CN113969151B - Biomass main emulsifier, preparation method and application thereof - Google Patents
Biomass main emulsifier, preparation method and application thereof Download PDFInfo
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- C09K8/02—Well-drilling compositions
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Abstract
The invention relates to the technical field of drilling fluid treatment agents, and provides a biomass main emulsifier, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine, and reacting in a solvent under the catalysis of composite lipase to obtain an amide biomass main emulsifier; the carbon number of the long-chain fatty acid methyl ester is more than 13; the enzymes in the compound lipase act on long-chain lipase methyl ester and short-chain fatty acid methyl ester respectively. The reaction system mainly uses biological enzyme catalysis to replace chemical catalysis, so that the reaction temperature can be reduced, the energy consumption is reduced, and the lipase has strong selectivity and specificity, so that the reaction conversion rate is improved, the byproducts are fewer, and the product performance is good. The preparation method has mild preparation conditions, high-efficiency preparation process, environment friendliness and capability of reducing the generation of three wastes, and the generated methanol can be recycled to produce fatty acid methyl ester.
Description
Technical Field
The invention relates to the technical field of drilling fluid treatment agents, in particular to a biomass main emulsifier, a preparation method and application thereof.
Background
Mineral oil-based and synthetic-based drilling fluids are widely used in oil and gas drilling due to their good temperature resistance, lubrication, inhibition properties, etc. The mineral oil-based and synthetic-based drilling fluid mainly comprises base oil, brine, organic soil, an emulsifying agent, a filtrate reducer, an alkalinity regulator, barite and the like. Among them, the base oil which is more environmentally friendly recently is a biomass base liquid. The stability of mineral oil-based, synthetic-based drilling fluids depends primarily on the performance of the emulsifier; some emulsifying systems include a primary emulsifier and a secondary emulsifier. Currently, emulsifiers for mineral oil-based and synthetic-based drilling fluids have been relatively mature, mainly including carboxylic acid soaps, sulfonic acid soaps, organic acid esters, amides, polyoxyethylene ethers, and the like. The emulsifier has been widely used, and has good emulsifying and temperature resisting properties.
For emulsifiers containing amide groups, they are generally prepared by reaction under chemically catalyzed conditions. However, the preparation process has the defects that conditions such as high temperature (generally more than 120 ℃) and pressurization are needed in the preparation process, the conversion rate is low, side reactions are easy to occur, and more byproducts are caused in the emulsifier; a large amount of three wastes and the like are generated in the preparation process, so that the production cost of the emulsifier is higher, and the adverse effect on the environment can be caused in part of the production process of the emulsifier, thereby being contrary to the advocated low-carbon environment-friendly concept.
Therefore, the development of the emulsifier preparation technology for mineral oil-based and synthetic-based drilling fluid, which has low energy consumption, mild preparation conditions, environmental protection and sustainable development, has important significance.
Disclosure of Invention
In view of the above, the application provides a biomass main emulsifier, a preparation method and application thereof, and the method for preparing the emulsifier is mild in condition, green and environment-friendly, and good in product performance and is beneficial to application.
The invention provides a preparation method of a biomass main emulsifier, which comprises the following steps:
mixing long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine, and reacting in a solvent under the catalysis of composite lipase to obtain an amide biomass main emulsifier;
the carbon number of the long-chain fatty acid methyl ester is more than 13; the enzymes in the compound lipase act on long-chain lipase methyl ester and short-chain fatty acid methyl ester respectively.
Preferably, the long-chain fatty acid methyl ester is saturated or unsaturated fatty acid methyl ester with 14-23 carbon atoms.
Preferably, the short chain fatty acid methyl ester is saturated or unsaturated fatty acid methyl ester with 5-13 carbon atoms.
Preferably, the complex lipase comprises a first lipase and a second lipase;
the first Lipase acts on long chain fatty acid methyl esters, preferably one of Novozym 435, lipozyme TLIM, lipozyme 435 and Lipase AYS Amano;
the second Lipase acts on short chain fatty acid methyl esters, preferably Lipase DF "Amano"15, lipozyme RMIM, lipomod TM One of L691MDP, lipase No.89445, and Lipase No. 62310.
