CN1359356A - 含醛的含水废物流的处理 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S210/902—Materials removed
- Y10S210/903—Nitrogenous
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及一种降低含水废物流中醛(类)和/或酮(类)浓度的方法,该方法包括用有效量的有机多胺碱处理含水废物流的步骤。此外,还涉及一种制备聚酯或多元醇的方法,该方法包括用有机多胺碱化合物处理醛(类)和/或酮(类),以除去含水废物流中至少50%的醛(类)和/或酮(类)。而且,还涉及一种制备聚(二羧酸1,3-丙二酯)的方法,包括使1,3-丙二醇同至少一种二羧酸或其低级二烷基酯反应,该方法包括用选自有机多胺和无机铵化合物的含氮碱处理含水废物流。
Description
发明领域
本发明涉及一种含醛(类)和/或酮(类)废水的处理方法,特别是含α,β-烯键式不饱和醛类,如丙烯醛。
发明技术背景
对废物生物处理系统而言,醛(类)和/或酮(类)、特别是α,β-烯键式不饱和醛(类)和/或酮(类)的毒性,即使是低浓度,也已被本领域的熟练技术人员所认识。V.T.Stack,Jr.在Industrialand Engineering Chemistry,49卷,第5期,913页(1975)中提出了关于该问题的评论文献。Stack报道了在这些化合物中,丙烯醛对生物学废物处理方法具有最大的毒性影响。含α,β-烯键式不饱和醛(类)和/或酮(类)的废水必须经过处理,以使这些物质的浓度降低到很低的量,才能用生物系统来进一步处理这些废水。不能充分地预处理该废水,将导致生物质有被灭或被抑制在活性水平很低的危险。
聚合物科学和技术百科全书(Encyclopedia of Polymer Scienceand Technology) (John Wliey & Sons,Inc.,1964),1卷,173页,报道了通过注入稀释的硫酸氢钠或氢氧化钠溶液来处理废丙烯醛。Kirk-Othmer化学技术百科全书(Encyclopedia of ChemicalTechnology)(第3版,John Wliey & Sons,Inc.,1978),1卷,290页,报道了加入亚硫酸氢钠或稀释的氢氧化钠水溶液赋予稀释的含水物流可生物降解性。
含α,β-烯键式不饱和醛(类)和/或酮(类)废物流的处理在本领域中是已知的。美国专利3923648公开了一种处理这种废水的方法,该方法包括使其同足够的碱接触,使废水的pH呈碱性,保持碱性废水在温度约25-100℃下至少约15分钟,然后使废水在含有活性生物质的生物系统中降解。优选的碱是碱金属氢氧化物。还公开了其它碱的使用,包括碱土金属氢氧化物、碱金属烷氧化物、季铵碱、氢氧化铵,可溶的有机胺类如甲胺、乙胺、二甲胺、三乙胺等,以及烷醇胺类包括单烷醇胺类、二烷醇胺类、三烷醇胺类、N-单烷基单烷醇胺类和N,N-二烷基烷醇胺类等。
美国专利5459229公开了一种1,3-丙二醇基聚酯的制备方法,其中用足够量的碱处理含丙烯醛的废物流,使pH值提高到7.5以上,其时间有效降低了丙烯醛的含量,接着,任选进行稀释和生物处理。使用的碱优选无机碱,最优选氢氧化钠。
本发明的一个目的是提供一种更加高效地降低废水中α,β-烯键式不饱和醛(类)和/或酮(类)含量的有效处理方法。
发明概述
根据本发明,降低含水废物流中醛(类)和/或酮(类)浓度的方法包括步骤(a)使含水废物流同有效量的有机多胺碱接触;以及(b)使接触过的废物流在基本上室温条件下保持足够长的时间,足以使所述的醛(类)和/或酮(类)的浓度降低至少50%。
本发明还涉及一种制备聚酯或多元醇的方法,包括(a)制备聚酯或多元醇,(b)形成含有醛(类)和/或酮(类)的含水废物流,以及(c)用有机多胺碱化合物处理醛(类)和/或酮(类),以除去含水废物流中至少50%的醛(类)和/或酮(类)。醛(类)和/或酮(类)优选自丙烯醛、异丁烯醛(甲基丙烯醛)、巴豆醛、2,4-己二烯醛、乙醛和甲基乙烯基酮。
本发明还涉及一种制备聚(二羧酸1,3-丙二酯)的方法,包括(a)1,3-丙二醇同至少一种选自对苯二甲酸、萘二甲酸和间苯二甲酸的二羧酸及其低级二烷基酯反应,获得聚(二羧酸1,3-丙二酯)和含有丙烯醛的废物流,以及(b)使用选自有机多胺和无机铵化合物的含氮碱处理含水废物流,最终从含水废物流中除去至少50%的丙烯醛。该聚(二羧酸1,3-丙二酯)优选聚(对苯二甲酸1,3-丙二酯),该二羧酸优选对苯二甲酸。含氮碱优选自有机多胺类。1,3-丙二醇同二羧酸的比率优选是50∶1-0.1∶1。
