CN103318984B - Method for treating polymer flooding oil extraction wastewater by using organic modified sepiolite - Google Patents
Method for treating polymer flooding oil extraction wastewater by using organic modified sepioliteDownload PDFInfo
- Publication number
- CN103318984B CN103318984BCN201310273191.4ACN201310273191ACN103318984BCN 103318984 BCN103318984 BCN 103318984BCN 201310273191 ACN201310273191 ACN 201310273191ACN 103318984 BCN103318984 BCN 103318984B
- Authority
- CN
- China
- Prior art keywords
- sepiolite
- organically
- polymer flooding
- sepiolite powder
- flooding oil
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及工业水处理领域，特别是涉及处理聚合物驱采油技术中的含聚废水，以此来有效吸附其中的部分水解聚丙烯酰胺（HPAM）。The invention relates to the field of industrial water treatment, in particular to the treatment of polymer-containing wastewater in polymer flooding and oil recovery technology, so as to effectively adsorb partially hydrolyzed polyacrylamide (HPAM) therein.
背景技术Background technique
由于我国油田开采已经步入中后期，为提高原油采收率，改善油水流速比，使采出物中原油含量提高，已经开始广泛采用聚合物驱采油技术，这种情况下相对廉价的部分水解聚丙烯酰胺(HPAM)在采油中被广泛使用。但是随之产生的含部分水解聚丙烯酰胺的采油废水由于处理难度增大，成为聚合物驱大面积推广应用的技术难题。因此，需要寻求一种能够有效处理污水中部分水解聚丙烯酰胺（HPAM）的方法。As my country's oilfield exploitation has entered the middle and late stage, in order to enhance the oil recovery rate, improve the oil-water flow rate ratio, and increase the crude oil content in the produced material, the polymer flooding recovery technology has been widely used. In this case, the relatively cheap partial hydrolysis Polyacrylamide (HPAM) is widely used in oil recovery. However, the resulting oil production wastewater containing partially hydrolyzed polyacrylamide has become a technical problem for the large-scale application of polymer flooding due to the increasing difficulty of treatment. Therefore, it is necessary to find a method that can effectively treat partially hydrolyzed polyacrylamide (HPAM) in sewage.
虽然部分水解聚丙烯酰胺没有毒性，然而其降解后的单体丙烯酰胺却是二类致癌物质，会对人和动物的周围神经系统造成伤害。同时，进入环境中的聚合物会成为微生物营养物质的来源，促进微生物的加速繁殖。Although partially hydrolyzed polyacrylamide is not toxic, its degraded monomer acrylamide is a second-class carcinogen, which can cause damage to the peripheral nervous system of humans and animals. At the same time, the polymers entering the environment will become a source of nutrients for microorganisms and promote the accelerated reproduction of microorganisms.
聚合物驱采油污水中含有大量的聚合物HPAM，增加了水相的粘度，使水相携油能力增强，极大地增加了含油污水的稳定性，增加了聚合物驱采油废水净化处理的难度，降低了处理效率。因而有必要将含聚废水中的部分水解聚丙烯酰胺从水中除去，提高废水的水质，降低水的粘度，以利于后续污染物的处理。Polymer flooding oil production wastewater contains a large amount of polymer HPAM, which increases the viscosity of the water phase, enhances the oil-carrying ability of the water phase, greatly increases the stability of oily sewage, and increases the difficulty of purification and treatment of polymer flooding oil production wastewater. Reduced processing efficiency. Therefore, it is necessary to remove the partially hydrolyzed polyacrylamide in the poly-containing wastewater from the water, improve the water quality of the wastewater, and reduce the viscosity of the water to facilitate the treatment of subsequent pollutants.
目前，对含HPAM采油污水的处理已成为影响油田生产的关键性难题。现有的聚合物驱采油污水处理技术主要有化学降解法、生物降解法、化学絮凝法以及吸附法。At present, the treatment of oil production wastewater containing HPAM has become a key problem affecting oilfield production. The existing polymer flooding wastewater treatment technologies mainly include chemical degradation, biodegradation, chemical flocculation and adsorption.
化学降解主要有氧化降解、光降解和光催化降解。其虽然可以将HPAM降解为丙烯酰胺单体，但是丙烯酰胺单体会对水资源造成二次污染，从而限制了化学降解法的应用范围。Chemical degradation mainly includes oxidative degradation, photodegradation and photocatalytic degradation. Although it can degrade HPAM into acrylamide monomer, acrylamide monomer will cause secondary pollution to water resources, thereby limiting the application range of the chemical degradation method.
生物方法处理含聚污水主要是利用微生物通过其特定酶的作用，以聚丙烯酰胺为营养源，在其生长和代谢过程中将聚丙烯酰胺转化为小分子有机物和无机物。但是由于生物降解要受到酸碱度、温度、盐分、氧、养料等因素的影响，因而其应用也受到了限制。Biological methods to treat poly-containing sewage mainly use microorganisms to convert polyacrylamide into small molecular organic and inorganic substances through the action of specific enzymes and polyacrylamide as a nutrient source during their growth and metabolism. However, because biodegradation is affected by factors such as pH, temperature, salinity, oxygen, and nutrients, its application is also limited.
