CN104662133B - 由污水污泥生产生物柴油的方法及设备 - Google Patents
由污水污泥生产生物柴油的方法及设备 Download PDFInfo
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 44
- 239000010801 sewage sludge Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000006184 cosolvent Substances 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 141
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 43
- 238000011084 recovery Methods 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229940072033 potash Drugs 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 26
- 238000009835 boiling Methods 0.000 abstract description 11
- 150000002148 esters Chemical group 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000000823 artificial membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009384 sea disposal Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
本发明涉及使用沸点比水的沸点高的二甲苯或甲苯作为助溶剂来由含水的污水污泥制备生物柴油的方法和设备。
Description
技术领域
本发明涉及一种由污水污泥生产生物柴油的方法和设备。更具体地,本发明涉及通过污水处理所产生的初级和次级污水污泥的油组分和脂肪酸的酯交换来生产生物柴油的方法和设备。
背景技术
在韩国,污水处理期间产生的污泥总计达约9000吨/天,并逐年增加。然而,当水含量为85%或更高时,已经禁止污水污泥的直接填埋,并且从2012年起也禁止海洋处置(主要的处理方法)。因此,迫切需要一种稳定地处理并处置污水污泥的技术方法。同时,随着能源安全和气候变化的国际意识增强,已经高度重视废物资源(诸如污水)的能源转化技术。
厌氧消化是当前使用的污水污泥的内陆处理技术,它引起了极大兴趣。然而,已知厌氧消化技术具有以下缺点:由于废物活化污泥(次级污泥)中的长链脂肪酸,消化速率很差;转化成燃料的污泥干燥中消耗的能量很高;并且产生难闻的气味。同时,特别是在美国,已经做出了积极尝试,将初级和次级污水污泥的油组分和活性污泥的(作为微生物的磷脂膜所使用的)脂肪酸转化成生物柴油。当产自诸如污水污泥的有机废物时,生物柴油相比于沼气在易于贮存和处理的方面上具有优点。进一步地,随着巨大的连锁反应的后续繁衍,由污水污泥生产生物柴油在可再生能源生产和资源回收的方面上非常有价值。生物柴油目前被视为传统石化柴油的重要替代。韩国贸易、工业和能源部制定了到2030年国内分配率达到7%的目标。然而,对于常规生物柴油的生产方法,在生产成本中在于非常高比例的材料成本。具体地讲,因为韩国的耕地资源有限,所以在韩国生产植物类原料是非常困难的。由于这些原因,韩国消耗的大多数生物柴油是进口的。于是,使用污水污泥作为新的生物柴油的原料在能源生产替代能源进口和难以处理的废物资源的回收管理的方面上是非常重要且有价值的。
