CN102167431A - Method for preparing cation type composite flocculant for treating waste drilling fluid - Google Patents
Method for preparing cation type composite flocculant for treating waste drilling fluid Download PDFInfo
- Publication number
- CN102167431A CN102167431A CN 201110060601 CN201110060601A CN102167431A CN 102167431 A CN102167431 A CN 102167431A CN 201110060601 CN201110060601 CN 201110060601 CN 201110060601 A CN201110060601 A CN 201110060601A CN 102167431 A CN102167431 A CN 102167431A
- Authority
- CN
- China
- Prior art keywords
- solution
- gelatin
- preparation
- waste
- waste drilling
- 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.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 238000005553 drilling Methods 0.000 title claims abstract description 34
- 239000012530 fluid Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 11
- 150000001768 cations Chemical class 0.000 title 1
- 108010010803 Gelatin Proteins 0.000 claims abstract description 52
- 229920000159 gelatin Polymers 0.000 claims abstract description 52
- 239000008273 gelatin Substances 0.000 claims abstract description 52
- 235000019322 gelatine Nutrition 0.000 claims abstract description 52
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 52
- 125000002091 cationic group Chemical group 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 102000008186 Collagen Human genes 0.000 claims abstract description 19
- 108010035532 Collagen Proteins 0.000 claims abstract description 19
- 229920001436 collagen Polymers 0.000 claims abstract description 19
- 238000005189 flocculation Methods 0.000 claims abstract description 14
- 230000016615 flocculation Effects 0.000 claims abstract description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims 5
- 239000000413 hydrolysate Substances 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 101000693530 Staphylococcus aureus Staphylokinase Proteins 0.000 claims 1
- 229940037003 alum Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008394 flocculating agent Substances 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 108090000145 Bacillolysin Proteins 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- 206010029350 Neurotoxicity Diseases 0.000 description 2
- 102000035092 Neutral proteases Human genes 0.000 description 2
- 108091005507 Neutral proteases Proteins 0.000 description 2
- 206010044221 Toxic encephalopathy Diseases 0.000 description 2
- 102000004142 Trypsin Human genes 0.000 description 2
- 108090000631 Trypsin Proteins 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007135 neurotoxicity Effects 0.000 description 2
- 231100000228 neurotoxicity Toxicity 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000012588 trypsin Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
本发明涉及一种用于处理石油钻井过程中产生的废弃钻井液的复合絮凝剂及其制备方法。首先通过碱法水解从废弃皮胶原中提取出相对分子质量较大的明胶，然后利用不同水解剂，将所提取的明胶进一步水解成相对分子质量适中的胶原蛋白，再利用制革化学中的鞣制机理，选取适当的金属离子负载在胶原蛋白上，即可得到一种阳离子型复合絮凝剂，并对呈阴离子性的废弃钻井液进行絮凝。本发明制备的复合絮凝剂具有成本低、易操作、絮凝效能高、对人体安全无毒等优点，是一种环境友好型产品。同时，将废弃皮胶原再利用，实现“以废治污”，避免对环境造成二次污染。The invention relates to a composite flocculant for treating waste drilling fluid produced in the oil drilling process and a preparation method thereof. Firstly, gelatin with a relatively large molecular weight is extracted from waste skin collagen by alkaline hydrolysis, and then the extracted gelatin is further hydrolyzed into collagen with a moderate molecular weight by using different hydrolyzing agents, and then tanned in tanning chemistry. Mechanism, choose appropriate metal ions to load on collagen, you can get a cationic composite flocculant, and flocculate the anionic waste drilling fluid. The composite flocculant prepared by the invention has the advantages of low cost, easy operation, high flocculation efficiency, safety and non-toxicity to human body, etc., and is an environment-friendly product. At the same time, the waste skin collagen is reused to realize "pollution control with waste" and avoid secondary pollution to the environment.