优选的有机多胺是有机二胺、有机三胺和有机四胺。优选的有机二胺包括六亚甲基二胺、2-甲基五亚甲基二胺、2-甲基六亚甲基二胺、3-甲基六亚甲基二胺、2,5-二甲基六亚甲基二胺、2,2-二甲基五亚甲基二胺、5-甲基壬烷二胺、十二亚甲基二胺、2,2,4-和2,4,4-三甲基六亚甲基二胺、2,2,7,7-四甲基1,8-亚辛基二胺、间二甲苯基亚基二胺、对二甲苯基亚基二胺、二氨基二环己基甲烷、任选被一个或多个烷基、N-烷基及其N’,N-二烷基衍生物取代的C2-C16脂肪族二胺。最优选的是六亚甲基二胺。
铵化合物中优选的是碳酸铵。
该方法还包括除去至少50%作为与碱的不溶产物的醛(类)和/或酮(类)(例如丙烯醛)。
待处理的废物流一般含有1-10000ppm(优选1-3000ppm)的醛(类)和/或酮(类)(例如丙烯醛)。优选处理进行足够长的时间以除去80-100%的醛(类)和/或酮(类)(例如丙烯醛)。优选的处理时间是1分钟至1小时。
处理过的废物流优选含有0-500ppm的醛(类)和/或酮(类)(例如丙烯醛)。
发明详述
本发明涉及一种含有对生物法废物处理系统有毒的醛(类)和/或酮(类),特别是α,β-烯键式不饱和醛类和/或酮(类)“废水”的处理方法,其使用选择的含氮的碱化合物来处理所述的废水。
优选含氮的碱化合物包括有机多胺,在此定义为含有二个或多个胺基的有机胺,优选二胺类如六亚甲基二胺、2-甲基五亚甲基二胺、2-甲基六亚甲基二胺、3-甲基六亚甲基二胺、2,5-二甲基六亚甲基二胺、2,2-二甲基五亚甲基二胺、5-甲基壬烷二胺、十二亚甲基二胺、2,2,4-和2,4,4-三甲基六亚甲基二胺、2,2,7,7-四甲基1,8-亚辛基二胺、间二甲苯基亚基二胺、对二甲苯基亚基二胺、二氨基二环己基甲烷、任选被一个或多个烷基、N-烷基及其N’,N-二烷基衍生物取代的C2-C16脂肪族二胺。最优选的二胺是六亚甲基二胺。其它含有多于2个胺基的含氮碱类在本发明中也是有用的。这些包括三胺类,例如双六亚甲基三胺、四胺类和其它的多胺类。
另外一类优选的含氮碱化合物是无机铵盐,优选碳酸铵。
对于本发明方法的应用,特别是当使用六亚甲基二胺来处理含丙烯醛的废物流时,一个特别的优点在于不溶性固体产物从反应系统中分离出来。这使得在将所述的废物流在向任选的后来所进行的生物法处理进料之前,大批量除去来自废物流的丙烯醛、反应产物和其所造成的碳负荷。该方法还消除了废物流中同丙烯醛反应产物相关的毒性。
所使用的处理温度并不是关键的。该方法对工业废物流的应用是在现有的废物流的温度下进行,约0-65℃,在此定义为“基本上室温条件”。通常进行足够时间的处理以除去至少50重量%的醛(类)和/或酮(类),优选约80-100%,更优选约99-100%。正常的处理时间达到1天,优选达到2小时,更优选约1分钟-约1小时,最优选约2-约30分钟。
可用本发明方法处理的α,β-烯键式不饱和醛(类)和/或酮(类)包括丙烯醛、异丁烯醛(甲基丙烯醛)、巴豆醛、2,4-己二烯醛、乙醛和甲基乙烯基酮。其它的醛类例如乙醛也用相似方法处理。
本发明处理方法对含有丙烯醛的含水废物流的处理特别有效,该丙烯醛来自1,3-丙二醇及其衍生的聚酯和多元醇的生产,例如聚(萘二甲酸1,3-丙二酯)。其中,优选应用于来自1,3-丙二醇基聚酯制备中的废物流,最特别是来自聚(对苯二甲酸1,3-丙二酯)(3GT)制备中的废物流。
1,3-丙二醇同二羧酸的重量比优选是50∶1-0.1∶1,优选约5∶1-1∶1。
3GT聚酯树脂的制备涉及在高温下,过量的1,3-丙二醇同对苯二甲酸或对苯二甲酸的低级二烷基酯反应。1,3-丙二醇同对苯二甲酸或对苯二甲酸的低级二烷基酯的重量比优选是约50∶1-0.1∶1,更优选约5∶1-1∶1,最优选约3∶1。温度达到约270℃,优选约180-270℃。该反应的主要毒副产物是丙烯醛和烯丙醇,含在蒸馏液中。来自3GT的废物流中,所形成的丙烯醛同1,3-丙二醇起始原料的比一般是约1-10000ppm,更优选约1-3000ppm。虽然这些副产品的量是很低的,但是仍希望进一步降低副产品在馏出物中的量,特别是对于由对苯二甲酸和过量的1,3-丙二醇制备3GT聚酯。
处理过的(也就是说在处理之后)含水废物流可以具有约0-500ppm,优选约0-50ppm,最优选约0-10ppm的醛(类)和/或酮(类)(例如丙烯醛)。
