阅读说明：本技术 一种复合木质素基表面活性剂的制备及其处理含油污泥的应用 (Preparation of composite lignin-based surfactant and application of composite lignin-based surfactant in treatment of oily sludge ) 是由 李一晗 赵林 汪伶俐 陈达颖 黄梦露 高敏 于 2021-08-24 设计创作，主要内容包括：本发明提出一种复合木质素基表面活性剂的制备及其处理含油污泥的应用；将木质素与氧化试剂混合加入进行反应,得到氧化木质素；将得到的氧化木质素与磺化试剂混合加入进行反应,得到氧化磺化木质素；将环氧丙烷与长链脂肪胺类物质混合添加到长链脂肪季铵盐中间体；将氧化磺化木质素与长链脂肪季铵盐中间体混合反应得到木质素磺酸胺基表面活性剂。将含油污泥样品油浴加热,加入木质素磺酸胺基表面活性剂和生物表面活性剂,在搅拌下反应,然后进行离心分离。原油采收率可达77％以上,高达采收率94％。(The invention provides a preparation method of a composite lignin-based surfactant and an application of the composite lignin-based surfactant in treating oily sludge; mixing lignin and an oxidizing reagent, and adding the mixture to react to obtain oxidized lignin; mixing the obtained oxidized lignin with a sulfonation reagent, adding the mixture to react to obtain oxidized sulfonated lignin; mixing propylene oxide and long-chain fatty amine substances and adding the mixture into a long-chain fatty quaternary ammonium salt intermediate; and mixing the oxidized sulfonated lignin and the long-chain fatty quaternary ammonium salt intermediate for reaction to obtain the lignosulfonic acid amine-based surfactant. Heating the oily sludge sample in an oil bath, adding the lignosulfonate amine-based surfactant and the biosurfactant, reacting under stirring, and then performing centrifugal separation. The recovery rate of crude oil can reach more than 77 percent and can reach as high as 94 percent.)

1. A preparation method of a composite lignin-based surfactant specifically comprises the following steps:

1) mixing and adding lignin and an oxidizing reagent for reaction, and reacting for 1-5 hours at the temperature of 50-100 ℃ to obtain oxidized lignin;

2) mixing the oxidized lignin obtained in the step 1) with a sulfonation reagent, adding the mixture into the mixture for reaction, and reacting the mixture for 1 to 12 hours at the temperature of between 50 and 300 ℃ to obtain oxidized sulfonated lignin;

3) mixing and adding propylene oxide and long-chain fatty amine substances, and reacting at the temperature of 20-120 ℃ for 1-10h to obtain a long-chain fatty quaternary ammonium salt intermediate;

4) mixing the oxidized sulfonated lignin obtained in the step 2) with the long-chain fatty quaternary ammonium salt intermediate obtained in the step 3), reacting at the temperature of 50-110 ℃ for 1-10h, and cooling to room temperature after the reaction is finished to obtain the lignosulfonic acid amine-based surfactant.

2. The method as claimed in claim 1, wherein in step 1), the lignin is hardwood lignin, softwood lignin, including lignosulfonate or kraft lignin; the oxidizing agent is hydrogen peroxide, sodium hypochlorite, potassium dichromate, sodium dichromate, potassium permanganate, nitric acid, chlorine or oxygen.

3. The method as set forth in claim 1, wherein in the step 1), the mass ratio of the lignin to the oxidizing agent is 0.1-4: 1.

4. The method as set forth in claim 1, wherein in the step 2), the sulfonating agent is sodium sulfite, sulfur trioxide, concentrated sulfuric acid, sulfur dioxide plus oxygen, chlorosulfonic acid, potassium sulfite, sodium metabisulfite or potassium metabisulfite.

5. The method as set forth in claim 1, wherein in the step 2), the mass ratio of the oxidized lignin to the sulfonating agent is 0.1-6: 1.