Description
技术领域technical field
本发明涉及废弃钻井液处理技术领域，具体涉及到一种以废弃皮胶原为基质，用于废弃钻井液处理的阳离子型复合絮凝剂的制备方法。The invention relates to the technical field of waste drilling fluid treatment, in particular to a preparation method of a cationic composite flocculant for waste drilling fluid treatment using waste skin collagen as a matrix.
背景技术Background technique
废弃钻井液与污油、污水一样，是油气田生产过程中的三大公害之一。它在自然状态下难以降解，堆积在作业区周围，占用大量耕地或草地，造成土壤板结、土地盐碱化，使被占有土地失去使用价值。同时，废弃钻井液长期累积渗透到地表下水层或随雨水外溢流入江河小溪，污染水源，危害人类身体健康。随着国家对环保要求的不断提高，对废弃钻井液的综合治理已经成为当前亟待解决的问题。Abandoned drilling fluid, like dirty oil and sewage, is one of the three major public hazards in the production process of oil and gas fields. It is difficult to degrade in the natural state, and it accumulates around the operation area, occupying a large amount of cultivated land or grassland, causing soil compaction, land salinization, and making the occupied land lose its use value. At the same time, the waste drilling fluid accumulates and infiltrates into the subsurface water layer for a long time or flows into rivers and creeks with rainwater overflow, polluting water sources and endangering human health. With the continuous improvement of the country's environmental protection requirements, the comprehensive treatment of waste drilling fluid has become an urgent problem to be solved.
废弃钻井液以粘土和水为基础，具有胶体和悬浮体的综合性质，是一种较稳定的分散体系。由于其中的悬浮微粒多带负电，在双电层的作用下，会使污水具有一定的稳定性，从而使得固化效果不理想，浸出液水质不达标。而在固化处理时适当添加絮凝剂，既可破除其中的乳化油，同时也能使胶体脱稳，显著提高浸出液的水质，避免污染环境。Waste drilling fluid is based on clay and water, has the comprehensive properties of colloid and suspension, and is a relatively stable dispersion system. Because the suspended particles in it are mostly negatively charged, under the action of the electric double layer, the sewage will have a certain stability, so that the curing effect is not ideal, and the water quality of the leachate is not up to standard. The appropriate addition of flocculants during curing treatment can not only break the emulsified oil, but also destabilize the colloid, significantly improve the water quality of the leachate, and avoid polluting the environment.
常见的絮凝剂主要分为无机高分子型和有机高分子型。其中以聚硅酸为代表的无机高分子絮凝剂稳定性差，制备时操作较为复杂，并未得到广泛的应用；而目前国内广泛使用的有机高分子絮凝剂——聚丙烯酰胺(PAM)，合成成本高，其聚合单体丙烯酰胺难于降解，具有强烈的神经毒性和致癌性，威胁人类健康，造成二次环境污染。Common flocculants are mainly divided into inorganic polymer type and organic polymer type. Among them, the inorganic polymer flocculant represented by polysilicic acid has poor stability, and the preparation operation is relatively complicated, so it has not been widely used; while the organic polymer flocculant widely used in China - polyacrylamide (PAM), synthesized The cost is high, and its polymerized monomer acrylamide is difficult to degrade, has strong neurotoxicity and carcinogenicity, threatens human health, and causes secondary environmental pollution.
发明内容： Invention content :
本发明的目的在于提供一种阳离子型复合絮凝剂的制备方法，以解决现有絮凝剂所存在的成本较高、合成或降解产物具有强烈的神经毒性和致癌性，会造成二次环境污染的问题。The purpose of the present invention is to provide a preparation method of a cationic composite flocculant to solve the problem of high cost existing in the existing flocculant, the synthesis or degradation product has strong neurotoxicity and carcinogenicity, and will cause secondary environmental pollution. question.
