CN104437381B - The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave - Google Patents
The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave Download PDFInfo
- Publication number
- CN104437381B CN104437381B CN201410543704.3A CN201410543704A CN104437381B CN 104437381 B CN104437381 B CN 104437381B CN 201410543704 A CN201410543704 A CN 201410543704A CN 104437381 B CN104437381 B CN 104437381B
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- microwave
- polycyclic aromatic
- aromatic hydrocarbons
- oil extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 56
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 56
- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 title claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 7
- 239000002594 sorbent Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000031018 biological processes and functions Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extraction Or Liquid Replacement (AREA)
- Fats And Perfumes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
技术领域technical field
本发明涉及废物资源化利用和污染控制的技术领域，具体涉及一种微波-有机改性凹凸棒土的方法以及应用该凹凸棒土处理采油废水中多环芳烃的方法。The invention relates to the technical field of waste resource utilization and pollution control, in particular to a method for microwave-organic modification of attapulgite and a method for using the attapulgite to treat polycyclic aromatic hydrocarbons in oil extraction wastewater.
背景技术Background technique
近年来，我国的水环境正遭受着前所未有的严重污染。在所有废水中，含油废水己成为不可忽视的污染水体。油类通过不同途径进入水体环境形成含油废水，含油废水是一种量大、面广且危害严重的废水，其来源很多。工业含油废水量最大，成分也很复杂，除了含有可溶性盐类和重金属、悬浮的乳化油、固体颗粒、硫化氢等天然的杂质外，还含有疏水性有机物多环芳烃。国际癌症研究中心（IARC）（1976年）列出的94种对实验动物致癌的化合物，其中15种属于多环芳烃。常规的去除多环芳烃的物理方法有加热法、混凝沉淀法，化学方法有光氧化和化学药剂氧化两类，此外还有微生物处理法。但一般的物理和化学方法无法彻底降解多环芳烃；生化法处理时间太长，且去除率只有30~40%。In recent years, my country's water environment is suffering unprecedented serious pollution. Among all wastewaters, oily wastewater has become a non-negligible polluted water body. Oil enters the water body environment through different channels to form oily wastewater. Oily wastewater is a large-volume, wide-ranging and seriously harmful wastewater with many sources. Industrial oily wastewater has the largest amount and complex composition. In addition to natural impurities such as soluble salts and heavy metals, suspended emulsified oil, solid particles, hydrogen sulfide, etc., it also contains hydrophobic organic polycyclic aromatic hydrocarbons. Of the 94 compounds that are carcinogenic to experimental animals listed by the International Cancer Research Center (IARC) (1976), 15 of them belong to polycyclic aromatic hydrocarbons. Conventional physical methods for removing PAHs include heating method and coagulation precipitation method, chemical methods include photooxidation and chemical agent oxidation, and microbial treatment methods. However, general physical and chemical methods cannot completely degrade PAHs; the biochemical treatment takes too long, and the removal rate is only 30-40%.
另一方面，吸附/解吸对疏水性有机污染物在环境中的迁移、转化、生物有效性及最终的环境归属起到关键性的作用，作为重要的分配过程之一，对有机污染物的环境行为有着显著的影响。凹凸棒粘土是指以凹凸棒土为主要矿物成份的一种天然非金属粘土矿物，在矿物学上隶属于海泡石族。凹凸棒土是一种优良的吸附剂和助滤剂。其具有空隙率高、比表面大、比重小、吸附性强等优良特性，因此被广泛地应用于水处理行业中。On the other hand, adsorption/desorption plays a key role in the migration, transformation, bioavailability and final environmental attribution of hydrophobic organic pollutants in the environment. Behavior has a significant impact. Attapulgite clay refers to a natural non-metallic clay mineral with attapulgite as the main mineral component, which belongs to the sepiolite family in mineralogy. Attapulgite is an excellent adsorbent and filter aid. It has excellent characteristics such as high porosity, large specific surface, small specific gravity, and strong adsorption, so it is widely used in the water treatment industry.
然而，目前鲜有将凹凸棒土用于处理采油废水中多环芳烃的报道，本发明人针对此不足，深入探寻用凹凸棒土去除采油废水中的多环芳烃，本案由此而产生。However, currently there are few reports on using attapulgite to treat polycyclic aromatic hydrocarbons in oil production wastewater. In view of this shortcoming, the inventors deeply explored the use of attapulgite to remove polycyclic aromatic hydrocarbons in oil production wastewater, and this case arose from this.
发明内容Contents of the invention
本发明所要解决的技术问题在于提供一种微波-有机改性凹凸棒土的方法以及应用该凹凸棒土处理采油废水中多环芳烃的方法，旨在拓宽凹凸棒土的应用领域，将凹凸棒土进行微波及有机改性，使之用于处理采油废水，深入探寻用凹凸棒土去除采油废水中的多环芳烃的最佳实验条件，为相关研究提供数据支持。The technical problem to be solved by the present invention is to provide a method for microwave-organic modification of attapulgite and a method for using the attapulgite to treat polycyclic aromatic hydrocarbons in oil production wastewater, aiming to broaden the application field of attapulgite, and to use attapulgite Soil was modified by microwave and organic, so that it can be used to treat oil production wastewater, and the best experimental conditions for using attapulgite to remove polycyclic aromatic hydrocarbons in oil production wastewater were explored in depth to provide data support for related research.
为解决上述技术问题，本发明的技术解决方案是：For solving the problems of the technologies described above, the technical solution of the present invention is:
一种微波-有机改性凹凸棒土的方法，包括如下步骤：A method for microwave-organic modification of attapulgite, comprising the steps of:
（1）首先将凹凸棒土20~30g置于250ml的锥形瓶中，加入1~1.5g的阳离子双子表面活性剂12-2-12，20~30ml、1mol/L的盐酸，和80~100ml去离子水，封好瓶口，放入50~60℃的培养箱，设置转速200rpm，反应3~5小时；(1) First put 20~30g of attapulgite in a 250ml Erlenmeyer flask, add 1~1.5g of cationic gemini surfactant 12-2-12, 20~30ml of 1mol/L hydrochloric acid, and 80~ 100ml of deionized water, seal the bottle, put it into an incubator at 50~60℃, set the speed at 200rpm, and react for 3~5 hours;
（2）将步骤（1）的混合液从培养箱中取出，放入微波炉中进行微波改性，设置微波强度为300~500W，微波改性时间为3~5min；(2) Take the mixture in step (1) out of the incubator, put it into a microwave oven for microwave modification, set the microwave intensity to 300~500W, and microwave modification time to 3~5min;
（3）将步骤（2）的混合液通过布氏漏斗抽滤，并用去离子水反复冲洗，直到淋洗液中不含Br-为止；(3) Suction filter the mixture in step (2) through a Buchner funnel, and rinse repeatedly with deionized water until the eluent does not contain Br- ;
（4）将步骤（3）滤出的粘土颗粒置于70~80℃的烘箱中烘干；(4) Dry the clay particles filtered out in step (3) in an oven at 70-80°C;
（5）将步骤（4）烘干的固体在100℃下活化1~2小时；(5) Activate the dried solid in step (4) at 100°C for 1-2 hours;
（6）将步骤（5）得到的土样，经过研钵和过筛处理后，即得微波-有机改性好的凹凸棒土。(6) After the soil sample obtained in step (5) is processed in a mortar and sieved, a microwave-organically modified attapulgite is obtained.
一种应用所述经过改性的凹凸棒土处理采油废水中多环芳烃的方法，将改性后的凹凸棒土吸附剂直接投放到采油废水中进行吸附反应，投放比例是吸附剂质量与废水体积比为20~100mg：10~20ml，常温下振荡一段时间，静置分离，即可达到净化目的。A method for applying the modified attapulgite to treat polycyclic aromatic hydrocarbons in oil production wastewater. The modified attapulgite adsorbent is directly put into the oil production wastewater for adsorption reaction. The volume ratio is 20~100mg: 10~20ml, shake at room temperature for a period of time, and stand for separation to achieve the purpose of purification.
所述多环芳烃在凹凸棒土上的吸附反应时间为24~48小时。The adsorption reaction time of the polycyclic aromatic hydrocarbons on the attapulgite is 24 to 48 hours.
所述多环芳烃在凹凸棒土上的吸附反应最佳pH为保持废水pH值，而废水pH值为7~8。The optimal pH of the adsorption reaction of the polycyclic aromatic hydrocarbons on the attapulgite is to maintain the pH value of the wastewater, and the pH value of the wastewater is 7-8.
所述反应过程中加入NaN3溶液以抑制生物作用。 NaN solution was added during the reaction to inhibit biological effects.
采用上述方案后，本发明具有如下优点：After adopting the above scheme, the present invention has the following advantages:
1）实验表明，改性后的凹凸棒土，有机官能团结构发生了明显改变。在波数3500和1500cm-1处出现了新的官能团或者官能团位移，增强了其吸附性质。1) Experiments show that the modified attapulgite has a significant change in the structure of organic functional groups. New functional groups or functional group displacements appeared at the wavenumbers of 3500 and 1500cm -1 , which enhanced its adsorption properties.
2）表面活性剂的量，凹凸棒土的使用量，微波时间，溶液pH，反应温度均可以对处理效果产生影响。表面活性剂的量，凹凸棒土的用量和微波时间对处理效果的影响曲线都存在一个最优值（即拐点），过了这个拐点，吸附效率增加缓慢，甚至下降。酸性pH下吸附效果好，碱性条件下的吸附效果相对较差。低温有利于吸附，高温有利于脱附。2) The amount of surfactant, the amount of attapulgite used, microwave time, solution pH, and reaction temperature can all affect the treatment effect. The amount of surfactant, the amount of attapulgite and the effect curve of microwave time on the treatment effect all have an optimal value (that is, an inflection point). After this inflection point, the adsorption efficiency increases slowly or even decreases. The adsorption effect is good under acidic pH, and the adsorption effect is relatively poor under alkaline conditions. Low temperature is conducive to adsorption, and high temperature is conducive to desorption.
3）凹凸棒土在我国的储量十分丰富，由于传统的吸附剂活性炭成本高及再生困难等原因，凹凸棒土将逐渐取代活性炭成为一种环保、廉价的吸附剂。3) Attapulgite has abundant reserves in my country. Due to the high cost and difficult regeneration of traditional adsorbent activated carbon, attapulgite will gradually replace activated carbon as an environmentally friendly and cheap adsorbent.
4）使用阳离子双子表面活性剂12-2-12对凹凸棒土进行有机改性，可大幅度提高凹凸棒土的吸附性能。4) The organic modification of attapulgite with cationic gemini surfactant 12-2-12 can greatly improve the adsorption performance of attapulgite.
总之，本发明拓宽了凹凸棒土的应用领域，将凹凸棒土进行微波及有机改性，使之用于处理采油废水，深入探寻用凹凸棒土去除采油废水中的多环芳烃的最佳实验条件，为相关研究提供数据支持。In a word, the present invention broadens the application field of attapulgite, carries out microwave and organic modification on attapulgite, makes it used for treating oil production wastewater, and deeply explores the best experiment of using attapulgite to remove polycyclic aromatic hydrocarbons in oil production wastewater Conditions to provide data support for related research.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步详述。The present invention will be described in further detail below in conjunction with specific examples.
本发明所揭示的是一种微波-有机改性凹凸棒土的方法，其具体实施例如下：What the present invention discloses is a kind of method of microwave-organic modification of attapulgite, and its specific examples are as follows:
实施例1Example 1
1）首先将凹凸棒土20g置于250ml的锥形瓶中，加入1g的阳离子双子表面活性剂12-2-12，20ml、1mol/L的盐酸，和80ml去离子水，封好瓶口，放入60℃的培养箱，设置转速200rpm，反应3小时。1) First put 20g of attapulgite in a 250ml Erlenmeyer flask, add 1g of cationic gemini surfactant 12-2-12, 20ml of 1mol/L hydrochloric acid, and 80ml of deionized water, seal the bottle, Put it into an incubator at 60° C., set the rotation speed at 200 rpm, and react for 3 hours.
2）将步骤1）的混合液从培养箱中取出，放入微波炉中，设置微波强度为400W，时间为3min。2) Take the mixture in step 1) out of the incubator, put it into a microwave oven, and set the microwave intensity to 400W for 3 minutes.
3）将步骤2）的混合液通过布氏漏斗抽滤，并用去离子水反复冲洗，直到淋洗液中不含Br-为止，可用AgNO3溶液滴定检验。3) Filter the mixture in step 2) through a Buchner funnel, and rinse repeatedly with deionized water until the eluent does not contain Br - , which can be tested by titration with AgNO 3 solution.
4）将步骤3）滤出的固体置于80℃的烘箱中烘干。4) Dry the filtered solid in step 3) in an oven at 80°C.
5）将步骤4）烘干的固体在100℃下活化1小时。5) Activate the dried solid in step 4) at 100°C for 1 hour.
6）将步骤5）得到的土样，经过研钵和过筛处理后，即得微波-有机改性好的凹凸棒土。将改性土样进行FTIR，XRD，TGA等分析，表征改性后的性质。剩余放入干燥器中备用。6) After the soil sample obtained in step 5) is subjected to mortar and sieve treatment, a microwave-organically modified attapulgite is obtained. The modified soil samples were analyzed by FTIR, XRD, TGA, etc. to characterize the modified properties. Put the rest in a desiccator for later use.
实施例2Example 2
1）首先将凹凸棒土30g置于250ml的锥形瓶中，加入1.5g的阳离子双子表面活性剂12-2-12，30ml、1mol/L的盐酸，和100ml去离子水，封好瓶口，放入60℃的培养箱，设置转速200rpm，反应5小时。1) First, put 30g of attapulgite in a 250ml Erlenmeyer flask, add 1.5g of cationic gemini surfactant 12-2-12, 30ml of 1mol/L hydrochloric acid, and 100ml of deionized water, and seal the bottle , put into an incubator at 60°C, set the rotation speed at 200rpm, and react for 5 hours.
2）将步骤1）的混合液从培养箱中取出，放入微波炉中，设置微波强度为500W，时间为4min。2) Take the mixture in step 1) out of the incubator, put it into a microwave oven, and set the microwave intensity to 500W for 4 minutes.
3）将步骤2）的混合液通过布氏漏斗抽滤，并用去离子水反复冲洗，直到淋洗液中不含Br-为止，可用AgNO3溶液滴定检验。3) Filter the mixture in step 2) through a Buchner funnel, and rinse repeatedly with deionized water until the eluent does not contain Br - , which can be tested by titration with AgNO 3 solution.
4）将步骤3）滤出的固体置于75℃的烘箱中烘干。4) Dry the filtered solid in step 3) in an oven at 75°C.
5）将步骤4）烘干的固体在100℃下活化2小时。5) Activate the dried solid in step 4) at 100°C for 2 hours.
6）将步骤5）得到的土样，经过研钵和过筛处理后，即得微波-有机改性好的凹凸棒土。将改性土样进行FTIR，XRD，TGA等分析，表征改性后的性质。剩余放入干燥器中备用。6) After the soil sample obtained in step 5) is subjected to mortar and sieve treatment, a microwave-organically modified attapulgite is obtained. The modified soil samples were analyzed by FTIR, XRD, TGA, etc. to characterize the modified properties. Put the rest in a desiccator for later use.
实施例3Example 3
1）首先将凹凸棒土25g置于250ml的锥形瓶中，加入1.2g的阳离子双子表面活性剂12-2-12，25ml、1mol/L的盐酸，和90ml去离子水，封好瓶口，放入50℃的培养箱，设置转速200rpm，反应4小时。1) First put 25g of attapulgite in a 250ml Erlenmeyer flask, add 1.2g of cationic gemini surfactant 12-2-12, 25ml of 1mol/L hydrochloric acid, and 90ml of deionized water, and seal the bottle , put into an incubator at 50°C, set the rotation speed at 200rpm, and react for 4 hours.
2）将步骤1）的混合液从培养箱中取出，放入微波炉中，设置微波强度为300W，时间为5min。2) Take the mixture in step 1) out of the incubator, put it into a microwave oven, and set the microwave intensity to 300W for 5 minutes.
3）将步骤2）的混合液通过布氏漏斗抽滤，并用去离子水反复冲洗，直到淋洗液中不含Br-为止，可用AgNO3溶液滴定检验。3) Filter the mixture in step 2) through a Buchner funnel, and rinse repeatedly with deionized water until the eluent does not contain Br - , which can be tested by titration with AgNO 3 solution.
4）将步骤3）滤出的固体置于70℃的烘箱中烘干。4) Dry the filtered solid in step 3) in an oven at 70°C.
5）将步骤4）烘干的固体在100℃下活化1.5小时。5) Activate the dried solid in step 4) at 100°C for 1.5 hours.
6）将步骤5）得到的土样，经过研钵和过筛处理后，即得微波-有机改性好的凹凸棒土。将改性土样进行FTIR，XRD，TGA等分析，表征改性后的性质。剩余放入干燥器中备用。6) After the soil sample obtained in step 5) is subjected to mortar and sieve treatment, a microwave-organically modified attapulgite is obtained. The modified soil samples were analyzed by FTIR, XRD, TGA, etc. to characterize the modified properties. Put the rest in a desiccator for later use.
本发明还揭示了一种利用上述改性后的凹凸棒土处理采油废水中多环芳烃的方法，其具体实施例如下：The present invention also discloses a method for using the modified attapulgite to treat polycyclic aromatic hydrocarbons in oil production wastewater, the specific examples of which are as follows:
实施例1Example 1
将凹凸棒土经过上述步骤进行改性处理后，进行批量的吸附实验。采油废水取自河北省冀东油田，已经过初步的油水分离。测得废水原水中萘129.8mg/L，菲10.4mg/L，远远超出一多环芳烃的排放限值。取25ml的玻璃管，每管中放入0.02g的改性凹凸棒土，倒入10ml的采油废水，加入200mg/L的NaN3溶液以抑制生物作用。之后用橡胶塞密封。将玻璃管置于25℃的培养箱中，200rpm的转速反应24小时，之后静置分离。为了尽快测定，可先不经过静置，直接将玻璃管取出，在离心机中离心30min（5000rpm），取上清液，经过针头过滤器过滤后，用紫外分光光度计对滤液中的多环芳烃含量进行分析。结果表明，萘和菲的去除效率分别到达了93.5和91.7%。After the attapulgite was modified through the above steps, a batch adsorption experiment was carried out. Oil production wastewater is taken from Jidong Oilfield, Hebei Province, and has undergone preliminary oil-water separation. Naphthalene 129.8mg/L and phenanthrene 10.4mg/L were measured in the raw water of wastewater, far exceeding the discharge limit of polycyclic aromatic hydrocarbons. Take 25ml glass tubes, put 0.02g of modified attapulgite into each tube, pour 10ml of oil production wastewater, and add 200mg/L NaN 3 solution to inhibit biological action. It is then sealed with a rubber stopper. The glass tube was placed in an incubator at 25° C., reacted at 200 rpm for 24 hours, and then left to separate. In order to measure as soon as possible, the glass tube can be taken out directly without standing still first, and centrifuged in a centrifuge for 30min (5000rpm), take the supernatant, filter it through a needle filter, and use a UV spectrophotometer to detect polycyclic compounds in the filtrate. Aromatic content was analyzed. The results showed that the removal efficiencies of naphthalene and phenanthrene reached 93.5 and 91.7%, respectively.
实施例2Example 2
将凹凸棒土经过上述步骤进行改性处理后，进行批量的吸附实验。采油废水取自山东省胜利油田，已经过初步的油水分离。测得废水原水中菲7.4mg/L，远超出菲的排放限值。取25ml的玻璃管，每管中放入0.03g的改性凹凸棒土，倒入10ml的采油废水。加入200mg/L的NaN3溶液以抑制生物作用。之后用橡胶塞密封。将玻璃管置于25℃的培养箱中，200rpm的转速反应48小时。之后将玻璃管取出，在离心机中离心30min（5000rpm）。取上清液，经过针头过滤器过滤后，用紫外分光光度计对滤液中的菲含量进行分析。结果表明，菲的去除效率到达了95.1%。After the attapulgite was modified through the above steps, a batch adsorption experiment was carried out. Oil production wastewater is taken from Shengli Oilfield in Shandong Province, and has undergone preliminary oil-water separation. The measured phenanthrene in the raw wastewater was 7.4 mg/L, far exceeding the discharge limit of phenanthrene. Take 25ml glass tubes, put 0.03g of modified attapulgite into each tube, and pour 10ml of oil recovery wastewater into each tube. Add 200mg/L NaN 3 solution to inhibit biological effects. It is then sealed with a rubber stopper. The glass tube was placed in an incubator at 25° C. and reacted at 200 rpm for 48 hours. Then the glass tube was taken out and centrifuged in a centrifuge for 30min (5000rpm). The supernatant was taken, filtered through a needle filter, and the phenanthrene content in the filtrate was analyzed with an ultraviolet spectrophotometer. The results showed that the removal efficiency of phenanthrene reached 95.1%.
以上所述，仅是本发明的较佳实施例而已，并非对本发明的技术范围作任何限制，故但凡依本发明的权利要求和说明书所做的变化或修饰，皆应属于本发明专利涵盖的范围之内。The above is only a preferred embodiment of the present invention, and does not limit the technical scope of the present invention in any way, so any changes or modifications made according to the claims of the present invention and the description should all be covered by the patent of the present invention. within range.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410543704.3A CN104437381B (en) | 2014-10-15 | 2014-10-15 | The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410543704.3A CN104437381B (en) | 2014-10-15 | 2014-10-15 | The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437381A CN104437381A (en) | 2015-03-25 |
| CN104437381B true CN104437381B (en) | 2017-05-31 |
Family
ID=52884590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410543704.3A Expired - Fee Related CN104437381B (en) | 2014-10-15 | 2014-10-15 | The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437381B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174278B (en) * | 2015-08-17 | 2018-04-17 | 天津大学 | A kind of method that soil conditioner is prepared using modified attapulgite as primary raw material |
| CN105233570B (en) * | 2015-10-27 | 2017-12-26 | 广东工业大学 | A kind of composite modified quartz sand filter media of metal oxide iron copper and its preparation method and application |
| CN106118680A (en) * | 2016-06-28 | 2016-11-16 | 安徽金联地矿科技有限公司 | A kind of preparation method of contaminated soil remediation material based on attapulgite |
| CN106591279A (en) * | 2017-02-08 | 2017-04-26 | 光合强化（北京）生物科技有限公司 | Modified attapulgite used for immobilizing polycyclic aromatic hydrocarbon degrading bacteria, and preparation method thereof |
| CN109985443A (en) * | 2019-04-02 | 2019-07-09 | 周振坤 | A kind of air purifier |
| CN111732156B (en) * | 2020-07-29 | 2022-07-19 | 东北农业大学 | A method for inhibiting the release of polycyclic aromatic hydrocarbons in the sediment of rice-crab co-cultivation paddy field contaminated with moderate and mild polycyclic aromatic hydrocarbons |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247799B (en) * | 2011-07-12 | 2012-11-07 | 陕西科技大学 | Method for removing humic acid in water by utilizing surfactant modified attapulgite |
| CN103071451A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Modified attapulgite clay capable of purifying heavy metal ions in waste water and preparation method thereof |
| CN103752274B (en) * | 2013-12-12 | 2015-12-30 | 西北农林科技大学 | A kind of both sexes-Gemini type cation compound adsorbent and preparation method thereof |
| CN104069822A (en) * | 2014-07-28 | 2014-10-01 | 武汉科技大学 | Microwave organic modified particle bentonite/attapulgite adsorbent and preparation method thereof |
-
2014
- 2014-10-15 CN CN201410543704.3A patent/CN104437381B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437381A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437381B (en) | The method of polycyclic aromatic hydrocarbon in the method and application attapulgite treatment oil extraction waste water of the organically-modified attapulgite of microwave | |
| Rwiza et al. | Comparative sorption isotherms and removal studies for Pb (II) by physical and thermochemical modification of low-cost agro-wastes from Tanzania | |
| Kazemi et al. | Thiol-incorporated activated carbon derived from fir wood sawdust as an efficient adsorbent for the removal of mercury ion: Batch and fixed-bed column studies | |
| Tang et al. | One-step calcination of the spent bleaching earth for the efficient removal of heavy metal ions | |
| CN103432986B (en) | Magnetic diatomite-based adsorbent and preparation method and application thereof | |
| Zhao et al. | Biosorption of methylene blue from wastewater by an extraction residue of Salvia miltiorrhiza Bge | |
| CN110813244B (en) | A modified zirconium-based organometallic framework adsorbent for adsorbing lead ions and its preparation method and application | |
| CN104528863B (en) | Surfactant-modified attapulgite is removed the method for heavy metal in percolate | |
| CN103480330B (en) | Biomass-modified adsorbent for adsorbing coking wastewater, and preparation method and application thereof | |
| Jeon et al. | Removal of nickel ions from industrial wastewater using immobilized sericite beads | |
| CN104888717A (en) | Modified vermiculite mercury removal adsorbent, preparation method and application thereof | |
| Han et al. | Characterization of pruned tea branch biochar and the mechanisms underlying its adsorption for cadmium in aqueous solution | |
| CN105126749A (en) | Domestic sludge-based charcoal preparation method, and application of charcoal | |
| CN102963953A (en) | Method for treating coal washing wastewater | |
| CN112340830B (en) | Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in treating high-salt organic wastewater by activating persulfate | |
| CN106732379A (en) | A kind of sludge-based activated carbon with efficient absorption PFOS and PFOA efficiency and preparation method and application | |
| Jiang et al. | Adsorption of Hg (II) ions from aqueous solution by thiosemicarbazide-modified cellulose adsorbent | |
| CN102430399A (en) | Modified polyaniline-palygorskite composite adsorbent and application | |
| Okoronkwo et al. | Biosorption of nickel using unmodified and modified lignin extracted from agricultural waste | |
| CN103272566B (en) | Method for preparing ammonia nitrogen adsorbent by using banana peel and application of ammonia nitrogen adsorbent | |
| CN104014299A (en) | Particulate attapulgite adsorbent and preparation method thereof | |
| CN102963952A (en) | Method for treating oily wastewater | |
| Astuti et al. | Adsorption of methyl violet dye by thermally modified ceiba pentandra sawdust | |
| CN104874360B (en) | Multiple-contaminated adsorbent and preparation method thereof | |
| CN105061796B (en) | A kind of preparation method and application of modification of chitosan sponge structure material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170531 Termination date: 20191015 |