Preferably, the first lipase is used in an amount of 1-5% of the mass of the long-chain fatty acid methyl ester; the dosage of the second lipase is 2-8% of the mass of the short chain fatty acid methyl ester.
Preferably, the polyamine is selected from one or more of aliphatic diamines and polyethylene polyamines; the polyamine is preferably selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentyenediamine, hexylenediamine, octylenediamine, nonylenediamine, decylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Preferably, the solvent is one of dodecyl methyl ether, lauryl amyl ether and tetradecyl butyl ether.
Preferably, the preparation method specifically comprises the following steps:
adding long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine into a reaction kettle according to the mole ratio of (0.9-1.1) in sequence under the stirring state; then adding composite lipase; adding solvent according to 20% -40% of total mass of long-chain fatty acid methyl ester, short-chain fatty acid methyl ester, polyamine and compound lipase, reacting for a certain time, decompressing and filtering to obtain the amide biomass main emulsifier, wherein unfiltered lipase can be repeatedly used.
Preferably, the temperature of the reaction is 40 to 80 ℃.
Preferably, the reaction time is 24-48 hours; the stirring speed is 200-350 rpm.
The invention provides a biomass main emulsifier which is prepared by the preparation method; the amine value of the biomass main emulsifier is 8.95-30.55 mgKOH/g.
The invention provides a drilling fluid, which comprises the biomass main emulsifier.
In the embodiment of the invention, long-chain fatty acid methyl ester (with more than 13 carbon atoms), short-chain fatty acid methyl ester, polyamine, compound lipase and solvent are added into a reaction kettle, and the compound lipase is used as a catalyst to react the fatty acid methyl ester and the polyamine for a certain time, so that an emulsifier product containing amide groups is obtained. The reaction system mainly uses biological enzyme catalysis to replace chemical catalysis, so that the reaction temperature can be reduced, the energy consumption is reduced, and the lipase has strong selectivity and specificity, so that the reaction conversion rate is improved, and the byproducts are few. The preparation method has mild preparation conditions, high-efficiency preparation process, environment friendliness and capability of reducing the generation of three wastes, and the generated methanol can be recycled to produce fatty acid methyl ester.
In addition, the amine value of the biomass main emulsifier prepared by the invention is 8.95-30.55 mgKOH/g, the biomass main emulsifier has the characteristics of environmental protection, greenness and easy biodegradation, and the emulsifying property of the biomass main emulsifier is equivalent to that of the conventional emulsifier for mineral oil-based and synthetic-based drilling fluids, and the biomass main emulsifier can be used for the mineral oil-based and synthetic-based drilling fluids with high temperature, high density and low oil-water ratio.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other examples of modifications and alterations will be apparent to those skilled in the art based on the examples herein, and are intended to be within the scope of the invention.
The invention provides a preparation method of a biomass main emulsifier, which comprises the following steps:
mixing long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine, and reacting in a solvent under the catalysis of composite lipase to obtain an amide biomass main emulsifier;
the carbon number of the long-chain fatty acid methyl ester is more than 13; the enzymes in the compound lipase act on long-chain lipase methyl ester and short-chain fatty acid methyl ester respectively.
The method for preparing the emulsifier has mild conditions, simple and feasible preparation process, high efficiency, environmental protection and good performance, and can reduce the generation of three wastes.
According to the embodiment of the invention, long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine can be sequentially added into a reaction kettle according to the molar ratio; the molar ratio of the three is preferably (0.9-1.1): 1.0, more preferably 1.0:1.0:1.0.
Wherein the long chain fatty acid methyl ester has 13 or more carbon atoms, preferably saturated or unsaturated fatty acid methyl ester having 14 to 23 carbon atoms, more preferably 15 to 19 carbon atoms, such as 17 to 19 carbon atoms. In some embodiments of the invention, the long chain fatty acid methyl ester is methyl oleate or methyl palmitoleate.