在下面的实施例中,举例说明了本发明,其中除非另有说明,所有的百分比按重量计算。
实施例
实施例1
用10%六亚甲基二胺(MHD)水溶液处理丙烯醛
向装有10%六亚甲基二胺水溶液(0.1g六亚甲基二胺和0.9g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶中抽样,用固相微提取法通过气相色谱分析。结果示于表1。
实施例2
用1%六亚甲基二胺水溶液处理丙烯醛
向装有1%六亚甲基二胺水溶液(0.01g六亚甲基二胺和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表1。
实施例3
用0.2%六亚甲基二胺水溶液处理丙烯醛
向装有0.2%六亚甲基二胺水溶液(0.002g六亚甲基二胺和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表1。
实施例4
用0.076%六亚甲基二胺水溶液处理丙烯醛
向装有0.076%六亚甲基二胺水溶液(0.76mg六亚甲基二胺和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表1。
如表1所示,本发明方法对于用六亚甲基二胺水溶液处理丙烯醛是有效的。当在室温下使用1%六亚甲基二胺水溶液时,丙烯醛的浓度在5分钟内从最初的2000ppm降低到7ppm,而且在15分钟内降到4ppm。甚至用更低浓度的HMD溶液(0.2%)仍然能观察到影响。
表1
室温下HMD溶液中丙烯醛浓度(ppm)随时间(min)的变化时间(min.) 10重量%HMD 1重量%HMD 0.2重量%HMD 0.076重量%HMD
0 2000 2000 2000 2000
5 7 7 30 226
15 5 4 6 149
25 3.7 4 111
35 3.7 90
实施例5
用10%碳酸铵((NH4)2CO3)水溶液处理丙烯醛
向装有10%碳酸铵水溶液(0.1g碳酸铵和0.9g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表II。
实施例6
用1%碳酸铵水溶液处理丙烯醛
向装有10%碳酸铵水溶液(0.01g碳酸铵和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表II。
实施例7
用0.2%碳酸铵水溶液处理丙烯醛
向装有0.2%碳酸铵水溶液(0.002g碳酸铵和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表II。
实施例8
用0.064%碳酸铵水溶液处理丙烯醛
向装有0.064%碳酸铵水溶液(0.64mg碳酸铵和1.0g水的混合物)的螺旋帽管形瓶中注入2mg丙烯醛,使掺入的丙烯醛浓度为2000ppm。将该管形瓶放置在室温下。定期从该管形瓶抽样,用固相微提取法通过气相色谱分析。结果示于表II。
如表II所示,通过碳酸铵水溶液也可以有效处理丙烯醛。用10%碳酸铵水溶液使丙烯醛的浓度在25分钟内从最初的2000ppm降低到3ppm。用更低浓度的碳酸铵溶液(1%)来处理,其效果仍然是很明显的。
表II
室温下碳酸铵溶液中的丙烯酸浓度(ppm)随时间(min)的变化
时间 10重量% 1重量% 0.2重量% 0.064重量%
(min.) (NH4)2CO3 (NH4)2CO3 (NH4)2CO3 (NH4)2CO3
0 2000 2000 2000 2000
5 115 513 1362 1857
15 50 359 1536
25 3 22 114 1077
35 2.7 12 47 855
45 9 26 680
55 4 16 538
125 180
Claims (12)
1.一种降低含水废物流中醛(类)和/或酮(类)浓度的方法,该方法包括步骤
(a)使含水废物流同有效量的有机多胺碱接触;
(b)使所述的接触过的废物流在基本上室温条件下保持足够长的时间,以使所述的醛(类)和/或酮(类)的浓度降低至少50%。
2.一种制备聚酯或多元醇的方法,包括(a)制备聚酯或多元醇,(b)形成含有醛(类)和/或酮(类)的含水废物流,和(c)用有机多胺碱化合物处理醛(类)和/或酮(类),以除去含水废物流中至少50%的醛(类)和/或酮(类)。
3.一种制备聚(二羧酸1,3-丙二酯)的方法,包括(a)1,3-丙二醇同至少一种选自对苯二甲酸、萘二甲酸和间苯二甲酸的二羧酸及其低级二烷基酯反应,获得聚(二羧酸1,3-丙二酯)和含有丙烯醛的废物流,和(b)使用选自有机多胺和无机铵化合物的含氮碱处理含水废物流,以便从含水废物流中除去至少50%的丙烯醛。