为了实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种用于废弃钻井液处理的阳离子型复合絮凝剂的制备方法，包括下述步骤：A preparation method for a cationic composite flocculant for waste drilling fluid treatment, comprising the steps of:
1）水解明胶的制备：以废弃皮胶原中提取出的明胶为原料，制备成质量分数8%~12%的明胶溶液，然后向其中加入不同类型的水解剂，水解温度为35~70℃，水解时间为2~6h，得到水解明胶溶液，备用；1) Preparation of hydrolyzed gelatin: use gelatin extracted from waste skin collagen as raw material to prepare a gelatin solution with a mass fraction of 8%~12%, and then add different types of hydrolyzing agents to it. The hydrolysis temperature is 35~70°C. The hydrolysis time is 2~6h, and the hydrolyzed gelatin solution is obtained, which is set aside;
2）阳离子型复合絮凝剂的制备：取1）中所得水解明胶溶液20mL，调节pH值至3，向其中加入质量分数5%的无机金属盐溶液35~140mL，常温下混合均匀后，在振荡的条件下，加碱将溶液的pH值调节至3.5~4.3，于30~55℃下反应10~16h，即得阳离子型复合絮凝剂。2) Preparation of cationic composite flocculant: take 20mL of the hydrolyzed gelatin solution obtained in 1), adjust the pH value to 3, add 35~140mL of inorganic metal salt solution with a mass fraction of 5% to it, mix well at room temperature, shake Under certain conditions, add alkali to adjust the pH value of the solution to 3.5~4.3, and react at 30~55°C for 10~16 hours to obtain a cationic composite flocculant.
上述水解剂是质量分数为10%的H2SO4溶液，明胶溶液与H2SO4溶液按体积比2.5:1混合。The above-mentioned hydrolyzing agent is a H 2 SO 4 solution with a mass fraction of 10%, and the gelatin solution and the H 2 SO 4 solution are mixed at a volume ratio of 2.5:1.
上述水解剂是质量分数为10%的柠檬酸溶液，明胶溶液与柠檬酸溶液按体积比4: 1混合。Above-mentioned hydrolyzing agent is the citric acid solution that mass fraction is 10%, and gelatin solution mixes with citric acid solution 4: 1 by volume.
上述水解剂是1398中性蛋白酶，其加入量是所用明胶质量的0.5~1.5%。The above-mentioned hydrolyzing agent is 1398 neutral protease, and its addition amount is 0.5-1.5% of the quality of gelatin used.
上述水解剂是胰蛋白酶，其加入量是所用明胶质量的1.5%。The above-mentioned hydrolyzing agent is trypsin, and its addition is 1.5% of the quality of gelatin used.
上述步骤2）中的无机金属盐溶液为硫酸铁溶液、氯化铁溶液和硫酸铝溶液中的一种。The inorganic metal salt solution in the above step 2) is one of ferric sulfate solution, ferric chloride solution and aluminum sulfate solution.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、原料来源广，成本低。我国是制革工业大国，但在制革过程中,仅有原料皮重约20%的物质转化为可售出的皮革,而在废弃皮胶原的成分中，约80%都是可利用的明胶，因而本发明中使用的原料来源广泛，且成本低廉，制备工艺条件温和，操作容易。1. Wide source of raw materials and low cost. my country is a big country in the tanning industry, but in the process of tanning, only about 20% of the skin weight of the raw material is converted into salable leather, and about 80% of the waste hide collagen is available gelatin , so the raw materials used in the present invention have a wide range of sources, low cost, mild preparation process conditions, and easy operation.
2、产品絮凝效能高。废弃钻井液因其有机质含量较高而呈现负价态，阳离子型絮凝剂可以与水中微粒起电中和及吸附架桥作用，从而使体系中的微粒脱稳、絮凝，有效地降低水中悬浮固体的质量分数，降低水质的COD含量。明胶水解后，胶原蛋白分子上含有大量羧基、羟基等活性基团，能够负载金属离子，且负载力强、负载量大、选择性高。同时，对于有机高分子絮凝剂，其分子上所带的-NH-、-COO-、-OH-等具有多种结构的亲水基团，有利于污染物进入絮凝体，脱色性好。2. The product has high flocculation efficiency. The waste drilling fluid presents a negative valence state due to its high content of organic matter. Cationic flocculants can act as charge neutralization and adsorption bridges with water particles, thereby destabilizing and flocculating the particles in the system and effectively reducing suspended solids in water. The mass fraction can reduce the COD content of water quality. After hydrolysis of gelatin, collagen molecules contain a large number of active groups such as carboxyl groups and hydroxyl groups, which can load metal ions with strong loading capacity, large loading capacity and high selectivity. At the same time, for organic polymer flocculants, the -NH-, -COO-, -OH- and other hydrophilic groups with various structures on the molecules are conducive to the entry of pollutants into the flocs and have good decolorization.