对由污水污泥生产生物柴油的酯化技术的研究仍停留在起步阶段,并且大多数研究仅限于使用干燥的污水污泥作为材料。
发明内容
本发明旨在通过使用具有高沸点的疏水性助溶剂的酯交换来由污水污泥生产具有高含量的脂肪酸甲酯的生物柴油。
另外,本发明旨在通过适当的温度控制而从污泥的水中分离出油和脂肪酸并且通过使油和脂肪酸与甲醇反应来提高由污水污泥生产生物柴油的酯化反应的效率。
为了实现上述目的,本发明提供了一种生产生物柴油的方法,包括:
(a)在反应罐30中将含水的污水污泥、混合溶液以及作为助溶剂的二甲苯或甲苯加热以诱发酯交换反应,该混合溶液包括体积比为1:0.01至1:0.05的甲醇或乙醇和酸催化剂;
(b)使步骤(a)中产生的混合蒸汽冷却并冷凝以分离水性甲醇或乙醇溶液和助溶剂的各层,随后使助溶剂循环至反应罐;
(c)将甲醇或乙醇进一步添加至反应罐以执行酯交换反应至完成,伴随产生生物柴油;和
(d)从水性甲醇或乙醇溶液、助溶剂和残余固体中分离并回收生物柴油。
另外,本发明提供了一种生产生物柴油的设备,包括:
助溶剂容器10;
溶剂容器20;
反应罐30,在反应罐的上部位置设置有溶剂供给单元90和污泥供给单元80,溶剂供给单元用于分别从助溶剂容器和溶剂容器中引入助溶剂和溶剂,在下部位置设置有用于从反应罐排出残余污泥的污泥排出单元120,在中间位置设置有生物柴油排出单元110,并且在顶部位置设置有水蒸汽排出单元100;
冷凝器40,冷凝器连接至水蒸汽排出单元;
液相分离器50,液相分离器用于从冷凝器中放出的冷凝的水性甲醇或乙醇的溶液进行分离;
溶剂回收单元41,溶剂回收单元用于回收从冷凝器中排出的冷凝的溶剂;
溶剂回收罐60,溶剂回收罐用于贮存由溶剂回收单元41回收的溶剂;和
溶剂循环泵70。
有益效果
以使用高沸点的二甲苯或甲苯作为助溶剂为特征,由污水污泥生产生物柴油的方法使得酯交换在没有水抑制的情况下进行,从而带来以下优点:降低待使用的甲醇量,并且提高由脂质或脂肪酸转化脂肪酸甲酯的转化率,以高产率地生产具有高含量的脂肪酸甲酯的生物柴油。
附图说明
图1是根据本发明的示例性实施方式生产生物柴油的设备的示意图。
(10:助溶剂容器,20:溶剂容器,30:反应罐,40:冷凝器,41:溶剂回收单元,50:液相分离器,51:输送机,52:碳酸钾供给泵,53:甲醇或乙醇回收单元,54:水排出单元,60:溶剂回收罐,70:溶剂循环泵,80:污泥供给单元,90:溶剂供给单元,100:水蒸汽排出单元,110:生物柴油排出单元,120:污泥排出单元)。
图2是使助溶剂与甲醇或乙醇分离的冷凝器的示意图。
图3是使甲醇或乙醇与水分离的液相分离器的示意图。
图4是示出实施例1的脂肪酸甲酯的质谱。
图5是示出比较例1的脂肪酸甲酯的质谱。
具体实施方式
下面,将给出本发明的详细描述。
本发明提出了一种由污水污泥生产生物柴油的方法。该方法包括:
(a)在反应罐中将含水的污水污泥、混合溶液以及作为助溶剂的二甲苯或甲苯加热以诱发酯交换反应,该混合溶液包括体积比为1:0.01至1:0.05的甲醇或乙醇和酸催化剂;
(b)使步骤(a)中产生的混合蒸汽冷却并冷凝以分离水性甲醇或乙醇溶液和助溶剂的各层,随后使助溶剂循环至反应罐;
(c)将甲醇或乙醇进一步添加至反应罐以执行酯交换反应至完成,伴随产生生物柴油;和
(d)从水性甲醇或乙醇溶液、助溶剂和残余固体中分离并回收生物柴油。