6. The method as set forth in claim 1, wherein in the step 3), the long-chain aliphatic amine is an organic amine compound having a carbon chain length in the range of 8 to 22, and is preferably dodecyl dimethyl primary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl primary amine, or tetradecyl dimethyl tertiary amine.

7. The method as set forth in claim 1, wherein in the step 3), the mixing ratio of the propylene oxide to the long-chain aliphatic amine is 0.5-2: 1.

8. The method as set forth in claim 1, wherein in the step 4), the molar ratio of the oxidized sulfonated lignin to the long-chain fatty quaternary ammonium salt intermediate is 0.5-2: 1.

9. The composite lignin-based surfactant prepared according to claim 1 is applied to a method for treating oil-containing sludge; the method is characterized in that an oily sludge sample is uniformly stirred and placed in a container, and is heated by an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant, wherein the mass ratio of the lignosulphonate amine surfactant to the biosurfactant is 1-10:1, stirring at the stirring speed of 300r/min-5000r/min, and then reacting at the temperature of 60-120 ℃ for 1-12 h; after the reaction, the reaction system was centrifuged.

10. The method as claimed in claim 9, wherein the biosurfactant is rhamnolipid, sophorolipid or algal glycolipid.

Technical Field

The invention belongs to the technical field of preparation of surfactants, and relates to preparation of a composite lignin-based surfactant and application thereof in treating oily sludge; in particular to a lignosulphonate amine surfactant and a small amount of biosurfactant composite system and application thereof in the aspect of strengthening the recovery of crude oil in oil-containing sludge.

Background

The surfactant can reduce the surface tension of a solution, change the interfacial state of the solution, and have the effects of emulsification, wetting, solubilization, penetration, and solubilization, etc. in use, thereby playing an important role in the industrial field. Most of the traditional surfactants are prepared by taking petroleum as a raw material, but the increasing exhaustion of petroleum resources causes the production cost of the surfactants to be remarkably increased, which is not favorable for the sustainable development of economy.

Lignin is an aromatic organic high polymer with a complex structure and is an important component of vascular plant cell walls. The lignin macromolecular structure is a three-dimensional space network structure formed by connecting three phenylpropane monomers (namely an syringyl propane structure S-unit, a p-hydroxyphenyl propane structure H-unit and a guaiacyl propane structure G-unit) through a large number of ether bonds (C-O) and carbon-carbon bonds (C-C). Meanwhile, lignin has many attractive advantages such as high carbon content, good thermal stability, biodegradability, excellent oxidation resistance, high hardness, low price, etc., which has led researchers to widely develop lignin in an attempt to apply its value-added products to various fields. Surfactants have received much attention from researchers as an important application area for lignin. Lignin is a natural surfactant, and has special structural properties, and contains both hydrophilic groups such as carboxyl, hydroxyl and carbonyl groups and lipophilic groups such as phenylpropane. Usually, lignin cannot be directly used as a surfactant to be applied to practice, and needs to be modified appropriately to increase the number of hydrophilic groups or lipophilic groups in lignin or enhance the hydrophilic-lipophilic strength so as to increase the surface activity of lignin. The application of the lignin in the field of the surfactant improves the use value of the lignin, relieves the problem of insufficient petroleum resources, and is beneficial to realizing the sustainable development of economy.