化学絮凝，运用絮凝剂对胶体颗粒的电压缩、静电中和、吸附等作用，破坏胶体的结构，使得胶体颗粒在水中脱稳、沉淀，然后通过卷扫聚集作用去除聚合物，对聚合物的去除率较高。但是此方法的不足之处是药剂用量较大，一般加药量与待处理的聚合物浓度相同。Chemical flocculation, the use of flocculants on the colloidal particles for electric compression, electrostatic neutralization, adsorption, etc., destroys the structure of the colloid, makes the colloidal particles destabilized and precipitated in water, and then removes the polymer through volume sweeping aggregation, and the polymer’s The removal rate is high. However, the disadvantage of this method is that the dosage of the drug is relatively large, and generally the dosage is the same as the concentration of the polymer to be treated.
以上这些方法在实际应用中存在或多或少的不足，诸如受限制条件多、成本高、效果不好、设备维护困难等问题。The above methods have more or less deficiencies in practical application, such as many restrictive conditions, high cost, poor effect, and difficult equipment maintenance.
发明内容Contents of the invention
本发明的目的在于提供一种有机改性海泡石处理聚合物驱采油废水的方法，该方法吸附效果明显，吸附量高。The object of the present invention is to provide a method for organically modified sepiolite to treat polymer flooding oil production wastewater, which has obvious adsorption effect and high adsorption capacity.
为实现上述目的，本发明所采用的技术方案是，一种有机改性海泡石处理聚合物驱采油废水的方法，其特征在于它包括如下步骤：In order to achieve the above object, the technical solution adopted in the present invention is a method for organically modified sepiolite treatment of polymer flooding oil production wastewater, which is characterized in that it comprises the steps:
1）酸活化：将海泡石原料加入浓度为13wt%-15wt%的盐酸溶液，混合搅拌，抽滤、洗涤、烘干得到酸活化海泡石粉；1) Acid activation: add sepiolite raw materials into hydrochloric acid solution with a concentration of 13wt%-15wt%, mix and stir, suction filter, wash, and dry to obtain acid-activated sepiolite powder;
2）热活化：将酸活化海泡石粉焙烧去水，冷却、研磨得到热活化后的海泡石粉；2) Heat activation: roast the acid-activated sepiolite powder to remove water, cool and grind to obtain heat-activated sepiolite powder;
3）有机改性：将热活化后的海泡石粉加入十六烷基三甲基溴化铵的乙醇水溶液中，其中热活化后的海泡石粉与十六烷基三甲基溴化铵的质量比在10-50:1，混合搅拌，过滤、洗涤、烘干、研磨制得有机改性海泡石粉；3) Organic modification: add heat-activated sepiolite powder to ethanol aqueous solution of cetyltrimethylammonium bromide, wherein heat-activated sepiolite powder and cetyltrimethylammonium bromide The mass ratio is 10-50:1, mixed and stirred, filtered, washed, dried, and ground to obtain organically modified sepiolite powder;
4）吸附：用酸调节聚合物驱采油废水的pH值到5-6，加入水可溶性铝盐使Al3+浓度为10mg/l—25mg/l，再加入步骤3）中所得的有机改性海泡石粉进行吸附，吸附过程温度在30℃到50℃，搅拌或震荡，然后静置沉降。4) Adsorption: Use acid to adjust the pH value of polymer flooding wastewater to 5-6, add water-soluble aluminum salt to make the concentration of Al3+ 10mg/l-25mg/l, and then add the organic modification obtained in step 3) Sepiolite powder is used for adsorption. The temperature of the adsorption process is 30°C to 50°C, stirred or shaken, and then left to settle.
优化的实施方案中，过程控制如下：In an optimized implementation, the process control is as follows:
步骤1）中固液比（海泡石与盐酸溶液的配比）在1:8-1:25g/ml（即1g:8-25ml），搅拌时间在1h-3h。Step 1) The solid-to-liquid ratio (the ratio of sepiolite to hydrochloric acid solution) is 1:8-1:25g/ml (ie 1g:8-25ml), and the stirring time is 1h-3h.
步骤2）中焙烧温度为250℃-350℃，焙烧时间在2h-8h，研磨达400目-800目。In step 2), the calcination temperature is 250°C-350°C, the calcination time is 2h-8h, and the grinding is 400-800 mesh.
步骤3）中固液比（热活化后的海泡石粉与十六烷基三甲基溴化铵的乙醇水溶液的配比）在1:8-1:25g/ml（即1g:8-25ml），搅拌时间1h-3h，研磨达600目-1000目。Step 3) The solid-to-liquid ratio (the ratio of heat-activated sepiolite powder to ethanol water solution of cetyltrimethylammonium bromide) is 1:8-1:25g/ml (ie 1g:8-25ml ), the stirring time is 1h-3h, and the grinding reaches 600-1000 mesh.
步骤4）中水可溶性铝盐为硫酸铝和氯化铝中的任意一种或两种按任意配比的混合，固液比（有机改性海泡石粉与聚合物驱采油废水的配比）为1:300-1:600g/ml，搅拌或震荡时间为1.5-3h。Step 4) The water-soluble aluminum salt is any one or two of aluminum sulfate and aluminum chloride mixed in any proportion, solid-to-liquid ratio (the proportion of organically modified sepiolite powder and polymer flooding oil production wastewater) 1:300-1:600g/ml, stirring or shaking time is 1.5-3h.