4.权利要求3的方法,其中聚(二羧酸1,3-丙二酯)是聚(对苯二甲酸1,3-丙二酯)和二羧酸是对苯二甲酸。
5.权利要求3-4的方法,其中含氮的碱选自有机多胺。
6.权利要求1-2任一项的方法,其中醛(类)和/或酮(类)选自丙烯醛、异丁烯醛(甲基丙烯醛)、巴豆醛、2,4-己二烯醛、乙醛和甲基乙烯基酮。
7.权利要求1-6任一项的方法,其中有机多胺选自有机二胺、有机三胺和有机四胺。
8.权利要求7的方法,其中含氮的碱是有机二胺,该有机二胺选自六亚甲基二胺、2-甲基五亚甲基二胺、2-甲基六亚甲基二胺、3-甲基六亚甲基二胺、2,5-二甲基六亚甲基二胺、2,2-二甲基五亚甲基二胺、5-甲基壬烷二胺、十二亚甲基二胺、2,2,4-和2,4,4-三甲基六亚甲基二胺、2,2,7,7-四甲基1,8-亚辛基二胺、间二甲苯基亚基二胺、对二甲苯基亚基二胺、二氨基二环己基甲烷、任选被一个或多个烷基、N-烷基及其N’,N-二烷基衍生物取代的C2-C16脂肪族二胺。
9.权利要求8的方法,其中含氮的碱是六亚甲基二胺。
10.权利要求3-4的方法,其中含氮的碱是铵化合物并且铵化合物是碳酸铵。
11.前述任一权利要求的方法,其中该方法还包括除去至少50%的醛(类)和/或酮(类),或者丙烯醛,其作为与碱不溶的产物。
12.前述任一权利要求的方法,其中待处理的废物流含有1-10000ppm的醛(类)和/或酮(类),或者丙烯醛;处理过的废物流含有1-500ppm的醛(类)和/或酮(类),或者丙烯醛;用足够的时间进行处理以除去80-100%的醛(类)和/或酮(类),或者丙烯醛;处理时间是1分钟-1小时,1,3-丙二醇同二羧酸的比是50∶1-0.1∶1。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102285697A (zh) * | 2011-06-08 | 2011-12-21 | 南京工业大学 | 一种不饱和聚酯树脂行业废水资源化工艺 |
CN102285697B (zh) * | 2011-06-08 | 2013-02-06 | 南京工业大学 | 一种不饱和聚酯树脂行业废水资源化工艺 |
CN109642048A (zh) * | 2016-08-30 | 2019-04-16 | 陶氏环球技术有限责任公司 | 减小丙烯醛浓度的方法 |
CN109996830A (zh) * | 2016-11-03 | 2019-07-09 | 可口可乐公司 | Ptf和其他1,3-丙二醇衍生的聚合物中的丙烯醛清除剂 |
CN109666136A (zh) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | 低乙醛含量的聚酯注塑件的制备方法 |
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JP2003503199A (ja) | 2003-01-28 |
AR024639A1 (es) | 2002-10-16 |
CA2375904C (en) | 2011-06-14 |
TR200103843T2 (tr) | 2002-04-22 |
JP4828750B2 (ja) | 2011-11-30 |
KR20020016878A (ko) | 2002-03-06 |
US6325945B2 (en) | 2001-12-04 |
KR100677784B1 (ko) | 2007-02-05 |
MXPA01013466A (es) | 2002-07-22 |
MY133359A (en) | 2007-11-30 |
EP1200358A1 (en) | 2002-05-02 |
WO2001002305A1 (en) | 2001-01-11 |
US20010011647A1 (en) | 2001-08-09 |
US6277289B1 (en) | 2001-08-21 |
CN100387566C (zh) | 2008-05-14 |
CA2375904A1 (en) | 2001-01-11 |
TW544440B (en) | 2003-08-01 |
BR0012191A (pt) | 2002-04-16 |
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