And the number of carbon atoms of the short chain fatty acid methyl ester is 13 or less. The short chain fatty acid methyl ester is preferably a saturated or unsaturated fatty acid methyl ester having 5 to 13 carbon atoms, more preferably a saturated or unsaturated fatty acid methyl ester having 6 to 11 carbon atoms, such as 9 to 11 carbon atoms. In some embodiments of the invention, the short chain fatty acid methyl ester is methyl octanoate or methyl decanoate. The fatty acid methyl esters used in the embodiment of the invention are all from vegetable oil, waste oil and the like, and have wide sources and excellent environmental protection.
In embodiments of the present invention, the polyamine may be selected from one or more of aliphatic diamines (preferably aliphatic diamines of short carbon chain, such as aliphatic diamines having 2 to 11 carbon atoms) and may also be selected from one or more of polyethylene polyamines. Preferably, the polyamine is one or more of ethylenediamine, propylenediamine, butylenediamine, pentyenediamine, hexylenediamine, octylenediamine, nonylenediamine, decylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, preferably butylenediamine, hexamethylenediamine, diethylenetriamine or triethylenetetramine, more preferably hexamethylenediamine.
The emulsifier preparation technology provided by the invention is a method for performing biocatalysis reaction by adopting biological enzyme, and specifically, the emulsifier is prepared by adding composite lipase serving as a catalyst in a targeted manner into a reaction system of fatty acid ester and polyamine. Biological enzyme is a nontoxic and environment-friendly biological catalyst, the chemical nature of the biological enzyme is protein, and the biological enzyme is widely applied to the fields of textile, papermaking, food processing, medicine and the like at present. The biological enzyme is used as an emerging catalyst, has outstanding characteristics and obvious advantages, and is mainly characterized by high efficiency, specificity, mild reaction conditions, recycling and the like. Therefore, the preparation of the emulsifier for mineral oil-based and synthetic-based drilling fluid by using biological enzyme catalysis has good prospect.
According to the high selectivity, the high specificity and the like of the enzyme, the composite lipase disclosed by the invention comprises two types of lipases, namely a first lipase and a second lipase (also called lipase A and lipase B), and the composite lipase plays a main role in long-chain lipase methyl ester and short-chain fatty acid methyl ester respectively.
In a specific embodiment of the invention, the complex lipases are all commercially available products; the first Lipase may be one of novozyme 435, lipozyme TLIM, lipozyme 435 (purchased from Biocatalysts novei company), and Lipase AYS Amano (purchased from the enzyme preparation of the world wide company), preferably novozyme 435 or Lipozyme 435, more preferably novozyme 435.
And, the second Lipase may be Lipase DF "Amano"15 (available from Amano England, inc.), lipozyme RMIM (available from Norwegian Co., ltd.), lipomod TM L691MDP (available from Biocatalysts), lipase No.89445 and Lipase No.62310 (available from Sigma-Aldrich), preferably Lipozyme RMIM, lipase DF "Amano"15 or Lipase No.89445, more preferably Lipase No.89445. The compound lipase provided by the embodiment of the invention has higher activity and selectivity in a preferable temperature range and a solvent, and has stronger specificity for fatty acid methyl esters with different chain lengths.
In the present invention, the mass of the first lipase is preferably 1% to 5% of the mass of the long chain fatty acid methyl ester, more preferably 3%. The mass of the second lipase is preferably 2% to 8%, more preferably 4% to 6%, and most preferably 4% of the mass of the short chain fatty acid methyl ester.
According to the embodiment of the invention, after the first lipase and the second lipase are sequentially added, a solvent can be added according to the total mass fraction of fatty acid methyl ester, polyamine and lipase of 20% -40%. In the present invention, the mass of the solvent is preferably 30% of the total mass of fatty acid methyl ester, polyamine and lipase. The solvent is preferably one of dodecyl methyl ether, lauryl amyl ether and tetradecyl butyl ether, preferably dodecyl methyl ether or lauryl amyl ether, and most preferably lauryl amyl ether; the complex lipase provided by the invention has higher activity and selectivity in the solvent.