3、产物对环境友好，实现“以废治污”，最大限度的节约资源。本发明以废弃皮胶原中提取的明胶和无机金属盐为原料，制备阳离子型复合絮凝剂，用于油气田废弃钻井液的絮凝，原料和产物均无毒副作用。贯彻“以废治污”的理念，对制革过程产生的废弃皮胶原进行回收利用，节约资源的同时，防止对环境造成二次污染。3. The product is friendly to the environment, realizes "using waste to control pollution" and saves resources to the greatest extent. The invention uses gelatin and inorganic metal salts extracted from waste skin collagen as raw materials to prepare cationic composite flocculants for flocculation of waste drilling fluids in oil and gas fields, and the raw materials and products have no toxic and side effects. Carrying out the concept of "using waste to control pollution", recycling the waste skin collagen produced in the tanning process, saving resources and preventing secondary pollution to the environment.
具体实施方式：Detailed ways:
下面将结合实施例对本发明做详细地说明。The present invention will be described in detail below in conjunction with examples.
在废弃皮胶原的成分中，约有80%都是可利用的明胶。明胶是一种两性物质，经水解后会暴露出大量的羧基、羟基等活性基团，这类天然高分子材料具有许多合成高分子材料无法比拟的特殊化学结构和超分子结构。利用其可制备出适合于不同分离对象的新型絮凝材料，这类絮凝材料可望在废弃钻井液处理、化工、冶金、环保及食品加工等领域产生重要影响。Among the components of waste skin collagen, about 80% are available gelatin. Gelatin is an amphoteric substance, which will expose a large number of active groups such as carboxyl and hydroxyl groups after hydrolysis. This type of natural polymer material has a special chemical structure and supramolecular structure that many synthetic polymer materials cannot match. It can be used to prepare new flocculation materials suitable for different separation objects. This kind of flocculation materials is expected to have an important impact in the fields of waste drilling fluid treatment, chemical industry, metallurgy, environmental protection and food processing.
本发明以制革过程中的废弃革屑为原料提取明胶，在适当条件下水解后，胶原蛋白分子上暴露出大量的羧基、羟基等活性基团，利用制革化学中的鞣制机理，将适当的金属离子负载在明胶水解后所得的胶原蛋白分子上，制备阳离子型复合絮凝剂，并将其用于油气田废弃钻井液的絮凝。In the present invention, gelatin is extracted from discarded leather shavings in the tanning process. After hydrolysis under appropriate conditions, a large number of active groups such as carboxyl and hydroxyl groups are exposed on the collagen molecules. The metal ions loaded on the collagen molecules obtained after hydrolysis of gelatin were used to prepare a cationic composite flocculant, which was used for the flocculation of waste drilling fluid in oil and gas fields.
实施例1：Example 1:
一种用于油气田废弃钻井液处理的阳离子复合絮凝剂的制备方法，包括下述步骤：A preparation method for a cationic composite flocculant for oil and gas field waste drilling fluid treatment, comprising the steps of:
1）以碱法(MgO)水解从废弃皮胶原中提取出的相对分子质量较大的明胶为原料，将质量分数同为10%的明胶溶液和H2SO4溶液按体积比2.5:1混合，于60℃下水解4h，得到水解明胶溶液。1) Using the gelatin with relatively large molecular weight extracted from waste skin collagen by hydrolysis of alkali method (MgO) as raw material, mix gelatin solution with the same mass fraction of 10% and H 2 SO 4 solution at a volume ratio of 2.5:1 , Hydrolyzed at 60°C for 4h to obtain a hydrolyzed gelatin solution.