污水污泥可以是初级或次级污水污泥,或可以是在干燥过程已经被执行之前的污水污泥。污水污泥的水含量可以优选为约0至85重量%,或者更优选为约80至85重量%。
甲醇或乙醇可被用作酯交换的溶剂。将酸催化剂添加至溶剂以提高初始反应速率。优选地,甲醇或乙醇与酸催化剂的体积比的范围为1:0.01至1:0.05。在该范围内,可以以高产率进行生产生物柴油。
此外,酸催化剂可以选自由以下物质组成的组,但不限于:硫酸、盐酸、磺酸以及它们的组合,且最优选硫酸。
二甲苯或甲苯可被用作助溶剂。因为这两种助溶剂的沸点分别为138.5℃和111℃,所以可以在酯交换反应中分离出水。也就是说,在加热时,污泥中的水在温度达到疏水性助溶剂的沸点之前被蒸发并排出。在此期间,疏水性油和脂肪酸迁移到并保留在疏水性助溶剂中,以提高生物柴油的产品产率和脂肪酸甲酯的含量,并降低甲醇的使用量。
甲醇或乙醇和酸催化剂的混合溶液可以与助溶剂优选以1:0.25至1:1的体积比,更优选以1:0.5至1:0.75的体积比进行混合。以甲醇和助溶剂的优选的体积比,通过酯交换提取的疏水性油和脂肪酸组分可以以最高的效率迁移到助溶剂中。
此外,酯交换反应可以优选在80℃至110℃更优选在90℃至105℃下进行4小时至8小时。在该温度范围内,相比于使用低沸点的助溶剂(诸如己烷),酯交换的时间可以减少4小时至8小时。
步骤(a)的酯交换期间所产生的混合气体包括水蒸汽、甲醇或乙醇气体和助溶剂气体,并在冷凝器40中冷却并冷凝。此时,层分离成水性甲醇或乙醇溶液层和助溶剂层。分离的助溶剂循环回到反应罐中。
随后,将甲醇或乙醇进一步添加至反应罐中以完成酯交换。将步骤(b)中分离出的甲醇或乙醇溶液引入液相分离器中,然后将盐添加至液相分离器以分离甲醇或乙醇与水。该甲醇或乙醇可被使用。也就是说,它可以再循环至酯交换反应完成的反应罐。该盐可以是碳酸钾或碳酸钠,但不限于此。
步骤(d)是在酯交换完成后通过重力沉降从甲醇或乙醇、助溶剂和残留物中分离并回收所产生的生物柴油。为了有效分离,可以进一步添加水。步骤(c)所产生的生物柴油中仍包含助溶剂。因此,额外需要分离助溶剂以提高生物柴油的纯度。通过进行步骤(a)至(d),可以以高产率生产具有高含量的脂肪酸甲酯的生物柴油。
另外,本发明提出了一种生产生物柴油的设备。该设备包括:助溶剂容器10;溶剂容器20;反应罐30,在其上部位置设置有溶剂供给单元90和污泥供给单元80,溶剂供给单元用于分别从助溶剂容器10和溶剂容器20中引入助溶剂和溶剂,在下部位置设置有用于从反应器罐中排出残余污泥的污泥排出单元120,在中间位置设置有生物柴油排出单元110,并且在顶部位置设置有水蒸汽排出单元100;冷凝器40,冷凝器40连接至水蒸汽排出单元;液相分离器50,液相分离器用于对从冷凝器中放出的冷凝的水性甲醇或乙醇溶液进行;溶剂回收单元41,溶剂回收单元用于回收从冷凝器中排出的冷凝的溶剂;溶剂回收罐60;和溶剂循环泵70。
在本发明的一个示例性实施方式中,通过输送机51将从冷凝器40中排出的水性甲醇或乙醇溶液传送至液相分离器50。通过碳酸钾供给泵52将碳酸钾引入至液相分离器中使得水性甲醇或乙醇溶液分离成水和甲醇或乙醇。使水排出至水排出单元54,同时通过甲醇或乙醇回收单元53使甲醇或乙醇朝着溶剂回收罐60流动。
通过用于说明而提出的而不被解释为限制本发明的下面的实施例可以更好地理解本发明。
实施例1:使用二甲苯由污水污泥生产生物柴油
