CN114057763A - Spiro compound for reducing viscosity and pour point of crude oil, crude oil viscosity reducing pour point depressant and preparation method of spiro compound - Google Patents
Spiro compound for reducing viscosity and pour point of crude oil, crude oil viscosity reducing pour point depressant and preparation method of spiro compound Download PDFInfo
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Abstract
The invention belongs to the field of crude oil treating agents, and particularly relates to a spiro compound for reducing viscosity and pour point of crude oil, a crude oil viscosity reduction pour point depressant and a preparation method thereof. The spiro compound for reducing viscosity and pour point of crude oil has the structures shown as the formula (1), the formula (2) and the formula (3). The spiro compound for reducing viscosity and pour point of crude oil provided by the invention has a double-helix structure with the tail end modified by long-chain aliphatic hydrocarbon or hydroxy aliphatic hydrocarbon, and can be eutectic with wax in the crude oil on two crossed planes according to the space characteristics of the double-helix structure, so that the growth direction of wax crystals can be changed, the structure is loose and is not easy to grow, and the pour point and the low-temperature viscosity of the crude oil are reduced; and the double-spiral structure has a stereo structure larger than a plane structure molecule, so that the colloid is not suitable for being tightly stacked, the interlayer distance is enlarged, and the interlayer distance is reducedLow viscosity due to gum.
Description
Technical Field
The invention belongs to the field of crude oil viscosity reduction pour point depressants, and particularly relates to a spiro compound for crude oil viscosity reduction and pour point depression, a crude oil viscosity reduction pour point depressant and a preparation method thereof.
Background
The crude oil fluidity improver can be added into crude oil to play roles of pour point depression, viscosity reduction, drag reduction and the like, thereby improving the fluidity of the crude oil. Types of crude oil fluidity improvers include primarily crude oil pour point depressants which lower the freezing point of the crude oil, crude oil drag reducers which lower the drag of the crude oil in the well or oil pipeline, and crude oil emulsification viscosity reducers which emulsify the crude oil into low viscosity oil-in-water emulsions.
The transportation of high-viscosity and high-condensation crude oil must adopt more powerful pumping equipment, and in order to achieve reasonable pumping capacity, the transportation system is required to be heated or the crude oil is required to be diluted. The viscosity and pour point of crude oils are currently reduced primarily by the use of viscosity reducing pour point depressants. Due to the use of the medicaments, the problems of poor fluidity, high viscosity and large flow resistance of the high-viscosity oil, heavy oil or thick oil in the process of production and transportation are solved.
At present, mainly used are comb polymers with alkyl long side chains, such as polyacrylic acid high-carbon alcohol ester, polyacrylic acid high-carbon amine amide, polymaleic acid high-carbon alcohol ester, polymaleic acid high-carbon amine amide and copolymers of monomers thereof or copolymers of monomers such as styrene and vinyl acetate. The polymer can be used as oil field chemicals such as a pour point depressant for high-freezing crude oil, a viscosity reducer for high-viscosity crude oil, a wax inhibitor for crude oil, a drag reducer for crude oil transportation and the like.
The Chinese patent with the granted publication number of CN106939157B discloses a double-chain oil-soluble thick oil viscosity reducer which takes styrene, vinyl acetate and double-long-chain maleic acid ester with the chain length of C12-C20 as raw materials, and carries out polymerization reaction in the presence of an initiator and a chain transfer agent to form a high-molecular chemical product.
Although the viscosity reduction effect of the polymer chemicals is good, the content of heavy components in the crude oil is increased, the quality of the crude oil is adversely affected, and the polymer chemicals are greatly affected by environmental factors such as temperature, illumination and the like and have poor stability.
Disclosure of Invention
The invention aims to provide a spiro compound for reducing viscosity and pour point of crude oil, which belongs to a micromolecule crude oil fluidity improver, does not increase the content of heavy components, and has no adverse effect on the quality of the crude oil; and the chemical composition is relatively stable, so that the stability of the product quality can be ensured.
The second purpose of the invention is to provide the crude oil viscosity-reducing pour-point depressant containing the spiro compound.
The third purpose of the invention is to provide a preparation method of the crude oil viscosity-reducing pour-point depressant.