2）取1）中水解明胶溶液20mL，调节其pH为3，加入质量分数5%的硫酸铝溶液140mL，常温下充分混合均匀后，在振荡的条件下，加碱将溶液的pH值提至4.3，于40℃下反应16h，即得阳离子型复合絮凝剂。2) Take 20mL of the hydrolyzed gelatin solution in 1), adjust its pH to 3, add 140mL of aluminum sulfate solution with a mass fraction of 5%, and mix well at room temperature, then add alkali to raise the pH value of the solution to 4.3. React at 40°C for 16 hours to obtain a cationic composite flocculant.
用本实施例所制得的絮凝剂对油气田废弃钻井液进行絮凝，使用时絮凝剂与废弃钻井液投加量之比为1︰3.5，COD去除率达到80.8%，悬浮物去除率达到78.2%。Use the flocculant prepared in this example to flocculate the waste drilling fluid in oil and gas fields. When using it, the ratio of the dosage of the flocculant to the waste drilling fluid is 1:3.5, the removal rate of COD reaches 80.8%, and the removal rate of suspended matter reaches 78.2%. .
实施例2：Example 2:
一种用于油气田废弃钻井液处理的阳离子复合絮凝剂的制备方法，包括下述步骤：A preparation method for a cationic composite flocculant for oil and gas field waste drilling fluid treatment, comprising the steps of:
1）以碱法(MgO)水解从废弃皮胶原中提取出的相对分子质量较大的明胶为原料，配制质量分数为12%的明胶溶液，向其中加入1.5%的1398中性蛋白酶（按所用明胶的质量计），于45℃下水解3h，得到水解明胶溶液。1) Using the gelatin with relatively large molecular weight extracted from waste skin collagen by hydrolysis of alkaline method (MgO) as raw material, prepare a gelatin solution with a mass fraction of 12%, and add 1.5% of 1398 neutral protease (according to the used The mass of gelatin) was hydrolyzed at 45°C for 3 hours to obtain a hydrolyzed gelatin solution.
2）取1）中水解明胶溶液20mL，调节其pH=3，加入质量分数5%的硫酸铝溶液70mL，常温下充分混合均匀后，在振荡的条件下，加碱将溶液的pH值提至3.8，于30℃下反应12h，即得阳离子型复合絮凝剂。2) Take 20mL of the hydrolyzed gelatin solution in 1), adjust its pH=3, add 70mL of aluminum sulfate solution with a mass fraction of 5%, and mix well at room temperature, then add alkali to raise the pH value of the solution to 3.8, react at 30°C for 12 hours to obtain a cationic composite flocculant.
用本实施例所制得的絮凝剂对油气田废弃钻井液进行絮凝，使用时絮凝剂与废弃钻井液投加量之比为1︰3.5，COD去除率达到83.9%，悬浮物去除率达到86.6%。Use the flocculant prepared in this example to flocculate the waste drilling fluid in oil and gas fields. When using it, the ratio of the dosage of the flocculant to the waste drilling fluid is 1:3.5, the removal rate of COD reaches 83.9%, and the removal rate of suspended matter reaches 86.6%. .
实施例3：Example 3:
一种用于油气田废弃钻井液处理的阳离子复合絮凝剂的制备方法，包括下述步骤：A preparation method for a cationic composite flocculant for oil and gas field waste drilling fluid treatment, comprising the steps of:
1）以碱法(MgO)水解从废弃皮胶原中提取出的相对分子质量较大的明胶为原料，配制质量分数为10%的明胶溶液，向其中加入1.5%的胰蛋白酶（按所用明胶的质量计），于35℃下水解3h，得到水解明胶溶液。1) Using the gelatin with relatively large molecular weight extracted from waste skin collagen by hydrolysis of alkaline method (MgO) as raw material, prepare a gelatin solution with a mass fraction of 10%, and add 1.5% trypsin to it (according to the amount of gelatin used). mass), and hydrolyzed at 35°C for 3 hours to obtain a hydrolyzed gelatin solution.