Oily sludge is a solid waste rich in mineral oil, which is generated in the petroleum exploration and development industry and the petrochemical industry production industry, and is not inherently present in nature. The oily sludge mainly comprises oil, silt and water, wherein the water content is 20-50%, the oil content is 30-60%, and the solid content is 10-40%. The crude oil yield is estimated to be 1.6 multiplied by 10 per year in China at present^-8The oil-containing sludge produced by the method accounts for about 0.5-1% of the crude oil yield (nearly millions of tons of oil sludge, oil sand and the like are produced every year), and the oil-containing sludge and the like are accumulated in an oil tank for a long time due to the oil sludge discharge restriction policy of the environmental protection department, so that the operation device is not burdened, and the normal operation of oil field production is seriously hindered. In addition, the oily sludge has complex components, contains a large amount of organic pollutants, inorganic matters, heavy metals and even radioactive toxic substances, and is difficult to settle, so that the land structure and the underground water quality are deeply affected, the ecological structure is damaged, and the health of human bodies is seriously threatened. The oily sludge also contains various pathogenic bacteria, parasitic ova, homologues of benzene, anthracene, pyrene and other highly toxic substances, and the substances are exposed in the air for a long time and then can be infected infinitely. Fossil energy such as petroleum is a non-renewable resource, so that the efficient treatment of the oily sludge to obtain good oil recovery ratio not only conforms to the development concept of sustainable development, but also conforms to the development requirement of building an environment-friendly society.

The patent CN1360969A carries out electrode oxidation, alkylation and sulfonation modification operations on alkali lignin in sequence, and the oil-water surface tension of the modified lignin surfactant compounded with petroleum sulfonate under the alkali condition reaches 10^-3mN/m, the oil content of the recovered oil reaches 78 percent; patent CN1327026A uses a long carbon chain-containing greaseThe fatty amide chemically modifies lignosulfonate, and the result shows that the lignosulfonate can enable the oil-water interfacial tension to reach 10^-3mN/m; in patent CN1123620C, lignosulfonate is compounded with petroleum carboxylate and alkylbenzene sulfonate respectively, and it is found that the oil-water interfacial tension of the complex system can reach 10 under the alkali condition^-3mN/m。

The composite surfactant provided by the invention aims to reduce the raw material cost, reduce the surface tension of oil and water to an ultra-low level without other specific conditions such as alkali and the like, and further improve the recovery rate of crude oil.

Disclosure of Invention

The invention aims to provide a method for preparing a lignosulphonate amine surfactant and a small amount of biosurfactant for recovering crude oil in oily sludge in a compounding way, the lignosulphonate amine surfactant takes lignin as a raw material, firstly reacts with an oxidant and a sulfonation reagent, hydrophilic groups are introduced to side chains of the lignin to obtain oxidized sulfonated lignin, then a long-chain quaternary ammonium salt substance, namely lipophilic group, is introduced into lignin molecules through alkylation reaction to obtain the lignosulphonate amine surfactant, and then the lignosulphonate amine surfactant and the small amount of biosurfactant are compounded to prepare the lignosulphonate amine surfactant,

the invention provides a preparation method of a composite lignin-based surfactant, which specifically comprises the following steps:

1) mixing and adding lignin and an oxidizing reagent for reaction, and reacting for 1-5 hours at the temperature of 50-100 ℃ to obtain oxidized lignin;

2) mixing the oxidized lignin obtained in the step 1) with a sulfonation reagent, adding the mixture into the mixture for reaction, and reacting the mixture for 1 to 12 hours at the temperature of between 50 and 300 ℃ to obtain oxidized sulfonated lignin;

3) mixing and adding propylene oxide and long-chain fatty amine substances, and reacting at the temperature of 20-120 ℃ for 1-10h to obtain a long-chain fatty quaternary ammonium salt intermediate;

4) mixing the oxidized sulfonated lignin obtained in the step 2) with the long-chain fatty quaternary ammonium salt intermediate obtained in the step 3), reacting at the temperature of 50-110 ℃ for 1-10h, and cooling to room temperature after the reaction is finished to obtain the lignosulfonic acid amine-based surfactant.

In the step 1), the lignin is specifically hardwood lignin and softwood lignin, and comprises lignosulfonate or kraft lignin.

In the step 1), the oxidizing reagent is hydrogen peroxide, sodium hypochlorite, potassium dichromate, sodium dichromate, potassium permanganate, nitric acid, chlorine or oxygen.

In the step 1), the mass ratio of the lignin to the oxidizing reagent is 0.1-4: 1.

In the step 2), the sulfonation reagent is sodium sulfite, sulfur trioxide, concentrated sulfuric acid, sulfur dioxide and oxygen, chlorosulfonic acid, potassium sulfite, sodium metabisulfite or potassium metabisulfite.

In the step 2), the mass ratio of the oxidized lignin to the sulfonation reagent is 0.1-6: 1.

In the step 3), the long-chain aliphatic amine substance is an organic amine compound with a carbon chain length within a range of 8-22, and is preferably dodecyl dimethyl primary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl primary amine or tetradecyl dimethyl tertiary amine.

In the step 3), the mixing molar ratio of the epoxypropane to the long-chain aliphatic amine substance is 0.5-2:1

In the step 4), the molar ratio of the oxidized sulfonated lignin to the long-chain fatty quaternary ammonium salt intermediate is 0.5-2: 1.

The composite lignin-based surfactant prepared by the invention is applied to a method for treating oily sludge; uniformly stirring an oil-containing sludge sample, placing the sample in a container, and heating the sample by using an oil bath to perform reaction; adding lignosulphonate amine surfactant and biosurfactant, wherein the mass ratio of the lignosulphonate amine surfactant to the biosurfactant is 1-10:1, stirring at the stirring speed of 300r/min-5000r/min, and then reacting at the temperature of 60-120 ℃ for 1-12 h; after the reaction is finished, carrying out centrifugal separation on the reaction system, and carrying out subsequent content determination.

The biosurfactant is rhamnolipid, sophorolipid or seaweed glycolipid.

The principle of the invention is that the surface tension of an oil-water interface is reduced, the wettability of the interface surface is changed, and a surfactant can be adsorbed to certain components of the structural crude oil, the interaction of the components is weakened, the viscosity of the crude oil is promoted to be reduced, and the purpose of oil extraction is realized.

According to the characteristics of the natural lignin surfactant and the excellent characteristics of low cost, rich raw material sources and biodegradability, the high-efficiency lignin-based surfactant is prepared for treating the oily sludge, and the oil displacement effect is realized by reducing the surface tension of an oil-water interface.

The invention has the beneficial effects that: (1) the raw material lignin is nontoxic and harmless, has rich content and low cost, and relieves the pressure of shortage of petroleum resources; (2) provides a new way for the value-added utilization of lignin; (3) the composite use of the lignin-based surfactant and the biosurfactant can reduce the oil-water interfacial tension to an ultra-low level, and obviously improve the recovery ratio of crude oil in oil sludge; the invention provides a novel efficient environment-friendly lignin-based amphoteric surfactant for enhancing the recovery ratio of crude oil in oily sludge.

Detailed Description

Example 1

1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 10g of hydrogen peroxide at 50 ℃ for 1h to obtain oxidized lignin;

2. adding 0.4g of sodium sulfite and sulfonating for 1h at 50 ℃ to obtain oxidized sulfonated lignin;

3. mixing 0.53g of propylene oxide and 3.85g of dodecyl dimethyl primary amine, and reacting for 1h at the temperature of 20 ℃ to obtain a long carbon chain fatty quaternary ammonium salt intermediate;

4. 2.878g of quaternary ammonium salt intermediate and 1.445g of oxidized sulfonated lignin are mixed and reacted for 1h at 50 ℃, and after the reaction is finished, the temperature is cooled to room temperature to prepare the lignosulfonate amine-based surfactant.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant rhamnolipid according to the mass ratio of 10:1, stirring at the speed of 300r/min, and then reacting at the temperature of 60 ℃ for 1 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery rate of crude oil obtained by recovering and weighing the oil on the upper layer can reach 77%.

Example 2

1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 3.3g of sodium hypochlorite at 65 ℃ for 4h to obtain oxidized lignin;

2. adding 1.5g of concentrated sulfuric acid, and sulfonating at 90 ℃ for 3h to obtain oxidized sulfonated lignin;

3. mixing 1.23g of propylene oxide and 2.52g of dodecyl dimethyl tertiary amine, and reacting for 4 hours at the temperature of 60 ℃ to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;

4. mixing 4.637g of quaternary ammonium salt intermediate with 3.245g of oxidized sulfonated lignin, reacting for 5h at 70 ℃, cooling to room temperature after the reaction is finished, and preparing the lignosulfonate amine-based surfactant.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant rhamnolipid according to the mass ratio of 8:1, stirring at the speed of 1000r/min, and then reacting at the temperature of 80 ℃ for 6 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 80%.

Example 3

1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 2g of potassium dichromate at 80 ℃ for 4h to obtain oxidized lignin;

2. adding 2g of chlorosulfonic acid, and sulfonating at 135 ℃ for 3h to obtain oxidized sulfonated lignin;

3. mixing 1.75g of propylene oxide and 3.75g of dodecyl dimethyl tertiary amine, and reacting for 2 hours at 70 ℃ to obtain a long carbon chain fatty quaternary ammonium salt intermediate;

4. mixing 4.9g of quaternary ammonium salt intermediate with 4.8g of oxidized sulfonated lignin, reacting for 6h at 90 ℃, cooling to room temperature after the reaction is finished, and preparing the lignosulfonate amine-based surfactant.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant sophorolipid according to the mass ratio of 6:1, stirring at the speed of 2500r/min, and then reacting at the temperature of 75 ℃ for 6 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 87%.

Example 4

1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 1g of sodium dichromate at 80 ℃ for 4 hours to obtain oxidized lignin;

2. adding 4g of potassium sulfite, and sulfonating at 200 ℃ for 8h to obtain oxidized sulfonated lignin;

3. mixing 2.188g of propylene oxide and 4.683g of tetradecyl dimethyl primary amine, and reacting at 90 ℃ for 7 hours to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;

4. 3.616g of quaternary ammonium salt intermediate and 5.424g of oxidized sulfonated lignin are mixed and reacted for 7 hours at the temperature of 90 ℃, and after the reaction is finished, the temperature is cooled to room temperature, so that the lignosulfonate amine-based surfactant is prepared.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant sophorolipid according to the mass ratio of 4:1, stirring at the speed of 3000r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 91%.

Example 5

1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 0.67g of potassium permanganate at 90 ℃ for 5 hours to obtain oxidized lignin;

2. adding 0.2g of sodium metabisulfite and sulfonating for 10 hours at the temperature of 250 ℃ to obtain oxidized sulfonated lignin;

3. mixing 2.625g of propylene oxide and 5.615g of tetradecyl dimethyl tertiary amine, and reacting at 110 ℃ for 9h to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;

4. 4.485g of quaternary ammonium salt intermediate and 6.728g of oxidized sulfonated lignin are mixed and react for 8 hours at the temperature of 100 ℃, and after the reaction is finished, the temperature is cooled to room temperature to prepare the lignosulfonate amine-based surfactant.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant algal glycolipid according to the mass ratio of 3:1, stirring at the speed of 4500r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery rate of crude oil obtained by recovering and weighing the oil on the upper layer can reach 94 percent.

Example 6

1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 0.25g of nitric acid at 100 ℃ for 5 hours to obtain oxidized lignin;

2. adding 0.2g of potassium metabisulfite, and sulfonating at 300 ℃ for 12 hours to obtain oxidized sulfonated lignin;

3. mixing 2.625g of propylene oxide and 5.615g of tetradecyl dimethyl tertiary amine, and reacting at 120 ℃ for 10h to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;

4. 3.613g of quaternary ammonium salt intermediate and 7.225g of oxidized sulfonated lignin are mixed and reacted for 10 hours at 110 ℃, and after the reaction is finished, the temperature is cooled to room temperature, so that the lignosulfonate amine-based surfactant is prepared.

Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulfonate amine-based surfactant and biological surfactant trehalose glycolipid according to the mass ratio of 1:1, stirring at the speed of 5000r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 89%.

While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention. The invention belongs to the known technology.