更优化的实施方案中，过程控制如下：In a more optimized implementation, the process control is as follows:
步骤2）中焙烧温度为300℃，研磨达600目。The calcination temperature in step 2) is 300°C, and the grinding is 600 mesh.
步骤3）中室温下搅拌混合1.5h，烘干温度在40℃，研磨达800目。Step 3) Stir and mix at room temperature for 1.5 hours, dry at 40°C, and grind to 800 mesh.
步骤4）中选用冰醋酸调节pH值到5-6，水可溶性铝盐选择硫酸铝，吸附过程温度为40℃，震荡时间为1.5h。In step 4), glacial acetic acid is used to adjust the pH value to 5-6, aluminum sulfate is selected as the water-soluble aluminum salt, the temperature of the adsorption process is 40°C, and the shaking time is 1.5h.
海泡石(Mg8(H2O)4[Si6O15]2(OH)4·8H2O)是一种天然纤维状含水的镁质硅酸盐粘土矿物,晶体结构模型属于链状和层状过渡型结构,其特点是在两层硅氧四面体片中间夹一层镁氧八面体，硅氧四面体和镁氧八面体通过共同顶点相互连接成的三维立体骨架结构，有贯穿整个结构的沸石孔道和空隙，比表面积大，拥有900m2/g的理论表面积。并且含有大量朝向外部的Si-OH基团，对有机化合物具有较强的亲和力，能与气态或液态的有机反应剂直接作用，生成有机矿物衍生物。而且在现实市场中，海泡石价格廉价，本发明因此选择海泡石作为原料对其进行活化改性。Sepiolite (Mg8 (H2 O)4 [Si6 O15 ]2 (OH)4 8H2 O) is a natural fibrous hydrous magnesia silicate clay mineral, and its crystal structure model belongs to chain And layered transitional structure, which is characterized in that a layer of magnesium-oxygen octahedron is sandwiched between two layers of silicon-oxygen tetrahedral sheets, and the silicon-oxygen tetrahedron and magnesium-oxygen octahedron are connected to each other through a common vertex to form a three-dimensional skeleton structure. The zeolite pores and voids in the entire structure have a large specific surface area, with a theoretical surface area of 900m2 /g. And it contains a large number of Si-OH groups facing the outside, has a strong affinity for organic compounds, and can directly interact with gaseous or liquid organic reactants to generate organic mineral derivatives. Moreover, in the actual market, sepiolite is cheap, so the present invention selects sepiolite as a raw material to activate and modify it.
海泡石的酸活化，一方面可以除去分布于海泡石矿中的碳酸盐杂质将样品纯化，清除其孔道内杂质，增加其孔容积；另一方面，酸中的氢离子取代其层间钙、镁、钾和钠离子，使其具有活性氢原子，生成新的表面而改善其表面特性，修饰其孔径和结构，增大微孔隙率，提高其吸附、净化和脱色能力。如果酸的浓度过大会直接破坏海泡石的结构，最后形成硅酸盐。而浓度过低则会使得处理不彻底，达不到活化效果。因此本发明采用了13%-15%盐酸。The acid activation of sepiolite, on the one hand, can remove the carbonate impurities distributed in the sepiolite ore to purify the sample, remove the impurities in its pores, and increase its pore volume; on the other hand, the hydrogen ions in the acid replace the interlayer Calcium, magnesium, potassium and sodium ions make it have active hydrogen atoms, generate new surfaces to improve its surface properties, modify its pore size and structure, increase microporosity, and improve its adsorption, purification and decolorization capabilities. If the concentration of acid is too high, the structure of sepiolite will be destroyed directly, and silicate will be formed at last. If the concentration is too low, the treatment will not be complete and the activation effect will not be achieved. Therefore the present invention has adopted 13%-15% hydrochloric acid.
在海泡石的结构中存在有三种形式的水，即吸附水、结晶水和羟基水。海泡石晶体结构中的水在加热过程中可以逐步失去。通过高温焙烧，能够有效除去晶体结构中吸附水(包括纤维间吸附水和孔道内的吸附水),在黏土中形成新的活性面,使Si-OH基转变为Si-O四面体结构,从而扩大了晶体中的通道,且结构格架不变,比表面积增加,表面活性提高,吸附能力增强。如果处理温度过高，则不仅除去了结构中的吸附水，而且会除去结晶水和羟基水，从而破坏晶体结构，实验表明结晶水和羟基水的失去，会使海泡石的吸附性能下降。因此本发明选择了250℃-300℃的温度进行焙烧。There are three forms of water in the structure of sepiolite, namely, adsorbed water, crystallized water and hydroxyl water. The water in the sepiolite crystal structure can be gradually lost during heating. Through high-temperature calcination, the adsorbed water in the crystal structure can be effectively removed (including the adsorbed water between the fibers and the adsorbed water in the pores), and a new active surface can be formed in the clay, so that the Si-OH group can be transformed into a Si-O tetrahedral structure, thereby The channel in the crystal is expanded, and the structural lattice remains unchanged, the specific surface area increases, the surface activity increases, and the adsorption capacity increases. If the treatment temperature is too high, not only the adsorbed water in the structure will be removed, but also the crystallization water and hydroxyl water will be removed, thereby destroying the crystal structure. Experiments show that the loss of crystallization water and hydroxyl water will reduce the adsorption performance of sepiolite. Therefore, the present invention selects a temperature of 250°C-300°C for firing.