2）取1）中水解明胶溶液20mL，调节其pH为3，加入质量分数5%的硫酸铝溶液100mL，常温下充分混合均匀后，在振荡的条件下，加碱将溶液的pH值提至4.0，于50℃下反应10h，即得阳离子型复合絮凝剂。2) Take 20mL of the hydrolyzed gelatin solution in 1), adjust its pH to 3, add 100mL of aluminum sulfate solution with a mass fraction of 5%, and mix well at room temperature, then add alkali to raise the pH value of the solution to 4.0, react at 50°C for 10 hours to obtain a cationic composite flocculant.
用本实施例所制得的絮凝剂对油气田废弃钻井液进行絮凝，使用时絮凝剂与废弃钻井液投加量之比为1︰3.5，COD去除率达到91.1%，悬浮物去除率达到88.2%。Use the flocculant prepared in this example to flocculate the waste drilling fluid in oil and gas fields. When using it, the ratio of the dosage of the flocculant to the waste drilling fluid is 1:3.5, the removal rate of COD reaches 91.1%, and the removal rate of suspended matter reaches 88.2%. .
实施例4：Example 4:
一种阳离子型复合絮凝剂的制备方法，包括下述步骤：A preparation method of cationic composite flocculant, comprising the steps of:
1）水解明胶的制备：以碱法(MgO)水解从废弃皮胶原中提取出的相对分子质量较大的明胶为原料，将质量分数12%的明胶溶液和质量分数10%的柠檬酸溶液按体积比4:1混合，于70℃下水解6h，得到水解明胶溶液。1) Preparation of hydrolyzed gelatin: using gelatin with relatively large molecular weight extracted from waste skin collagen by hydrolysis with alkali method (MgO) as raw material, gelatin solution with a mass fraction of 12% and citric acid solution with a mass fraction of 10% were pressed Mix at a volume ratio of 4:1 and hydrolyze at 70°C for 6 hours to obtain a hydrolyzed gelatin solution.
2）阳离子型复合絮凝剂的制备：取1）中水解明胶溶液20mL，调节其pH为3，加入质量分数5%的硫酸铁溶液45mL，常温下充分混合均匀后，在振荡的条件下，加碱将溶液的pH值提至3.5，于55℃下反应14h，即得阳离子型复合絮凝剂。2) Preparation of cationic composite flocculant: take 20mL of hydrolyzed gelatin solution in 1), adjust its pH to 3, add 45mL of ferric sulfate solution with a mass fraction of 5%, mix well at room temperature, and then add Alkali raises the pH value of the solution to 3.5, and reacts at 55°C for 14 hours to obtain a cationic composite flocculant.
用本实施例所制得的絮凝剂对油气田废弃钻井液进行絮凝，使用时絮凝剂与废弃钻井液投加量之比为1︰3.5，COD去除率达到83.9%，悬浮物去除率达到85.1%。Use the flocculant prepared in this example to flocculate the waste drilling fluid in oil and gas fields. When using it, the ratio of the dosage of the flocculant to the waste drilling fluid is 1:3.5, the removal rate of COD reaches 83.9%, and the removal rate of suspended matter reaches 85.1%. .
实施例5：Example 5:
一种阳离子型复合絮凝剂的制备方法，包括下述步骤：A preparation method of cationic composite flocculant, comprising the steps of:
1）水解明胶的制备：以碱法(MgO)水解从废弃皮胶原中提取出的相对分子质量较大的明胶为原料，配制质量分数为8%的明胶溶液，向其中加入0.5%的1398中性蛋白酶（按所用明胶的质量计），于40℃下水解2h，得到水解明胶溶液。1) Preparation of hydrolyzed gelatin: using gelatin with relatively large molecular weight extracted from waste skin collagen by hydrolysis with alkali method (MgO) as raw material, prepare a gelatin solution with a mass fraction of 8%, and add 0.5% of 1398 to it Protease (according to the mass of gelatin used), hydrolyze at 40°C for 2 hours to obtain a hydrolyzed gelatin solution.