将150g的水含量为85重量%的污水污泥引入至烧瓶。然后,将300mL的甲醇和15mL的硫酸的混合溶液连同300mL的二甲苯一起添加至该烧瓶。在次级污水污泥完全溶解在溶剂混合物中之后,在105℃下进行4小时的酯交换。使加热期间所产生的混合蒸汽在冷凝器中冷却以形成二甲苯和水性甲醇溶液的两个分离层。在分离后,使用碳酸钾使水性甲醇溶液进一步分离成水和甲醇。使由此分离的甲醇和二甲苯都循环至反应罐30。当酯交换完成时,将水添加至反应罐以通过重力沉降从水性甲醇溶液和残余固体中分离出生物柴油。
比较例1:使用己烷由污水污泥生产生物柴油
重复与实施例1相同的过程,不同的是使用己烷代替二甲苯,并且酯交换在55℃不是在105℃下进行4小时。
实验例1:由污水污泥生产生物柴油的产品产率
对实施例1和比较例1中的生物柴油的产品产率进行测量,其结果总结在表1中。
表1
溶剂 | 反应温度(℃) | 反应时间(小时) | 生物柴油产率(%) |
实施例1(二甲苯) | 105 | 4 | 15.9 |
比较例1(己烷) | 55 | 8 | 8.22 |
在采用沸点为69℃(比水的沸点低)的己烷用作溶剂的比较例1中,得到低产品产率的生物柴油。与此相对,使用沸点高于水的二甲苯的实施例1的生物柴油的产品产率高达15.9%。因为当溶剂的沸点比水低时难以从生物柴油中提取污水的水,反应不容易进行,因而由污水生产生物柴油是低效率的。
此外,使用二甲苯的实施例1比使用己烷的比较例1给予生物柴油更高含量的脂肪酸甲酯。结果示于图4和图5。
Claims (4)
1.一种由污水污泥生产生物柴油的方法,包括:
(a)在反应罐(30)中将含水的污水污泥、混合溶液以及作为助溶剂的二甲苯或甲苯加热以诱发酯交换反应,所述混合溶液包括体积比为1:0.01至1:0.05的甲醇或乙醇和酸催化剂;
(b)使步骤(a)中产生的混合蒸汽冷却并冷凝以分离水性甲醇或乙醇溶液和所述助溶剂的各层,随后使所述助溶剂循环至所述反应罐;
(c)将甲醇或乙醇进一步添加至所述反应罐以执行酯交换反应至完成,伴随产生生物柴油;和
(d)从水性甲醇或乙醇溶液、助溶剂和残余固体中分离并回收生物柴油,
其中,所述混合溶液与步骤(a)中的助溶剂以1:0.25至1:1的体积比混合,并且酯交换反应在80℃至110℃下进行4小时至8小时。
2.根据权利要求1所述的方法,进一步包括对步骤(b)中冷凝并分离的水性甲醇或乙醇溶液添加盐以将所述水性甲醇溶液分离成甲醇或乙醇和水,并使所述甲醇或乙醇循环至所述反应罐中。
3.一种生产生物柴油的设备,包括:
助溶剂容器(10);
溶剂容器(20);
反应罐(30),在所述反应罐的上部位置设置有用于分别从所述助溶剂容器和溶剂容器中引入助溶剂和溶剂的溶剂供给单元(90)和污泥供给单元(80),在下部位置设置有用于从所述反应罐排出残余污泥的污泥排出单元(120),在中间位置设置有生物柴油排出单元(110),并且在顶部位置设置有水蒸气排出单元(100);
冷凝器(40),所述冷凝器连接至所述水蒸气排出单元;
液相分离器(50),所述液相分离器用于分离出从所述冷凝器中释放出的冷凝的水性甲醇或乙醇的溶液;
溶剂回收单元(41),所述溶剂回收单元用于回收从所述冷凝器中排出的冷凝的溶剂;
溶剂回收罐(60),所述溶剂回收罐用于贮存由所述溶剂回收单元(41)回收的溶剂;和
溶剂循环泵(70)。
4.根据权利要求3所述的设备,进一步包括液相分离器(50),从所述冷凝器(40)中排出的水性甲醇或乙醇溶液通过输送机(51)传送至所述液相分离器,所述液相分离器(50)设置有碳酸钾供给泵(52),在上部位置设置有甲醇或乙醇回收单元(53)和水排出单元(54)。
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