In a specific embodiment of the invention, dodecyl methyl ether is from patent application No. 201811002980.3 and amyl laurate is prepared according to patent application No. 201710845975.8, and tetradecyl butyl ether is from patent application No. 201811003858.0. The solvent has the characteristics of green, environmental protection and the like, and can be directly used as the solvent; mainly because the stability of the drilling fluid system is destroyed by the traditional solvent existing in the emulsifier, reduced pressure distillation is needed to remove the solvent. The solvent can be used as the base oil for preparing the drilling fluid, so that the solvent does not need to be removed. The embodiment of the invention selects the solvents, not only simplifies the preparation process, but also can improve the compatibility of the emulsifying agent and the drilling fluid system, and is beneficial to the emulsification stability of the drilling fluid.
In the specific embodiment of the invention, preferably, long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine are added into a reaction kettle in a mol ratio of (0.9-1.1) to (0.9-1.1) 1 in sequence under the stirring state; then adding lipase A and lipase B in sequence according to a certain mass fraction; adding a solvent (preferably a solvent which is not required to be distilled off) according to 20% -40% of the total mass of fatty acid methyl ester, polyamine and lipase, reacting for a certain time, and then filtering under reduced pressure to obtain the emulsifier containing amide groups, wherein the emulsifier can be used as a main emulsifier in drilling fluid.
In the present invention, the temperature of the reaction is preferably 40 to 80 ℃, more preferably 50 to 70 ℃, and most preferably 60 ℃. The reaction time is preferably 24 to 48 hours, more preferably 36 hours; the stirring speed is preferably 200 to 350rpm, more preferably 300rpm. The invention has mild reaction conditions, is only carried out at lower temperature and normal pressure, and has simple and easy preparation process.
The invention provides a biomass main emulsifier which is prepared by the preparation method; the amine value of the biomass main emulsifier is 8.95-30.55 mgKOH/g.
The invention provides a drilling fluid comprising the biomass main emulsifier. Specifically, the embodiment of the invention provides a drilling fluid, which comprises a biomass main emulsifier, base oil, an auxiliary emulsifier, a calcium chloride aqueous solution, organic soil, a filtrate reducer, calcium oxide and barite, wherein the biomass main emulsifier, the base oil, the auxiliary emulsifier, the calcium chloride aqueous solution, the organic soil, the filtrate reducer, the calcium oxide and the barite are prepared by the scheme. Wherein the base oil comprises diesel oil, white oil and biomass synthesis base liquid; the organic soil can be modified bentonite by quaternary ammonium salt, and the auxiliary emulsifier can be modified fatty acid derivatives and fatty acid amide derivatives. The filtrate reducer can adopt modified asphalt and modified humic acid.
Compared with the traditional chemical synthesis method for preparing the amide emulsifier, the method for preparing the emulsifier by adopting the biocatalysis method has the characteristics of mild reaction conditions, high efficiency of the preparation process, environment friendliness, high reaction specificity, few byproducts and the like, and the biological enzyme can be recycled for 10-20 times and still maintain high yield, and the biological enzyme can recycle products and reduce production cost. In addition, the invention can reduce the generation of three wastes, and the generated methanol can be recycled to produce fatty acid methyl ester.
The biomass main emulsifier prepared by the embodiment of the invention is obtained by modifying natural materials, and has the characteristics of wide raw material sources, excellent environmental protection and easiness in biodegradation. The determination is carried out according to the standard, and the experimental result shows that the emulsifier for the biomass synthesis base drilling fluid has low toxicity and is easy to be biodegraded, and the LD thereof 50 Greater than 5000mg/kg, biochemical BOD 5 /COD Cr 0.50 to 0.70.