2）阳离子型复合絮凝剂的制备：取1）中水解明胶溶液20mL，调节其pH=3，加入质量分数5%的氯化铁溶液35mL，常温下充分混合均匀后，在振荡的条件下，加碱将溶液的pH值提至3.8，于50℃下反应12h，即得阳离子型复合絮凝剂。2) Preparation of cationic composite flocculant: take 20mL of hydrolyzed gelatin solution in 1), adjust its pH=3, add 35mL of ferric chloride solution with a mass fraction of 5%, mix well at room temperature, and shake Add alkali to raise the pH value of the solution to 3.8, and react at 50°C for 12 hours to obtain a cationic composite flocculant.
用本实施例所制得的絮凝剂对油气田废弃钻井液进行絮凝，使用时絮凝剂与废弃钻井液投加量之比为1︰3.5，COD去除率达到77.8%，悬浮物去除率达到73.6%。Use the flocculant prepared in this example to flocculate the waste drilling fluid in oil and gas fields. When using it, the ratio of the dosage of the flocculant to the waste drilling fluid is 1:3.5, the removal rate of COD reaches 77.8%, and the removal rate of suspended matter reaches 73.6%. .
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110060601 CN102167431B (en) | 2011-03-14 | 2011-03-14 | A preparation method of cationic composite flocculant for waste drilling fluid treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110060601 CN102167431B (en) | 2011-03-14 | 2011-03-14 | A preparation method of cationic composite flocculant for waste drilling fluid treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167431A true CN102167431A (en) | 2011-08-31 |
| CN102167431B CN102167431B (en) | 2013-01-30 |
Family
ID=44488786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110060601 Expired - Fee Related CN102167431B (en) | 2011-03-14 | 2011-03-14 | A preparation method of cationic composite flocculant for waste drilling fluid treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167431B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328979A (en) * | 2011-09-06 | 2012-01-25 | 陕西科技大学 | Cationic flocculant based on collagen modification and preparation method thereof |
| CN102391844A (en) * | 2011-10-16 | 2012-03-28 | 天津科技大学 | Chrome leather shavings well-drilling leakage-stopping material |
| CN103183405A (en) * | 2013-04-19 | 2013-07-03 | 四川大学 | Collagen-inorganic metal salt flocculating agent and preparation method thereof |
| CN104229966A (en) * | 2014-08-30 | 2014-12-24 | 齐鲁工业大学 | Magnetic collagen starch modified cationic flocculant and preparation method thereof |
| CN104341035A (en) * | 2014-08-30 | 2015-02-11 | 齐鲁工业大学 | Magnetic collagen modified cationic flocculant and preparation method thereof |
| CN105502616A (en) * | 2015-12-21 | 2016-04-20 | 陕西科技大学 | Anion flocculating agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619272A1 (en) * | 1993-04-05 | 1994-10-12 | Agfa-Gevaert N.V. | Method for the purification of waste water containing silver |
| JPH1110169A (en) * | 1997-06-18 | 1999-01-19 | Hymo Corp | Treatment process for waste water |
| CN101717144A (en) * | 2009-11-19 | 2010-06-02 | 四川农业大学 | Composite flocculant and preparation method thereof |
-
2011
- 2011-03-14 CN CN 201110060601 patent/CN102167431B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619272A1 (en) * | 1993-04-05 | 1994-10-12 | Agfa-Gevaert N.V. | Method for the purification of waste water containing silver |
| JPH1110169A (en) * | 1997-06-18 | 1999-01-19 | Hymo Corp | Treatment process for waste water |
| CN101717144A (en) * | 2009-11-19 | 2010-06-02 | 四川农业大学 | Composite flocculant and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328979A (en) * | 2011-09-06 | 2012-01-25 | 陕西科技大学 | Cationic flocculant based on collagen modification and preparation method thereof |
| CN102391844A (en) * | 2011-10-16 | 2012-03-28 | 天津科技大学 | Chrome leather shavings well-drilling leakage-stopping material |
| CN102391844B (en) * | 2011-10-16 | 2013-06-12 | 天津科技大学 | Chrome leather shavings well-drilling leakage-stopping material |
| CN103183405A (en) * | 2013-04-19 | 2013-07-03 | 四川大学 | Collagen-inorganic metal salt flocculating agent and preparation method thereof |