泡石为由于其独特的多孔道和微孔结构使其本身具备吸附性能，加之海泡石由硅氧骨架组成因而呈现负电性，这使其对阳离子的吸附能力尤为明显。带正电性的阳离子表面活性剂嫁接到海泡石上时，异性电荷相吸很容易实现，并使海泡石由原来的负电性转变为带正电性的有机化活化海泡石，从而对带负电性物质具有强大的吸附功能。并且由于表面引入不同的碳氢链，改善了表面的疏水亲油性，增加了对有机物的粘结性能。本发明根据理论，选择了阳离子表面活性剂十六烷基三甲基溴化铵（CTAB），作为对海泡石进行改性的有机改性剂。十六烷基三甲基溴化铵（CTAB）不仅能有效吸附于海泡石表面，而且其适中的碳氢链长度不会堵塞海泡石孔道，并能增加对高分子材料HPAM的粘结能力。Because of its unique porous channel and microporous structure, sepiolite has adsorption properties, and sepiolite is composed of silicon-oxygen skeleton, so it exhibits negative charge, which makes its adsorption capacity for cations particularly obvious. When a positively charged cationic surfactant is grafted onto the sepiolite, the attraction of opposite charges is easy to achieve, and the sepiolite is converted from the original negative charge to a positively charged organically activated sepiolite, thereby Negatively charged substances have a strong adsorption function. And because of the introduction of different hydrocarbon chains on the surface, the hydrophobicity and lipophilicity of the surface are improved, and the binding performance to organic matter is increased. According to the theory, the present invention selects the cationic surfactant cetyltrimethylammonium bromide (CTAB) as the organic modifier for modifying sepiolite. Cetyltrimethylammonium bromide (CTAB) can not only be effectively adsorbed on the surface of sepiolite, but also its moderate hydrocarbon chain length will not block the pores of sepiolite, and can increase the bonding ability to the polymer material HPAM .
温度的由低升高，使HPAM分子慢慢解离，长分子链便柔顺，粘度变小，使HPAM更容易吸附在吸附剂上，这时的吸附速率大于其脱附速率，使吸附剂吸附HPAM分子的量逐渐增加，直至达到动态平衡。当温度太高时，会使其脱附速率的增加量大于吸附速率的增加量，而使吸附剂吸附HPAM分子的量逐渐减少，直至新的动态平衡。经过实验，也在40℃左右时，吸附剂的吸附量出现极大值。这也正好与采油废水的温度一致，因此本发明处理采油废水，可以节约加热而消耗的能源。在吸附时间超过了1.5h后，吸附剂的吸附量基本保持不变。As the temperature rises from low to low, the HPAM molecules will slowly dissociate, the long molecular chains will be soft, and the viscosity will become smaller, making it easier for HPAM to adsorb on the adsorbent. At this time, the adsorption rate is greater than its desorption rate, making the adsorbent adsorb The amount of HPAM molecules increases gradually until a dynamic equilibrium is reached. When the temperature is too high, the desorption rate will increase more than the adsorption rate, and the amount of HPAM molecules adsorbed by the adsorbent will gradually decrease until a new dynamic equilibrium is reached. Through experiments, it is also found that the adsorption capacity of the adsorbent has a maximum value at around 40°C. This is also just consistent with the temperature of the oil production wastewater, so the present invention can save the energy consumed by heating when treating the oil production wastewater. After the adsorption time exceeds 1.5h, the adsorption capacity of the adsorbent remains basically unchanged.
由于铝离子（Al3+）对HPAM有絮凝作用，能够使得HPAM降粘、脱稳、聚集，使得大分子HPAM不会堵塞海泡石吸附孔道，甚至包裹吸附剂。降粘、脱稳、聚集后的HPAM，使得吸附剂对其的吸附效率成倍的增加。并且Al3+的加入使吸附剂分散的更加均匀，沉降速度更快。在此基础上采用800目的改性海泡石粉吸附剂，吸附完毕，静置30min后就有良好分离效果。Because aluminum ions (Al3+ ) have a flocculation effect on HPAM, it can reduce the viscosity, destabilize and aggregate HPAM, so that macromolecular HPAM will not block the adsorption pores of sepiolite, and even wrap the adsorbent. The reduced viscosity, destabilized, and aggregated HPAM doubles the adsorption efficiency of the adsorbent. And the addition of Al3+ made the adsorbent more evenly dispersed and settling faster. On this basis, the 800-mesh modified sepiolite powder adsorbent is used. After the adsorption is completed, a good separation effect can be obtained after standing for 30 minutes.
本发明的有益效果是：采用海泡石为原材料廉价易得，对其活化改性工艺简单，且无毒无害。另外，本方法用量少但是吸附效果明显且处理迅速，吸附量高。对于处于偏僻地区的采油基地，能够就地处理，就地排放，设备需求少，成本低，相当适合用于处理采油废水中的聚合物。The beneficial effect of the invention is that the raw material of the sepiolite is cheap and easy to obtain, the activation and modification process of the sepiolite is simple, and it is non-toxic and harmless. In addition, the method uses less amount but has obvious adsorption effect, rapid treatment and high adsorption capacity. For oil production bases in remote areas, it can be treated on-site, discharged on-site, requires less equipment, and has low cost. It is quite suitable for treating polymers in oil production wastewater.
