4种破乳剂在石油树脂沉降水洗生产中的运用
卢建国，赵洪福
(新疆天利石化控股集团有限公司，新疆克拉玛依833699)
摘要针对石油树脂生产水洗沉降系统经常产生大量碱泥，各沉降水洗罐压差增大， 导致管线堵塞等的问题，考察了4种破乳剂的破乳效果及对废水的影响。结果表明，A
型和D型破乳效果相当，沉降水洗系统的油相中没有W/O乳状液，水相中没有0/W乳
状液。未加破乳剂前的废水，C0D>5g/L、油的质量浓度>40m g/L，碱泥产生量>2
t/d，加入A型或D型破乳剂（加入量0.15~0.550m g/L)后外排污水C O D<1.2g/L、油
的质量农度<30 m g/L，碱泥产生量<1.5 1/d，大大降低了后期的污水处理成本。该方
法指导工业装置生产。
关键词聚偏氟乙烯；悬浮聚合；分散剂；形貌；粒径：
中图分类号 TQ326.8+2 文献标识码 A D O I10.3969/j.issn. 1006-6829.2019.01.009
间戊二烯石油树脂在生产过程中，原料按照一 定的配比进人到聚合反应釜，聚合反应后，经过碱 洗和水洗系统脱出催化剂，然后在经过脱出溶剂和 低聚物即得到间戊二稀石油树脂。碱洗、水洗所用 的催化剂无水三氯化铝被裹在聚合液粗树脂中，这 部分无水三氯化铝无法与碱液中和，悬浮在沉降水 洗系统的中间层，形成大量碱泥，造成沉降水洗系 统内各个沉降水洗罐之间压差增大，常会导致管线 堵塞，沉降水洗系统无法运行，运行周期缩短，一般 3个月就得停工，进行沉降水洗系统管线的疏通。另外，沉降水洗系统水洗后的污水，都存在水包油 (0/W型乳化液），造成外排污水COD大于5 g/L，水 中油的质量浓度大于40 m g/L。基于这些生产问 题，探索通过加人不同的破乳剂来改善和解决碱泥 过多、污水各项指标超标等问题。
1实验部分
1.1破乳剂
破乳剂分为水溶性破乳剂和油溶性破乳剂2大 类[1]。破乳剂属表面活性剂类型，破乳剂分子由亲 油、亲水基团组成，亲油部分为碳氢基团，特别是长 链碳氢基团构成；而亲水部分则由离子或非离子型 的亲水基所构成。在石油树脂生产中，主要加入的 是非离子型水溶性破乳剂。
实验所用4种破乳剂，A型破乳剂主要成分是 乙氧基化丙氧基化聚合物，是亲水基破乳剂，其亲 水基是通过分子中的羟基（_ OH)、醚基（_ 0_ )与 7J C作用形成氢键而达到亲水的目的，进而达到油水 分离的目的[2];B型稠油破乳剂由多种非离子聚醚通 过改性交联复配制得;C型破乳剂主要成分为聚醚; D型破乳剂是一种高效表面活性剂，具有破乳、缓蚀 和阻垢等作用。
1.2实验方法
将不同类型的非离子水溶性破乳剂加人到水 洗沉降系统中。在第1次的碱洗、7jC洗过程中，通 过搅拌器对聚合液进行首次的物理机械破乳，再 通过化学方法，加人非离子型水溶性破乳剂进行二次破乳。
在石油树脂生产工艺参数不变的前提下，聚合 液中破乳剂按质量浓度0.1〜0.6 g/L加人，通过加人 不同种破乳剂和不同的数量，来考察对石油树脂污 水的影响，及评定破乳剂使用的效果。
2结果与讨论
2.1 A型破乳剂
石油树脂生产工艺操作参数不变，聚合液中破 乳剂A加入质量浓度p(A)为0.18、0.36 g/L，实验结果见表1。
收稿日期:2018-12-03；修回日期:2018-12-09
表1破乳剂A加入量对石油树脂水洗污水的影响Tab 1Effect of demulsifier A addition on
petroleum resin washing wastewater
P(破)/ (g'L1)
水性墨水COD/
(m g-L1)
藤蔓根茎
p(油)/
(m g-L1)
w(碱泥)/
(k g'd1)
0.1872923.3 2.7
0.1851517.6 2.5
0.1882021.8 3.2
0.3672623.1 1.5
0.3657020.3 2.0
0.3683420.9 2.5
由表1可知，加人A型破乳剂后石油树脂水洗 污水的COD、油含量大幅降低，与0.36 g/L的用量相 比,0.18 g/L的用量碱泥的变化不大。且2种加人量 对污水中的COD和油含量影响不大。
对沉降水洗系统内的油相和水相取样，进行静 置分层，观察油相中没有W/0乳状液，水相中没有 O/W乳状液，在表面活性剂破乳剂的作用下，油相 中W/O乳状液通过破乳剂在油水界面大量聚集，形 成中间乳化层。
经核算，树脂A型破乳剂单耗0.65 kg/t，成本 34 元/t〇
2.2B型破乳剂
石油树脂生产工艺操作参数不变，聚合液中B 型破乳剂加人质量浓度p(B)为0.18 g/L，实验结果见 表2〇
表2破乳剂B加入量对石油树脂水洗污水的影响
Tab 2 Effect of demulsifier B addition on
petroleum resin washing wastewater
COD/(mg-L')p(油M mg-L-1)w(碱泥y fe.c T1) 78918.31131
138424.2905
132520.51358
由表2可知，B型破乳剂加人后碱泥大量增加, 平均每天产生碱泥1.131 t,l个月产生碱泥33.93 t，操作人员的劳动强度加大，存在人身伤害隐患，后续处理压力大。且碱泥的增加，每月树脂产量减少 301。
对污水的COD和油含量影响不大。试用B型 6个月后停止使用。
对于沉降水洗系统操作，沉降水洗系统污水线 频繁堵塞，造成生产波动；其次，污水收集池，有大 量的油气自污水中溢出，挥发性有机物(VOCs)含 量严重超标。2.3C型破乳剂
石油树脂生产工艺操作参数不变，破乳剂加入 质量浓度P(A)为0.11、0.18 m g/L，实验结果见表3。
表3破乳剂C加入量对石油树脂水洗污水的影响
Tab 3 Effect of demulsifier C addition on
petroleum resin washing wastewater
p(破)/
(g'L1)
COD/
(m g.L1)
p(油)/
(m g-L1)
m(碱泥)/
金银花采摘机(k g'd1)
0.11120623.18
3d蓝光播放器
0.1857020312
0.3870230.123
由表3可知，在使用C型破乳剂后，碱泥数量开 始增加；提高加人量后，碱泥数量依然在增加，说明 C型破乳效果不好。对污水的COD和油含量影响 不大。
对沉降水洗系统内的油相和水相取样，进行静 置分层，观察油相中存在明显的W/0乳状液，水相 中存在明显的O/W乳状液。
馈线卡2.4D型破乳剂
石油树脂生产工艺操作参数不变，破乳剂加入 质量浓度/3(D)为0.540、0.405、0.180外，实验结果见
表4。
表4破乳剂D加入量对石油树脂水洗污水的影响
Tab 4 Effect of demulsifier D addition on
petroleum resin washing wastewater
p(破)/
(g'L')
COD/
(m g.L1)
p(油y
(mg-L-1)
w(碱泥)/
(k g-d.自动泄压阀
0.18040318.45
0.18049322.52
0.40573017.48
0.40548124.45
0.54056321.45
0.540102223.15
0.54033729.75
由表4可知，D型破乳剂加入量增大对石油树 脂污水的COD、油含量影响不大。
对沉降水洗系统内的油相和水相取样，进行静 置分层，观察油相中没有W/0乳状液，水相中没有 0/W乳状液，在表面活性剂破乳剂的作用下，油水 界面没有中间乳化层，说明D型破乳剂破乳速度快，很快能够将聚合液与水分层。
经核算，树脂D型礙關单耗1kg/t，鉢17元/t。
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水洗样品；在90 T：下在2 m o l/L的H2S04中熟化1h；水洗并干燥样品。
2)评估在70丈下在质量分数30%的H20+质量 分数2〇x1〇_6的Fe2+(FeS04)介质里30 h的抗氧化 性。如果失量不超过5%，则样品通过测试。试验结 束以后，冷却样品到室温，用蒸馏水洗涤，用滤纸干 燥，完全脱除水滴，在1min内称量，精确度达到0.2 m g〇实验结果见表1。
表1氟改性聚合物材料样品的氧化稳定性
Tab 1Oxidation stability of the samples
of polymer materials modified with fluorine
薄膜改性方法
nalg
氧化前
Am/
氧化后%
SM C〇F3(80 T)0.1770.1760.6 ST C〇F3(80 t)0.1450.1440.7 ST未处理0.0880.084 5.1 SM未处理0.0760.072 5.3表2为样品热处理l h的结果。
表2聚合物材料经处理的样品热稳定性
Tab 2 Thermal stability of the treated samples
of p olymer materials
薄膜改性方法
mlg
-表面外观起始H O T：120 T：
SM c〇f3(8〇r.)0.176 0.1760.176没有改变
ST C〇F3(80 ■〇0.147 0.1440.144在120 T；下熔化由表2可知，用高价过渡金属氟化物改性的薄 膜在氧化和高温下是稳定的。
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3结论
1)4种破乳剂对石油树脂污水的COD和水中油 影响不大，较不加人破乳剂污水中COD和水中油明 显降低。
2)B型和C型破乳剂破乳效果不好，沉降水洗 系统内的油相中存在明显W/0乳状液,7jC相中存在 明显0/W乳状液；污水收集池，有大量的油气自污 水中溢出；沉降水洗系统形成的碱泥多，污水管线 频繁堵塞，石油树脂转化率降低。
3) A型和D型破乳效果相当。沉降水洗系统的
油相中没有W/0乳状液，水相中没有O/W乳状液,
沉降水洗系统形成的碱泥少。
4) 单从破乳剂单耗上考虑,A型单耗低于D型; 从成本考虑,D型吨树脂成本是A型的一半。
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2019,25(1)Chemical Production and Technology ABSTRACTS
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washing times reduced to 6 times, the time reduced to 6 h per batch, the consumption of pure hot water reduced to 60 ton per ton product, the resin loss reduced to 6 kg per batch, and the labor required reduced to 1person per shift, it not only improved the appearance of t he product，but also caused the material consumption, the amount of l abor, and the intensity of l abor to drop significantly，and had achieved good results.
Keywords: polyvinylidene fluoride (PVDF); washing; extractionflltration; plate-frame pressure filtration
Study on Mass Transfer Process of Desulphurization by Ammonia in Packed Tower
L I Chenglong1, ZHONGXiaowef, LIANGXiaotong2, ZHANG Xubin2
(1. Hubei Shaxing Technology Co., Ltd, Taizhou, Zhejiang, 317021;
2. School o f C hemical Engineering and Technology, Tianjin University, Tianjin 300354)
Abstract: In order to meet the requirement of technological design of ammonia desulphurization, the gas phase volume mass transfer coefficient (Kgq) of ammonia desulphurization in 0-ring packed tower was measured and calculated. And the effect of gas flow rate，spray density of absorbing liqui
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Keywords: packed tower; ammonia method; desulfurization; volume mass transfer coefficient
Application of Four Demulsifiers in the Petroleum Resin Settlement Washing Production
L U J ianguo,ZHA O Hongfu
(Xinjiang Tianli Petrochemical Holding Group Co., Ltd. Karamay, Xinjiang 833699)
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Keywords: demulsifier; petroleum resin washing settlement sewage; COD; oil in water; alkali mud
Study on the Preparation Technology and Properties of Bio-Filtration Automotive Interior Materials
LIANG Jinking, FU H uakang, SHENG Jian
(Zhejiang Juhua New Material Research Institute Co., Ltd, Hangzhou 311600)
Abstract：Based on the polyurethane foam roof, activated carbon was introduced into the composite material structure by three processes, and the compound biological enzyme agent was sprayed on t
he surface of the composite plate by surface spraying method to develop the low odor and low volatile organic compound (VOC) bio-filtration automotive interior material. The effects o f material structure optimization on the odor, VOC, mechanical and acoustic properties of composite materials were studied, and the effects of preparation processeson the odor and VOC of automobile roof compositematerials. The results showed that theadsorption layer