| CN104229966A (en) * | 2014-08-30 | 2014-12-24 | 齐鲁工业大学 | Magnetic collagen starch modified cationic flocculant and preparation method thereof |
| CN104341035A (en) * | 2014-08-30 | 2015-02-11 | 齐鲁工业大学 | Magnetic collagen modified cationic flocculant and preparation method thereof |
| CN104229966B (en) * | 2014-08-30 | 2016-04-06 | 齐鲁工业大学 | A kind of magnetic collagen aleurone modified cation flocculation agent and preparation method thereof |
| CN105502616A (en) * | 2015-12-21 | 2016-04-20 | 陕西科技大学 | Anion flocculating agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167431B (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016058437A1 (en) | Treatment method for deep dewatering of sludge | |
| Gao et al. | Removal of microplastics by coagulation treatment in waters and prospect of recycling of separated microplastics: A mini-review | |
| CN103922449B (en) | A kind of high-efficiency environment friendly flocculation agent administered for black smelly river | |
| CN102328979B (en) | Cationic flocculant based on collagen modification and preparation method thereof | |
| CN102167431A (en) | Method for preparing cation type composite flocculant for treating waste drilling fluid | |
| CN102701496A (en) | Method and process for treating high-concentration organic wastewater difficult to degrade | |
| CN102910793A (en) | Joint-conditioning dehydration method for sludge | |
| CN103145313B (en) | Sludge conditioning agent appropriate for sludge incineration handling and conditioning method | |
| CN108083609A (en) | A kind of method that municipal sludge is nursed one's health by composite reagent | |
| CN116161848A (en) | Tannic acid compounded polyacrylamide efficient sludge conditioner and application thereof | |
| CN106186635A (en) | A method for advanced dehydration treatment of beer sludge and beer waste liquid | |
| CN105645732A (en) | Combined chemical conditioning method for deep drying of dehydrated sludge | |
| CN101468838B (en) | Method for preparing composite water purification agent | |
| CN104150741A (en) | Sludge chemical conditioning method and conditioner | |
| CN110436594A (en) | A kind of Sodium Polyacrylate sewage-treating agent and preparation method thereof | |
| CN102408145B (en) | Composite flocculant and use thereof | |
| CN103588273B (en) | A kind of Collagen Hydrolysate-inorganic metal salt flocculation agent and preparation method thereof | |
| CN104118925B (en) | A kind of composite inorganic flocculation agent | |
| CN105693065A (en) | Deep dewatering method for municipal sludge | |
| CN103172160A (en) | Composite powdery blue algae treatment agent and preparation method thereof | |
| CN106587571A (en) | Method for co-conditioning of sludge through multiple types of agents | |
| CN102491465B (en) | Flocculant and preparation method thereof | |
| CN103626367A (en) | Method for recycling polymer-containing air flotation oil sludge | |
| CN106673400A (en) | Sludge dewatering conditioner and application thereof in dewatering | |
| CN100441518C (en) | Fluorite mineral processing wastewater treatment flocculant |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201130 Address after: No.288, Changjiang West Road, Huji street, Hai'an City, Nantong City, Jiangsu Province, 226600 Patentee after: Jiangsu Zhaofang Intelligent Equipment Co.,Ltd. Address before: 808, floor 8, building B, business center, gangzhilong science and Technology Park, No. 6, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd. Effective date of registration: 20201130 Address after: 808, floor 8, building B, business center, gangzhilong science and Technology Park, No. 6, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd. Address before: 710021 Shaanxi city of Xi'an province Weiyang University City Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130130 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |