O	4-环庚烯-1-酮 cyclohepT-4-enone	163.0	0.71
31	8.012	C₆H₁₀O₃	丙酸酐 propionic anhydride	167.0	4.93
32	5.725	C₆H₈O	2-环己烯-1-酮 cyclohexenone	171.0	0.81
33	7.171	C₈H₁₆O₃	2, 5-二乙氧基四氢呋喃 2, 5-diethoxytetrahydrofuran,	171.1	0.11
34	7.600	C₇H₁₀O	2, 3-二甲基-2-环戊烯酮 2-cyclopenten-1-one, 2, 3-dimethyl	172.3	0.57
35	4.521	C₅H₈O₃	2, 4-戊二酮过氧化物 2, 4-pentanedione peroxide solution	174.0	2.68
36	6.649	C₆H₆O	苯酚 phenol	181.8	5.28
37	8.478	C₆H₁₄O₃	1, 2, 3-己三醇 1, 2, 3-trihydroxyhexane	188.0	0.24
38	7.952	C₇H₈O	2-甲基苯酚 2-methylphenol	191.2	2.98
39	7.237	C₆H₈O₂	1, 2-环己二酮 1, 2-cyclohexanedione	195.0	0.41
40	8.100	C₇H₁₂O₄	丙二酸二乙酯 diethyl malonate	198.9	0.72
41	8.337	C₇H₈O	3-甲基苯酚 3-methylphenol	202.3	1.76
42	8.504	C₇H₈O₂	愈创木酚 guaiacol	205.1	3.54
43	9.566	C₈H₁₀O	2，4-二甲基苯酚 2, 4-dimethylphenol	210.9	1.32
44	5.221	C₆H₈O₂	甲基环戊烯醇酮 methylcyclopentenone;	212.2	0.68
45	9.892	C₈H₁₀O	4-乙基苯酚 4-ethyl-phenol	217.9	1.17
46	10.386	C₈H₁₀O₂	4-甲基愈创木酚 4-methylguaiacol	219.5	1.48
47	7.679	C₅H₆O₂	4-甲基-2(5H)-呋喃酮 4-methyl-2(5H)-furanone	222.4	0.63
48	6.461	C₅H₆O₂	3-甲基-2(5H)-呋喃酮 3-methyl-2(5H)-furanone	222.4	0.56
49	4.817	C₅H₄O₂	4-环戊烯-1, 3-二酮 4-cyclopentene-1, 3-dione	226.3	0.43
50	6.611	C₅H₆O₂	1, 2-环辛烷二酮 1, 2-cyclopentanedione	234.5	3.25
51	10.798	C₁₃H₂₈	正十三烷烃 tridecane	235.5	0.08
52	11.233	C₉H₁₀O	4-烯丙基苯酚 4-allyl phenol	235.6	0.76
53	11.869	C₇H₈O₂	3-甲基邻苯二酚 3-methyl-pyrocatecho	241.2	2.31
54	11.417	C₉H₈O	1-茚酮 1-indone	244.0	0.88
55	13.567	C₆H₈O₂	3-甲基环戊烷-1, 2-二酮 3-methylcyclopentane-1, 2-dione	245.2	3.41
56	14.170	C₁₀H₁₄O₂	2-甲氧基-4-丙基-苯酚 2-methoxy-4-propylphenol	268.2	0.42
57	13.890	C₃₆H₇₄	正三十六烷 hexatriacontane	278.0	0.05
58	13.135	C₈H₈O₃	3-羟基-4, 5-二甲氧基苯甲醛 3-hydroxy-4, 5-dimethoxy benzaldehyde	284.8	0.68
59	13.395	C₉H₁₀O₃	香草乙酮 acetovanillone	297.5	1.29
60	15.107	C₁₀H₁₂O₃	4-羟基-3-甲氧基苯丙酮 4-hydroxy-3-methoxyphenylacetone	305.6	0.46
61	15.678	C₉H₈O₄	5-甲基-1, 3-苯二甲酸 5-methyl-1, 3-benzenedicarboxylic acid	315.7	0.40
62	17.601	C₁₀H₁₂O₄	乙酰丁香酮 acetosyringone	334.7	0.76
63	17.783	C₃₀H₆₂	三十烷 triacontane	449.8	0.11
64	17.892	C₃₂H₆₆	三十二烷 dotriacontane	467.0	0.09

表2

表3

图3

表4

表5

表6

表7

参考文献 16

1	BRIDGWATER A V . Review of fast pyrolysis of biomass and product upgrading[J]. Biomass and Bioenergy, 2012, 38, 68- 94. doi: 10.1016/j.biombioe.2011.01.048
2	吕东灿, 刘运权, 王夺, 等. 生物油的分离及其产品应用[J]. 林产化学与工业, 2013, 33 (4): 137- 143. doi: 10.3969/j.issn.0253-2417.2013.04.026
	LÜ D C , LIU Y Q , WANG D , et al. Separation of chemicals from bio-oil and their application prospects[J]. Chemistry and Industry of Forest Products, 2013, 33 (4): 137- 143. doi: 10.3969/j.issn.0253-2417.2013.04.026
3	BULUSHEV D A , ROSS J R H . Catalysis for conversion of biomass to fuels via pyrolysis and gasification: A review[J]. Catalysis Today, 2011, 171 (1): 1- 13.
4	姚倩, 徐禄江, 张颖. 催化快速热解生物质制备高附加值化学品研究进展[J]. 林产化学与工业, 2015, 35 (4): 138- 144. doi: 10.3969/j.issn.0253-2417.2015.04.022
	YAO Q , XU L J , ZHANG Y . Production of high value-added chemicals by catalytic fast pyrolysis of biomass[J]. Chemistry and Industry of Forest Products, 2015, 35 (4): 138- 144. doi: 10.3969/j.issn.0253-2417.2015.04.022
5	GUO S J , LU J X , CHANG J . Catalytic upgrading bio-oil by mean of H₂O₂ oxidation and esterification to improve fuel characteristics[J]. Acta Energiae Solaris Sinica, 2017, 38 (7): 2020- 2026.
6	ZHANG X H , CHEN L G , KONG W , et al. Upgrading of bio-oil to boiler fuel by catalytic hydrotreatment and esterification in an efficient process[J]. Energy, 2015, 84, 83- 90. doi: 10.1016/j.energy.2015.02.035
7	许细薇, 李治宇, 庄文俞, 等. 超声波与添加醇和乳化剂乳化提质热解生物油研究[J]. 农业机械学报, 2017, 48 (5): 320- 326.
	XU X W , LI Z N , ZHUANG W Y , et al. Upgrading of bio-oil and its heavy composition by using emulsification[J]. Transactions of the Chinese Society for Agricultural Machinery, 2017, 48 (5): 320- 326.
8	邹勇, 尉芹, 郑冀鲁, 等. 生物油中酚类物质的富集工艺优化研究[J]. 西北林学院学报, 2016, 31 (1): 226- 230, 242. doi: 10.3969/j.issn.1001-7461.2016.01.39
	ZOU Y , WEI Q , ZHENG J L , et al. Optimization of the technology of enriching phenolic components from bio-oil[J]. Journal of Northwest Forestry University, 2016, 31 (1): 226- 230, 242. doi: 10.3969/j.issn.1001-7461.2016.01.39
9	WANG S R , WANG Y R , CAI Q J , et al. Multi-step separation of monophenols and pyrolytic lignins from the water-insoluble phase of bio-oil[J]. Separation & Purification Technology, 2014, 122 (3): 248- 255.
10	张洪勋,庄续亮,杨建州.自热解油中制备1, 6-脱水-β-D-吡喃葡萄糖的方法: CN1162440C[P]. 2004-08-18.
	ZHANG H X, ZHUANG X L, YANG J Z. Method for preparing 1, 6-anhydro-β-D-glucopyranose from pyrolysis oil: CN1162440C[P]. 2004-08-18.
11	何寿林, 杨昌炎, 关媛. 生物油分离制备化学品和燃油的研究进展[J]. 现代化工, 2008, 28 (s2): 79- 82, 84.
	HE S L , YANG C Y , GUAN Y . Advance in fractional separation of bio-oil for chemicals and fuel oil[J]. Modern Chemical Industry, 2008, 28 (s2): 79- 82, 84.
12	WANG Y R , WANG S R , LENG F R , et al. Separation and characterization of pyrolytic lignins from the heavy fraction of bio-oil by molecular distillation[J]. Separation & Purification Technology, 2015, 152, 123- 132.
13	蒋恩臣, 熊磊明, 王明峰, 等. 生物质热解挥发物两级冷凝器的设计[J]. 东北农业大学学报, 2014, 45 (5): 110- 115.
	JIANG E C , XIONG L M , WANG M F , et al. Development of biomass pyrolysis volatiles fractional condenser[J]. Journal of Northeast Agricultural University, 2014, 45 (5): 110- 115.
14	武立斌.林业生物质直接脱氧液化制取液体燃油和酚类化学品研究[D].北京:中国科学院研究生院(理化技术研究所), 2009.
	WU L B. Research on direct deoxy-liquefy biomass of forest to obtain fuel and phenolics compounds[D]. Beijin: Technical Institute of Physics and Chemistry, CAS, 2009.
15	姚燕.生物油的分馏及品位提升试验研究[D].杭州:浙江大学, 2008.
	YAO Y. Separation and upgrading of bio-oil[D]. Hangzhou: Zhejiang University, 2008.
16	周岭, 蒋恩臣, 张强, 等. 木醋液的精制方法及其在农林生产上的应用[J]. 可再生能源, 2007, 25 (4): 56- 60. doi: 10.3969/j.issn.1671-5292.2007.04.016
	ZHOU L , JIANG E C , ZHANG Q , et al. The wood vinegar refining methods and theirapplicationin agricultural and forestry production[J]. Renewable Energy Resources, 2007, 25 (4): 56- 60. doi: 10.3969/j.issn.1671-5292.2007.04.016

精馏塔 distillation tower	进料量/(kg·h^-1) feed amount	塔板数 number of plates	进料位置¹⁾ feeding position	回流比 reflux ratio	操作压力/kPa operating pressure	温度 temperature /℃
精馏塔 distillation tower	进料量/(kg·h^-1) feed amount	塔板数 number of plates	进料位置¹⁾ feeding position	回流比 reflux ratio	操作压力/kPa operating pressure	塔顶 tower top	塔底 tower bottom
T-1	1000.0	20	18	15	50	44	77
T-2	680.0	20	4	15	30	61	99
T-3	430.0	30	10	15	20	62	92

沸点分布/℃ boiling point distribution	GC含量 GC content /%
沸点分布/℃ boiling point distribution	酮类 ketones	酚类 phenols	醇类 alcohol	酯类 ester	酸类 acid	其他 other
0~180	11.81	0.00	5.65	8.70	2.55	12.41
180~280	10.25	21.02	0.24	0.72	0.40	0.13
＞280	2.51	0.00	0.00	0	0	0.72

精馏塔 distillation tower	进料量/(kg·h^-1) feed amount	塔板数 plates number	进料位置 feeding position	回流比 reflux ratio	操作压力/kPa operating pressure	温度temperature /℃
精馏塔 distillation tower	进料量/(kg·h^-1) feed amount	塔板数 plates number	进料位置 feeding position	回流比 reflux ratio	操作压力/kPa operating pressure	塔顶 tower top	塔底 tower bottom
T-1	1000.0	56	18	15	5	8	113
T-2	285.0	50	20	15	5	11	181
T-3	261.0	80	15	15	5	98	119
T-4	201.5	60	25	20	5	104	125
T-5	165.9	81	23	20	5	114	150

初步分离产物 preliminary separation product	酮类 ketones	酚类 phenols	醇类 alcohol	酯类 ester	酸类 acid	其他 other
燃油粗品 crude fuel	49.45	0.15	12.93	9.64	3.58	24.25
富酚油 phenol-rich oil	1.40	85.71	0	8.94	2.75	1.20
生物质沥青 biomass asphalt	7.70	0.06	0	22.42	0	69.82

产品 product	质量 quality/kg	单价 price/(元·kg^-1)	总价 total price/元
脱酸脱水热解液相产物 deacidification dehydration pyrolysis liquid product	1000.00	2.00	2000.00
燃油粗品 crude fuel	715.00	3.00	2145.00
生物质沥青 biomass asphalt	24.00	0.8	19.2
苯酚类 phenol	59.50	6.00	357.00
邻甲苯酚类 2-methylphenol	36.00	9.00	324.00
医药原料 pharmaceutical raw materials	61.00	15.00	915.00
香料 perfumery	50.00	18.00	900.00
染料 dye	54.00	13.00	702.0
冷凝水 condensate	40000.00	0.0015	60.00
蒸汽 steam	2716.07	0.15	407.41
循环水 recycled water	1000000	0.0003	30.00
产品毛利润 roduct gross profit/元	2864.79