The emulsifying property of the biomass main emulsifying agent prepared by the invention is equivalent to that of the emulsifying agent for the traditional mineral oil-based and synthetic-based drilling fluid, and the biomass main emulsifying agent is suitable for the mineral oil-based and synthetic-based drilling fluid with high temperature, high density and low oil-water ratioVarious drilling fluid systems, including diesel oil, white oil, synthetic base and the like, with the density of 1.2-2.5 g/cm 3 The drilling fluid system of the (C) has excellent temperature resistance, which can reach 200 ℃.
For a further understanding of the present invention, the biomass primary emulsifier provided herein, its preparation method and application are specifically described below in connection with examples. It is to be understood that these examples are provided for the purpose of illustrating the details of the invention and the particular process and are not intended to limit the scope of the invention, which is defined solely by the claims, but not by the way of limitation.
In the following examples:
the methyl oleate, methyl palmitoleate, methyl caprylate, methyl caprate, hexamethylenediamine, diethylenetriamine referred to were all purchased from guangdong Weng Jiang chemical reagent company, inc;
novozym 435, lipozyme 435 were purchased from Novozymes corporation; lipase DF "Amano"15 was purchased from Amano, inc.; lipase No.89445 was purchased from Sigma-Aldrich;
the mineral oil is No. 0 diesel oil and No. 3 white oil; the biomass base fluid is from drilling engineering technical institute of China petroleum engineering, inc., patent application number is 201810743989.3; the organic soil is purchased from Sichuan new energy petroleum engineering technology Co., ltd; the auxiliary emulsifier SMEMUL-2 is purchased from Tiancheng chemical industry Co., ltd in Jiyuan; calcium oxide was purchased from Hubei Longhai chemical Co., ltd; oxidized asphalt was purchased from henna flying petroleum auxiliary company; barite is purchased from new zheng Mei Jiu, a real company, zheng state, inc.
The amine number in the examples according to the invention was determined according to the standard HG/T3503-1989 octadecylamine. LD of the embodiment of the invention 50 The value is according to the standard of chemical acute oral toxicity test method (GB/T21603-2008), chemical acute inhalation toxicity test method (GB/T21605-2008) and BOD 5 /COD Cr The values were determined according to the standard Water soluble field chemistry environmental protection technology requirements (SY/T6787-2010).
Example 1
51.0g of methyl oleate, 27.2g of methyl octoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle in a molar ratio of 1.0:1.0:1.0 under stirring, and 1.53g of Lipase Novozym 435 and 1.08g of Lipase No.89445 are sequentially added according to 3% of the mass of the methyl oleate and 4% of the mass of the methyl octoate; 30.2g of lauryl amyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture is reacted at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and then the mixture is decompressed and filtered to obtain the biomass main emulsifier.
Example 2
45.9g of methyl oleate, 24.5g of methyl octoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to the molar ratio of 0.9:0.9:1.0, and 0.46g of Lipase Novozym 435 and 0.49g of Lipase No.89445 are sequentially added according to the mass of 1% of methyl oleate and the mass of 2% of methyl octoate; 18.3g of lauryl amyl ether is added according to 20 percent of the total mass of fatty acid methyl ester and lipase, the mixture reacts at the stirring speed of 200rpm and the temperature of 50 ℃ for 48 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 3
56.1g of methyl oleate, 30.0g of methyl octoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to a molar ratio of 1.1:1.1:1.0, and 2.8g of Lipase Novozym 435 and 2.4g of Lipase No.89445 are sequentially added according to the mass of 5% of methyl oleate and the mass of 8% of methyl octoate; 44.5g of lauryl amyl ether is added according to 40 percent of the total mass of fatty acid methyl ester and lipase, the mixture reacts at the stirring speed of 350rpm and the temperature of 70 ℃ for 24 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 4
57.5g of methyl oleate, 30.7g of methyl octoate and 20g of diethylenetriamine are sequentially added into a reaction kettle according to the molar ratio of 1.0:1.0:1.0, and 1.7g of Lipase Novozym 435 and 1.2g of Lipase No.89445 are sequentially added according to the mass of 3% of methyl oleate and the mass of 4% of methyl octoate; 33.3g of lauryl amyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture is reacted at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 5
46.2g of methyl palmitoleate, 27.2g of methyl caprylate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to a molar ratio of 1.0:1.0:1.0, and 1.4g of Lipase Novozym 435 and 1.1g of Lipase No.89445 are sequentially added according to the mass of 3% of methyl palmitoleate and the mass of 4% of methyl caprylate; 28.8g of lauryl amyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture reacts at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 6
51.0g of methyl oleate, 32.1g of methyl decanoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to the molar ratio of 1.0:1.0:1.0, and 1.5g of Lipase Novozym 435 and 1.3g of Lipase No.89445 are sequentially added according to the mass of 3% of methyl palmitoleate and the mass of 4% of methyl octanoate; 31.8g of lauryl amyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture reacts at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 7
51.0g of methyl oleate, 27.2g of methyl octoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to the molar ratio of 1.0:1.0:1.0, and 1.53g of Lipase Novozym 435 and 1.08g of Lipase No.89445 are sequentially added according to the mass of 3% of methyl oleate and the mass of 4% of methyl octoate; 30.2g of dodecyl methyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture is reacted at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and the biomass main emulsifier is obtained by decompression and filtration.
Example 8
51.0g of methyl oleate, 27.2g of methyl octoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle according to the molar ratio of 1.0:1.0:1.0, and 1.53g of Lipase 435 and 1.08g of Lipase DF 'Amano' 15 are sequentially added according to the mass of 3% of methyl oleate and the mass of 4% of methyl octoate; 30.2g of lauryl amyl ether is added according to 30 percent of the total mass of fatty acid methyl ester and lipase, the mixture is reacted at the stirring speed of 300rpm and the temperature of 60 ℃ for 36 hours, and then the mixture is decompressed and filtered to obtain the biomass main emulsifier.
Example 9
A biomass primary emulsifier was obtained according to the preparation method of example 1, except that lipase was used 20 times as in example 1.
Comparative example 1
A biomass primary emulsifier was obtained according to the preparation method of example 1, except that no lipase was added as in example 1.
Comparative example 2
51.0g of methyl oleate, 27.2g of methyl octanoate and 20g of hexamethylenediamine are sequentially added into a reaction kettle, 0.78g of potassium hydroxide is added according to 1% of the total mass of the methyl oleate and the methyl octanoate, the mixture is reacted at the stirring speed of 300rpm and the temperature of 160 ℃, nitrogen is introduced for reaction for 8 hours, and then the mixture is cooled and discharged to obtain the emulsifier.
Comparative example 3
A biomass primary emulsifier was obtained according to the preparation method of example 1, except that Lipase No.89445 was not added as in example 1.
The amine number, LD, of the emulsifiers prepared in examples 1 to 9 and comparative example, respectively, of the present invention 50 、BOD 5 /COD Cr The detection is carried out, and the detection results are shown in table 1.
Table 1 performance test of the primary biomass emulsifier
As is clear from Table 1, the main emulsifiers for biomass prepared in examples 1 to 9 of the present invention have amine values in the range of 8.95 to 30.55mgKOH/g, LD 50 ＞5000，BOD 5 /COD Cr 0.51 to 0.69. Moreover, example 9 shows that the biological enzyme has good catalytic ability after multiple uses.
Comparative analysis was conducted with comparative example 1, and the amine value of the product of comparative example 1, to which no bio-enzyme was added, was 705mgKOH/g, which is far higher than that of the emulsifiers prepared in examples 1 to 9, indicating that the emulsifiers of the present invention could not be prepared under low-temperature and normal-pressure conditions without adding bio-enzyme.
Comparative analysis was performed with comparative example 2, which is an emulsifier prepared by a general chemical method (the chemical method is generally not added with a solvent), requires a higher temperature and is fed with inert gas to prevent oxidation of the raw materials at a high temperature, and the emulsifier product has a higher amine value and a lower conversion rate.
Comparative analysis was performed with comparative example 3, which shows that the amine value of the product without the addition of the second lipase is 216mgKOH/g, which is far higher than the emulsifiers prepared in examples 1 to 9, indicating that the addition of only one lipase results in lower conversion of the product and affects the product properties.
In Table 1, the LDs of comparative examples 1 to 3 50 Value, BOD 5 /COD Cr The horizontal line at the value represents: because of higher amine number, lower conversion of product, LD 50 And BOD 5 /COD Cr No detection is required.
Example 10
The base oil is diesel oil: 80% (volume fraction), 20% calcium chloride aqueous solution: 20% (volume fraction)
Based on the total volume of diesel oil and calcium chloride aqueous solution: sequentially adding 2% of organic soil, 2% of biomass main emulsifier, 2% of auxiliary emulsifier and 4% of oxidized asphalt, stirring at high speed for 10 min, adding calcium chloride aqueous solution, stirring at high speed for 5 min, adding 3% of calcium oxide, stirring at high speed for 2 min, and barytes to adjust the drilling fluid density to 2.1g/cm 3 Stirring at high speed for 20min to obtain drilling fluid.
Example 11
The drilling fluid was obtained according to the preparation method of example 10, except that the volume ratio of diesel oil to calcium chloride aqueous solution was 65:35, the mass volume ratio of the biomass main emulsifier prepared in example 1 was 3%, the mass volume ratio of the auxiliary emulsifier was 3%, and the density was 1.2g/cm, as in example 10 3 。
Example 12
Drilling fluid obtained according to the preparation method of example 10, and example10 except that the volume ratio of diesel oil to calcium chloride aqueous solution was 100:0, the mass-to-volume ratio of the biomass main emulsifier prepared in example 1 was 3%, the mass-to-volume ratio of the auxiliary emulsifier was 3%, and the density was 2.1g/cm 3 。
Example 13
The drilling fluid was obtained according to the preparation method of example 10, except that the volume ratio of diesel oil to calcium chloride aqueous solution was 95:5, the mass volume ratio of the biomass main emulsifier prepared in example 1 was 3%, the mass volume ratio of the auxiliary emulsifier was 3%, and the density was 2.5g/cm, as in example 10 3 。
Example 14
The drilling fluid was obtained according to the preparation method of example 10, except that the biomass main emulsifier prepared in example 4 was used, unlike example 10.
Example 15
A drilling fluid was obtained according to the method of example 10, except that the biomass main emulsifier prepared in example 8 was used, unlike in example 10.
Example 16
Drilling fluids were obtained according to the method of example 10, except that the base oil was white oil, as in example 10.
Example 17
A drilling fluid was obtained according to the preparation method of example 10, except that the base oil was a biomass synthesis base fluid, unlike example 10.
Comparative example 4
A drilling fluid was obtained according to the preparation method of example 10, except that the main emulsifier SMEMUL-1 for oil-based mud and the auxiliary emulsifier SMEMUL-2 for oil-based mud purchased from Tiancheng chemical Co., ltd. In Jiyuan city were used in an amount of 3.0% and the auxiliary emulsifier was used in an amount of 3.0% respectively, as in example 10.
Example 18
The drilling fluids prepared in examples 10 to 17 and comparative example 4 were charged into an aging kettle, placed in a roller furnace, rolled at 130 to 200 ℃ for 16 hours according to the method described above, and then the properties of the drilling fluids were measured according to national standard GB/T16783.2-2012 drilling fluid field test part 2: oil-based drilling fluids were run at 65 ℃.
The test results are shown in Table 2, and Table 2 shows the results of performance tests of drilling fluids prepared in examples and comparative examples of the present invention.
Table 2 drilling fluid performance
Wherein AV is apparent viscosity, PV is plastic viscosity, YP is dynamic shear force, gel is initial and final shear, ES is demulsification voltage, and HTHP is high-temperature high-pressure fluid loss. The horizontal line in table 2 indicates that the maximum value of the instrument detection was reached, and the upper limit value thereof was 2048V.
As can be seen from Table 2, the drilling fluid prepared by using the biomass main emulsifier of the invention is suitable for a density of 1.2g/cm 3 ～2.5g/cm 3 The mineral oil-based and biomass synthesis-based drilling fluid system has good temperature resistance, the temperature resistance can reach 200 ℃, the rheological property is good, the high-temperature and high-pressure filtration loss is low, the minimum oil-water ratio can reach 65:35, and the demulsification voltage is more than 700V.
Compared with comparative example 4, the emulsion is comparable to the conventional oil-based drilling fluid formulated with the emulsifier. It can be seen that the drilling fluid prepared by the biomass main emulsifier has good rheological property and fluid loss control capability.
The biomass main emulsifier provided by the invention is prepared by adopting a biocatalysis method, and has the advantages of mild preparation conditions, low energy consumption in the preparation process, simplicity, convenience, easiness in implementation, environment friendliness and the like. The emulsifier prepared by the invention has the characteristics of environmental protection, no toxicity and easy biodegradation, and the applicable density is 1.2g/cm 3 ～2.5g/cm 3 The temperature resistance of the mineral oil-based and synthetic-based drilling fluid can reach 200 ℃, and the mineral oil-based and synthetic-based drilling fluid has good emulsifying effect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications to these embodiments can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications should also be considered as the scope of the present invention.
Claims (9)
1. The preparation method of the biomass main emulsifier comprises the following steps:
mixing long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine, and reacting in a solvent under the catalysis of composite lipase to obtain an amide biomass main emulsifier;
the long-chain fatty acid methyl ester is saturated or unsaturated fatty acid methyl ester with 14-23 carbon atoms; the short chain fatty acid methyl ester is saturated or unsaturated fatty acid methyl ester with 5-13 carbon atoms; the complex lipase comprises a first lipase acting on long chain lipase methyl ester and a second lipase acting on short chain fatty acid methyl ester, wherein the first lipase is selected from one of Novozym 435, lipozyme TLIM, lipozyme 435 and LipaseAYS Amano;
the second Lipase is selected from Lipase DF "Amano"15, lipozyme RMIM, lipomod TM One of L691MDP, lipase No.89445, and Lipase No. 62310.
2. The preparation method according to claim 1, wherein the first lipase is used in an amount of 1% -5% by mass of the long-chain fatty acid methyl ester; the dosage of the second lipase is 2-8% of the mass of the short chain fatty acid methyl ester.
3. The method of claim 1, wherein the polyamine is selected from one or more of aliphatic diamines and polyethylene polyamines; the polyamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentyenediamine, hexamethylenediamine, octylenediamine, nonylenediamine, decylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
4. The method according to claim 1, wherein the solvent is one of dodecyl methyl ether, amyl laurate and butyl tetradecyl ether.
5. The preparation method according to claim 1, characterized in that it comprises in particular:
adding long-chain fatty acid methyl ester, short-chain fatty acid methyl ester and polyamine into a reaction kettle according to the mole ratio of (0.9-1.1) in sequence under the stirring state; then adding composite lipase; adding solvent according to 20% -40% of total mass of long-chain fatty acid methyl ester, short-chain fatty acid methyl ester, polyamine and compound lipase, reacting for a certain time, decompressing and filtering to obtain the amide biomass main emulsifier, wherein unfiltered lipase can be reused.
6. The process according to claim 5, wherein the temperature of the reaction is 40 to 80 ℃.
7. The method according to claim 6, wherein the reaction time is 24 to 48 hours; the stirring speed is 200-350 rpm.
8. A biomass main emulsifier produced by the production method of any one of claims 1 to 7; the amine value of the biomass main emulsifier is 8.95-30.55 mgKOH/g.
9. A drilling fluid comprising the biomass main emulsifier of claim 8.
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