具体实施方式Detailed ways
实施例1：Example 1:
改性海泡石粉制备：取6g湖南浏阳产精制海泡石粉，加入到100ml、浓度为15wt%的盐酸溶液，在25℃下混合搅拌1.5h。真空泵抽滤，洗涤，烘干得到酸活化海泡石粉；上一步得到的酸活化海泡石粉，置于马弗炉中，调节温度为300℃，焙烧4h后，取出冷却，研磨达600目得到热活化后的海泡石粉；取上一步得到的热活化后的海泡石粉5g，加入0.3g十六烷基三甲基溴化铵，一起置于100ml乙醇水（乙醇与水体积比1:1）溶液中，25℃下混合搅拌1.5h，真空泵抽滤，蒸馏水与乙醇交替洗涤多次，然后烘箱中40℃烘干，最后研磨达800目得到有机改性海泡石粉。Preparation of modified sepiolite powder: Take 6g of refined sepiolite powder produced in Liuyang, Hunan, add it to 100ml of hydrochloric acid solution with a concentration of 15wt%, and mix and stir at 25°C for 1.5h. Vacuum pump filtration, washing, and drying to obtain acid-activated sepiolite powder; the acid-activated sepiolite powder obtained in the previous step was placed in a muffle furnace, and the temperature was adjusted to 300 ° C. After 4 hours of roasting, it was taken out and cooled, and ground to 600 mesh to obtain The sepiolite powder after thermal activation; Get the sepiolite powder 5g after the thermal activation that last step obtains, add 0.3g cetyltrimethyl ammonium bromide, place 100ml ethanol water together (ethanol and water volume ratio 1: 1) In the solution, mix and stir at 25°C for 1.5h, filter with a vacuum pump, wash with distilled water and ethanol alternately for several times, then dry in an oven at 40°C, and finally grind to 800 mesh to obtain organically modified sepiolite powder.
聚合物驱采油废水的处理：取100ml HPAM浓度为100mg/l的聚合物驱采油废水，冰醋酸调节pH值为5，加入硫酸铝的水溶液调节Al3+浓度至25mg/l，加入0.0200g的有机改性海泡石粉，将溶液控温在40℃，振荡1.5h，，静置0.5h沉降。Treatment of polymer flooding oil production wastewater: Take 100ml of polymer flooding oil production wastewater with HPAM concentration of 100mg/l, adjust pH value to 5 with glacial acetic acid, add aluminum sulfate aqueous solution to adjust Al3+ concentration to 25mg/l, add 0.0200g of For organically modified sepiolite powder, the temperature of the solution was controlled at 40°C, shaken for 1.5h, and allowed to stand for 0.5h to settle.
吸附效果表征方法：取上清液，运用淀粉-碘化镉法，测量其吸光度，并根据该HPAM溶液的浓度与吸光度标准曲线得到上清液的浓度；然后根据
吸附性能：处理HPAM浓度为100mg/l的聚合物驱采油废水，测得其平均吸附量为477mg/g，处理HPAM浓度为200mg/l的聚合物驱采油废水，测得其平均吸附量为920.5mg/g，处理HPAM浓度为300mg/l的聚合物驱采油废水，测得其平均吸附量为1413.4mg/g。该方法吸附效果明显，吸附高。Adsorption performance: Treating polymer flooding oil production wastewater with HPAM concentration of 100mg/l, the measured average adsorption capacity is 477mg/g, and treating polymer flooding oil production wastewater with HPAM concentration of 200mg/l, the measured average adsorption capacity is 920.5 mg/g, to treat polymer flooding wastewater with HPAM concentration of 300mg/l, the average adsorption capacity was measured to be 1413.4mg/g. The method has obvious adsorption effect and high adsorption.
实施例2：Example 2:
一种改性海泡石吸附水解聚丙烯酰胺的方法，它包括如下步骤：A method for modifying sepiolite to adsorb hydrolyzed polyacrylamide, comprising the steps of:
1）酸活化：将海泡石原料加入浓度为13wt%的盐酸溶液，混合搅拌，抽滤、洗涤、烘干得到酸活化海泡石粉；固液比（海泡石与盐酸溶液的配比）在1:8g/ml，搅拌时间在1h。1) Acid activation: add sepiolite raw materials into hydrochloric acid solution with a concentration of 13wt%, mix and stir, filter, wash, and dry to obtain acid-activated sepiolite powder; solid-to-liquid ratio (ratio of sepiolite to hydrochloric acid solution) At 1:8g/ml, the stirring time is 1h.
2）热活化：将酸活化海泡石粉焙烧去水，冷却、研磨得到热活化后的海泡石粉；焙烧温度为250℃，焙烧时间在2h，研磨达400目；2) Thermal activation: roast the acid-activated sepiolite powder to remove water, cool and grind to obtain heat-activated sepiolite powder; the roasting temperature is 250°C, the roasting time is 2 hours, and the grinding reaches 400 mesh;
3）有机改性：将热活化后的海泡石粉加入十六烷基三甲基溴化铵的乙醇水溶液中（乙醇与水体积比1:1），其中热活化后的海泡石粉与十六烷基三甲基溴化铵的质量比在10:1，混合搅拌，过滤、洗涤、烘干、研磨制得有机改性海泡石粉；固液比（热活化后的海泡石粉与十六烷基三甲基溴化铵的乙醇水溶液的配比）在1:8g/ml，搅拌时间1h，研磨达600目；3) Organic modification: add heat-activated sepiolite powder into ethanol aqueous solution of cetyltrimethylammonium bromide (volume ratio of ethanol to water: 1:1), wherein the heat-activated sepiolite powder is mixed with ten The mass ratio of hexaalkyltrimethylammonium bromide is 10:1, mixed and stirred, filtered, washed, dried, and ground to obtain organically modified sepiolite powder; The proportion of hexaalkyltrimethylammonium bromide in ethanol water solution) is 1:8g/ml, the stirring time is 1h, and the grinding reaches 600 mesh;
4）吸附：用酸调节含水解聚丙烯酰胺聚合物驱采油废水的pH值到5，加入水可溶性铝盐使Al3+浓度为10mg/l，再加入步骤3）中所得的有机改性海泡石粉进行吸附，吸附过程温度在30℃，搅拌或震荡，然后静置沉降。4) Adsorption: Use acid to adjust the pH value of oil flooding wastewater containing hydrolyzed polyacrylamide polymer to 5, add water-soluble aluminum salt to make the concentration of Al3+ 10 mg/l, and then add the organically modified seawater obtained in step 3). The pumice powder is used for adsorption, and the temperature of the adsorption process is 30°C, stirred or shaken, and then left to settle.
所述水可溶性铝盐为硫酸铝，固液比（有机改性的海泡石粉与聚合物驱采油废水的配比）为1:300g/ml，吸附过程温度在30℃，搅拌或震荡时间为3h，静置沉降。The water-soluble aluminum salt is aluminum sulfate, the solid-to-liquid ratio (the ratio of organically modified sepiolite powder and polymer flooding oil production wastewater) is 1:300g/ml, the temperature of the adsorption process is 30°C, and the stirring or shaking time is 3h, let stand to settle.
吸附效果表征方法同实施例1。吸附性能：处理HPAM浓度为100mg/l的聚合物驱采油废水，测得其平均吸附量为483.6mg/g，处理HPAM浓度为200mg/l的聚合物驱采油废水，测得其平均吸附量为948.3mg/g，处理HPAM浓度为300mg/l的聚合物驱采油废水，测得其平均吸附量为1446.5mg/g。该方法吸附效果明显，吸附量高。The adsorption effect characterization method is the same as in Example 1. Adsorption performance: Treating polymer flooding oil production wastewater with HPAM concentration of 100mg/l, the measured average adsorption capacity is 483.6mg/g, and treating polymer flooding oil production wastewater with HPAM concentration of 200mg/l, the measured average adsorption capacity is 948.3mg/g, to treat polymer flooding wastewater with HPAM concentration of 300mg/l, the measured average adsorption capacity is 1446.5mg/g. The method has obvious adsorption effect and high adsorption capacity.
实施例3：Example 3:
一种改性海泡石吸附水解聚丙烯酰胺的方法，它包括如下步骤：A method for modifying sepiolite to adsorb hydrolyzed polyacrylamide, comprising the steps of:
1）酸活化：将海泡石原料加入浓度为15wt%的盐酸溶液，混合搅拌，抽滤、洗涤、烘干得到酸活化海泡石粉；固液比（海泡石与盐酸溶液的配比）在1:25g/ml，搅拌时间在3h。1) Acid activation: add sepiolite raw materials into hydrochloric acid solution with a concentration of 15wt%, mix and stir, filter, wash, and dry to obtain acid-activated sepiolite powder; solid-to-liquid ratio (ratio of sepiolite to hydrochloric acid solution) At 1:25g/ml, the stirring time is 3h.
2）热活化：将酸活化海泡石粉焙烧去水，冷却、研磨得到热活化后的海泡石粉；焙烧温度为350℃，焙烧时间在8h，研磨达800目；2) Heat activation: roast the acid-activated sepiolite powder to remove water, cool and grind to obtain heat-activated sepiolite powder; the roasting temperature is 350°C, the roasting time is 8 hours, and the grinding reaches 800 mesh;
3）有机改性：将热活化后的海泡石粉加入十六烷基三甲基溴化铵的乙醇水溶液中（乙醇与水体积比1:1），其中热活化后的海泡石粉与十六烷基三甲基溴化铵的质量比在50:1，混合搅拌，过滤、洗涤、烘干、研磨制得有机改性海泡石粉；3) Organic modification: add heat-activated sepiolite powder into ethanol aqueous solution of cetyltrimethylammonium bromide (volume ratio of ethanol to water: 1:1), wherein the heat-activated sepiolite powder is mixed with ten The mass ratio of hexaalkyltrimethylammonium bromide is 50:1, mixed and stirred, filtered, washed, dried and ground to obtain organically modified sepiolite powder;
固液比（热活化后的海泡石粉与十六烷基三甲基溴化铵的乙醇水溶液的配比）在1:25g/ml，搅拌时间3h，研磨达1000目；The solid-to-liquid ratio (the ratio of heat-activated sepiolite powder to ethanol aqueous solution of cetyltrimethylammonium bromide) is 1:25g/ml, stirring time is 3h, and the grinding reaches 1000 mesh;
4）吸附：用酸调节含水解聚丙烯酰胺聚合物驱采油废水的pH值到6，加入水可溶性铝盐使Al3+浓度为25mg/l，再加入步骤3）中所得的有机改性海泡石粉进行吸附，吸附过程温度在50℃，搅拌或震荡，然后静置沉降。4) Adsorption: Use acid to adjust the pH value of oil flooding wastewater containing hydrolyzed polyacrylamide polymer to 6, add water-soluble aluminum salt to make the concentration of Al3+ 25 mg/l, and then add the organically modified seawater obtained in step 3). The pumice powder is used for adsorption, and the temperature of the adsorption process is 50°C, stirred or shaken, and then left to settle.
所述水可溶性铝盐为硫酸铝和氯化铝的混合（硫酸铝和氯化铝的质量各占1/2），固液比（有机改性的海泡石粉与聚合物驱采油废水的配比）为1:600g/ml，吸附过程温度在50℃，搅拌或震荡时间为3h。The water-soluble aluminum salt is a mixture of aluminum sulfate and aluminum chloride (the mass of aluminum sulfate and aluminum chloride each accounts for 1/2), and the solid-to-liquid ratio (the mixture of organically modified sepiolite powder and polymer flooding oil production wastewater Ratio) is 1:600g/ml, the temperature of the adsorption process is 50°C, and the stirring or shaking time is 3h.
吸附效果表征方法同实施例1。吸附性能：处理HPAM浓度为100mg/l的聚合物驱采油废水，测得其平均吸附量为462.2mg/g，处理HPAM浓度为200mg/l的聚合物驱采油废水，测得其平均吸附量为853.3mg/g，处理HPAM浓度为300mg/l的聚合物驱采油废水，测得其平均吸附量为1286.3mg/g。该方法吸附效果明显，吸附量高。The adsorption effect characterization method is the same as in Example 1. Adsorption performance: Treating polymer flooding oil production wastewater with HPAM concentration of 100mg/l, the measured average adsorption capacity is 462.2mg/g, and treating polymer flooding oil production wastewater with HPAM concentration of 200mg/l, the measured average adsorption capacity is 853.3mg/g, to treat polymer flooding wastewater with HPAM concentration of 300mg/l, the measured average adsorption capacity is 1286.3mg/g. The method has obvious adsorption effect and high adsorption capacity.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310273191.4ACN103318984B (en) | 2013-07-01 | 2013-07-01 | Method for treating polymer flooding oil extraction wastewater by using organic modified sepiolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310273191.4ACN103318984B (en) | 2013-07-01 | 2013-07-01 | Method for treating polymer flooding oil extraction wastewater by using organic modified sepiolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103318984A CN103318984A (en) | 2013-09-25 |
| CN103318984Btrue CN103318984B (en) | 2014-06-11 |
Family
ID=49188085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310273191.4AExpired - Fee RelatedCN103318984B (en) | 2013-07-01 | 2013-07-01 | Method for treating polymer flooding oil extraction wastewater by using organic modified sepiolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103318984B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528743A (en)* | 2015-01-16 | 2015-04-22 | 中国地质大学（武汉） | A kind of preparation method of high specific surface area mesoporous one-dimensional silica nanofiber |
| CN104741078B (en)* | 2015-03-05 | 2017-03-22 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing biological carbon/sepiolite nano composite material by virtue of sepiolite and swill oil |
| CN105195086A (en)* | 2015-10-16 | 2015-12-30 | 中国环境科学研究院 | Adsorbent for treating oily waste water, as well as preparation method, regeneration method and application of adsorbent |
| CN105617981B (en)* | 2016-01-30 | 2016-11-30 | 湘潭大学 | The application in the treatment of waste water of the method for modifying of a kind of meerschaum and modified meerschaum |
| CN106362687B (en)* | 2016-10-20 | 2019-03-15 | 湘潭大学 | Sepiolite adsorbent and preparation method and regeneration method thereof |
| CN106734875B (en)* | 2016-12-26 | 2019-07-23 | 中国地质大学（武汉） | A kind of light-colored casting alcohol-based paint and preparation method thereof |
| CN106861641B (en)* | 2017-04-21 | 2019-12-24 | 中国地质大学（北京） | A preparation method of organically modified sepiolite and the application of the organically modified sepiolite |
| CN107262044A (en)* | 2017-07-01 | 2017-10-20 | 湘潭大学 | It is a kind of to Congo red magnetic coupling functional material with efficient clearance and preparation method thereof in water |
| CN107321316B (en)* | 2017-08-25 | 2019-11-29 | 山东大学 | A kind of method of oil emulsion in removal ternary compound oil drive water exit |
| CN107986417B (en)* | 2017-12-28 | 2021-05-14 | 芜湖市创源新材料有限公司 | Preparation method of sepiolite/starch grafted polyacrylamide composite flocculant for papermaking sewage treatment |
| CN108187649A (en)* | 2017-12-28 | 2018-06-22 | 合肥小小作为信息科技有限公司 | A kind of processing method of tail gas catalyzed agent carrier newly developed |
| CN109985600B (en)* | 2019-04-25 | 2021-12-24 | 湖南工程学院 | Modified sepiolite and application thereof in wastewater treatment |
| CN110078327A (en)* | 2019-05-06 | 2019-08-02 | 知合环境（北京）有限责任公司 | A kind of polymer-containing oil sludge cleaning agent and its preparation method and application |
| CN111977873B (en)* | 2020-08-31 | 2023-04-07 | 湖南工程学院 | Method for using photoactivated sepiolite Si-OH for adsorption and photodegradation of water-soluble organic pollutants |
| CN112299771B (en)* | 2020-11-05 | 2022-04-19 | 四川鼎德商品混凝土有限公司 | Super-dispersion-resistant and segregation-resistant concrete and preparation method and construction process thereof |
| CN113399117B (en)* | 2021-06-02 | 2023-12-19 | 杭州诗蓝过滤科技有限公司 | Progressive dust-holding electrostatic filter cotton with good adsorption performance |
| CN113683247B (en)* | 2021-08-31 | 2023-04-18 | 湖南工程学院 | Method for treating reverse osmosis concentrated water of grinding wastewater by activating sepiolite through cooperation of light and heat |
| CN115646428A (en)* | 2022-10-19 | 2023-01-31 | 陈星言 | Heavy metal contaminated soil remediation agent and preparation method thereof |
| CN115894121A (en)* | 2022-12-30 | 2023-04-04 | 黑龙江八一农垦大学 | Soil conditioner and preparation method thereof |
| CN118594507B (en)* | 2024-08-07 | 2024-10-25 | 湖南工程学院 | A modified sepiolite adsorbent and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007103391A1 (en)* | 2006-03-09 | 2007-09-13 | Amcol International Corporation | Concentrate method of ion-exchanging aluminosilicates and use in phosphate and oxyanion adsorption |
| CN101215031A (en)* | 2007-12-28 | 2008-07-09 | 江西理工大学 | A kind of preparation method of clay composite flocculant |
| CN101569851A (en)* | 2009-03-06 | 2009-11-04 | 西南科技大学 | Method for preparing magnetic meerschaum |
| CN102614827A (en)* | 2012-04-20 | 2012-08-01 | 哈尔滨工业大学 | Preparation method of modified sepiolite supported nano iron material |
- 2013
- 2013-07-01CNCN201310273191.4Apatent/CN103318984B/ennot_activeExpired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007103391A1 (en)* | 2006-03-09 | 2007-09-13 | Amcol International Corporation | Concentrate method of ion-exchanging aluminosilicates and use in phosphate and oxyanion adsorption |
| CN101215031A (en)* | 2007-12-28 | 2008-07-09 | 江西理工大学 | A kind of preparation method of clay composite flocculant |
| CN101569851A (en)* | 2009-03-06 | 2009-11-04 | 西南科技大学 | Method for preparing magnetic meerschaum |
| CN102614827A (en)* | 2012-04-20 | 2012-08-01 | 哈尔滨工业大学 | Preparation method of modified sepiolite supported nano iron material |
Non-Patent Citations (2)
| Title |
|---|
| 张江凤等.海泡石的性能及其应用.《中国非金属矿工业导刊》.2009,(第04期), |
| 海泡石的性能及其应用;张江凤等;《中国非金属矿工业导刊》;20090825(第04期);全文* |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103318984A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103318984B (en) | Method for treating polymer flooding oil extraction wastewater by using organic modified sepiolite | |
| CN104289185B (en) | A granular filter material for adsorbing and removing heavy metals in water and its preparation method | |
| CN103848469A (en) | Method for processing municipal wastewater | |
| CN103111256B (en) | Preparation method of efficient calcium-based sepiolite phosphorus adsorbent and application thereof | |
| CN102963953A (en) | Method for treating coal washing wastewater | |
| CN103755107B (en) | A method for advanced treatment of urban reclaimed water | |
| CN103933936B (en) | A kind of preparation method and application of antibiotic compound adsorbent | |
| CN104888717A (en) | Modified vermiculite mercury removal adsorbent, preparation method and application thereof | |
| CN102527328A (en) | A method for preparing an adsorption material for removing phosphate in sewage | |
| CN104001479B (en) | A kind of inorganic mineral water treatment agent and preparation method thereof | |
| CN102963951A (en) | Method for treating papermaking wastewater | |
| CN102963952A (en) | Method for treating oily wastewater | |
| CN103693758B (en) | Method for treating methylene blue dye wastewater | |
| CN103055828B (en) | Diatomite/cellulose inorganic-organic composite filter aid for directly filtering micro-polluted water source as well as preparation method and application of diatomite/cellulose inorganic-organic composite filter aid | |
| CN103055824B (en) | Calcium bentonite -AA- (AA-Na) composite cadmium ion adsorbent | |
| CN104478029A (en) | A water treating agent and a preparing method thereof | |
| CN102951697A (en) | Method for treating electroplating wastewater | |
| CN103030421A (en) | Preparation method of diatom mud wall material with hygroscopic property, respiratory property and antibacterial property | |
| CN101734678A (en) | Organic modified bentonite and preparation method thereof | |
| CN101215031A (en) | A kind of preparation method of clay composite flocculant | |
| CN118878149A (en) | A process for removing calcium and magnesium ions from wastewater and reusing it for water quality reuse | |
| CN109985600B (en) | Modified sepiolite and application thereof in wastewater treatment | |
| CN104773802B (en) | A kind of composite flocculation agent aeroge of high absorption property and preparation method thereof | |
| CN106396447A (en) | Method for preparing high-performance building sand by desalting sea sand | |
| CN102886251B (en) | Preparation method of filtering material with removal effect on heavy metals in water and soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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:20140611 Termination date:20170701 |