In order to achieve the purpose, the technical scheme of the spiro compound for reducing viscosity and pour point of crude oil is as follows:
the spiro compound for reducing viscosity and pour point of crude oil has the structures shown as the formula (1), the formula (2) and the formula (3):
in the formula (1) -formula (3), R1、R2Each independently selected from: an aliphatic hydrocarbon group or a hydroxyaliphatic hydrocarbon group having 7 or more carbon atoms; the aliphatic hydrocarbon group is selected from saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group; the hydroxyl aliphatic hydrocarbon group is a hydroxyl group connected to at least one carbon of the carbon chain of the aliphatic hydrocarbon group.
The spiro compound for reducing viscosity and pour point of crude oil has a double-helix structure with the tail end modified by long-chain aliphatic hydrocarbon or hydroxy aliphatic hydrocarbon, and can be eutectic with wax in the crude oil on two crossed planes according to the space characteristics of the double-helix structure, so that the growth direction of wax crystals can be changed, the structure is loose and is not easy to grow, and the pour point and the low-temperature viscosity of the crude oil are reduced; and the double-spiral ring structure has a larger three-dimensional structure than a planar structure molecule, so that the colloid is not suitable for being tightly stacked, the interlayer distance is enlarged, and the viscosity caused by the colloid is reduced.
The spiro compound belongs to a micromolecular crude oil fluidity improver, the content of heavy components cannot be increased, and no adverse effect is caused on the quality of crude oil; and the chemical composition is relatively stable, so that the stability of the product quality can be ensured.
The saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group are the residual hydrocarbon groups of the saturated fatty acid and the unsaturated fatty acid after the carboxyl group is removed, and can be selected according to the type of the actual oil product and the affinity with the oil product, preferably, the structural general formula of the saturated aliphatic hydrocarbon group is CnH2n+1The structural general formula of the unsaturated aliphatic hydrocarbon group is CnH2n-1Wherein n is more than or equal to 7 and less than or equal to 22.
The hydroxyl aliphatic hydrocarbon group is a group remaining after carboxyl group removal of a hydroxyl fatty acid such as ricinoleic acid and the like, which is directly purchased from a commercial route or prepared by referring to the prior art such as CN110093213A, CN104099381A and the like. The selection can also be determined by referring to the corresponding crude oil variety, preferably, the structural general formula of the hydroxyl aliphatic hydrocarbon group is CnH2n-1O, wherein n is more than or equal to 7 and less than or equal to 22.
The technical scheme of the viscosity-reducing pour point depressant for crude oil is as follows:
the viscosity-reducing pour point depressant for crude oil comprises the spiro compound and a dispersant.
The crude oil viscosity-reducing pour point depressant is prepared by taking the spiro compound as a main material and matching with a dispersing agent, can be further dissolved by organic solvents such as benzene, toluene, xylene, n-butanol, coal tar and the like to be conveniently mixed and dispersed when being applied, and is added into crude oil according to the concentration of 100-1000mg/L in the crude oil, and the good viscosity-reducing pour point depressing effect can be achieved after uniform stirring.
The auxiliary agent can be selected by referring to the selection of the existing long-chain fatty acid ester crude oil viscosity-reducing pour-point depressant, preferably, the dispersing agent comprises polyoxyethylene ether and polyethylene glycol, and the mass ratio of the polyoxyethylene ether to the polyethylene glycol is (10-30) to (5-10); the polyoxyethylene ether is selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.
The technical scheme of the preparation method of the crude oil viscosity-reducing pour point depressant is as follows:
the preparation method of the crude oil viscosity-reducing pour point depressant comprises the following steps: performing condensation reaction on cyclohexanedione and a dihydroxy compound in a solvent in the presence of a catalyst to generate a spiro compound, wherein the dihydroxy compound is selected from fatty acid monoglyceride and/or monohydroxy fatty acid glyceride; and then mixing with the dispersant.
The preparation method of the crude oil viscosity-reducing pour point depressant provided by the invention utilizes the condensation reaction of cyclohexanedione and two dihydroxy compounds to form a double-spiro structure to prepare the double-spiro crude oil treating agent, and the raw material cost is low, the process is simple, and the preparation method is very suitable for large-scale popularization and application.
The catalyst is preferably selected from one or more of sodium hydrogen sulfate, potassium hydrogen sulfate, aluminum chloride, ferric chloride and zinc chloride, and the amount of the catalyst is 5-10% of the mass of the cyclohexanedione.
In order to simplify the reaction process and improve the condensation reaction efficiency, the condensation reaction is preferably a heating reflux reaction for 2-8 hours.
In order to increase the reaction yield and improve the industrial economy, it is preferable that the molar ratio of the dihydroxy compound to the cyclohexanedione is 100 (50-60).
In order to promote the rapid dispersion of the spiro compound in the crude oil, preferably, the dispersing agent comprises polyoxyethylene ether and polyethylene glycol, and the polyoxyethylene ether is selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether; the dosage of the polyoxyethylene ether is 10-30% of the mass of the dihydroxy compound, and the dosage of the polyethylene glycol is 5-10% of the mass of the dihydroxy compound.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
First, the specific embodiment of the spiro compound for reducing viscosity and pour point of crude oil
Example 1
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
example 2
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
example 3
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
example 4
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
example 5
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
example 6
The spiro compound for viscosity reduction and pour point depression of crude oil of the embodiment has the following structural formula:
second, specific examples of the viscosity-reducing pour-point depressant for crude oil of the present invention
Example 7
The crude oil viscosity-reducing pour-point depressant of the embodiment comprises the spiro compound of the embodiment 1 and a dispersant, wherein the dispersant comprises lauryl polyoxyethylene ether and polyethylene glycol (molecular weight is 200), and the mass ratio of the lauryl polyoxyethylene ether to the polyethylene glycol is 2: 1.
Example 8
The crude oil viscosity-reducing pour-point depressant of the embodiment comprises the spiro compound of the embodiment 2 and a dispersant, wherein the dispersant comprises cetyl alcohol polyoxyethylene ether and polyethylene glycol (molecular weight is 500), and the mass ratio of the cetyl alcohol polyoxyethylene ether to the polyethylene glycol is 3: 1.
Example 9
The crude oil viscosity-reducing pour-point depressant of the embodiment comprises the spiro compound of the embodiment 3 and a dispersant, wherein the dispersant comprises nonylphenol polyoxyethylene ether and polyethylene glycol (molecular weight is 1000), and the mass ratio of the nonylphenol polyoxyethylene ether to the polyethylene glycol is 3: 1.
Example 10
The crude oil viscosity-reducing pour-point depressant of the embodiment consists of the spiro compound of the embodiment 4 and a dispersant, wherein the dispersant consists of behenyl alcohol polyoxyethylene ether and polyethylene glycol (molecular weight is 2000), and the mass ratio of the behenyl alcohol polyoxyethylene ether to the polyethylene glycol is 4: 1.
Example 11
The crude oil viscosity-reducing pour-point depressant of the embodiment comprises the spiro compound of the embodiment 5 and a dispersant, wherein the dispersant comprises polyoxyethylene ether and polyethylene glycol (with a molecular weight of 10000) according to a mass ratio of 5:1, and the polyoxyethylene ether is a composition of octadecanol polyoxyethylene ether and nonylphenol polyoxyethylene ether with a mass ratio of 1: 2.
Third, the concrete embodiment of the preparation method of the viscosity-reducing pour-point depressant for crude oil of the invention
Example 12
The preparation method of the viscosity-reducing pour-point depressant for crude oil in this example is described in example 7, and specifically includes the following steps:
1) dispersing single-long-chain fatty glyceride into an organic solvent of which the volume is 2 times that of the single-long-chain fatty glyceride at normal temperature in a reaction container, and uniformly stirring, wherein the single-long-chain fatty glyceride is industrial monopalmitin and the organic solvent is industrial benzene;
2) adding cyclohexanedione with the amount of 50% of that of the monoglyceride of the single-long-chain fatty acid into the reaction vessel, adding a catalyst with the mass of 5% of that of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for 8 hours (the reflux temperature is 195 ℃) under stirring, and cooling to room temperature, wherein the cyclohexanedione is industrial-grade 1, 4-cyclohexanedione, and the catalyst is industrial-grade anhydrous sodium hydrogen sulfate;
3) adding polyoxyethylene ether accounting for 20% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 10% of the mass of the single long-chain fatty glyceride into the reaction container, and uniformly stirring, wherein the polyoxyethylene ether is industrial-grade lauryl polyoxyethylene ether, and the polyethylene glycol is a product with the industrial-grade molecular weight of 200; the mass ratio of the spiro compound to the lauryl alcohol polyoxyethylene ether to the polyethylene glycol is 7: 2: 1;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the reaction product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain spiro compound (crude oil treating agent with double spiro structure) derived from natural oil for nuclear magnetic resonance analysis.
The analysis result is as follows:1H NMR (D-DMSO,400MHz), δ:4.42(2H, b),4.36(4H, m),4.12(4H, s),3.96(4H, t, J ═ 7.6Hz),2.35(4H, t, J ═ 7.6Hz),1.61(4H, t, J ═ 7.6Hz),1.54(8H, t, J ═ 7.6Hz),1.26-1.34(48H, m),0.85(4H, t, J ═ 7.6 Hz). From the above analysis results, it was confirmed that the obtained product was the spiro compound of example 1.
Example 13
The preparation method of the viscosity-reducing pour-point depressant for crude oil in this example is described in example 8, and specifically includes the following steps:
1) dispersing single-long-chain fatty glyceride into an organic solvent of which the volume is 4 times that of the monoglyceride in a reaction vessel at normal temperature, and uniformly stirring, wherein the single-long-chain fatty glyceride is analytically pure glyceryl monooleate, and the organic solvent is analytically pure toluene;
2) adding cyclohexanedione with the amount of 60% of that of the monoglyceride of the single-long-chain fatty acid into the reaction vessel, adding a catalyst with the mass of 10% of that of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for 4 hours (the reflux temperature is 195 ℃) under stirring, and cooling to room temperature, wherein the cyclohexanedione is analytically pure 1, 4-cyclohexanedione, and the catalyst is analytically pure anhydrous potassium hydrogen sulfate;
3) adding polyoxyethylene ether accounting for 30% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 10% of the mass of the single long-chain fatty glyceride into the reaction container, and uniformly stirring, wherein the polyoxyethylene ether is analytically pure cetyl alcohol polyoxyethylene ether, and the polyethylene glycol is a product with the analytically pure molecular weight of 500; the weight ratio of the spiro compound to the cetyl alcohol polyoxyethylene ether to the polyethylene glycol is 6: 3: 1;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the reaction product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain spiro compound derived from natural oil for nuclear magnetic resonance analysis.
The analysis result is as follows:1h NMR (D-DMSO,400MHz), δ:5.38(4H, b),4.52(2H, m),4.12(4H, s),3.96(4H, t, J ═ 7.6Hz),2.37(4H, t, J ═ 7.6Hz),2.16(8H, t, J ═ 7.6Hz),1.58(8H, t, J ═ 7.6Hz),1.29-1.31(40H, m),0.85(4H, t, J ═ 7.6 Hz). From the above analysis results, it was confirmed that the obtained product was the spiro compound of example 2.
Example 14
The preparation method of the viscosity-reducing pour-point depressant for crude oil in this example is described in example 9, and specifically includes the following steps:
1) dispersing single-long-chain fatty glyceride into 5 times of organic solvent at normal temperature in a reaction vessel, and uniformly stirring, wherein the single-long-chain fatty glyceride is chemically pure glyceryl monostearate, and the organic solvent is chemically pure dimethylbenzene;
2) adding cyclohexanedione with the amount of 55% of that of the monoglyceride of the single-long-chain fatty acid into the reaction vessel, adding a catalyst with the mass of 8% of that of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for 5 hours (the reflux temperature is 195 ℃) under stirring, and cooling to room temperature, wherein the cyclohexanedione is chemically pure 1, 2-cyclohexanedione, and the catalyst is chemically pure anhydrous aluminum chloride;
3) adding polyoxyethylene ether accounting for 15% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 5% of the mass of the single long-chain fatty glyceride into the reaction container, and uniformly stirring, wherein the polyoxyethylene ether is chemically pure nonylphenol polyoxyethylene ether, and the polyethylene glycol is a product with the chemically pure molecular weight of 1000; the mass ratio of the spiro compound to the polyoxyethylene nonyl phenyl ether to the polyethylene glycol is 6: 3: 1;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the reaction product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain spiro compound derived from natural oil for nuclear magnetic resonance analysis.
The analysis result is as follows:1h NMR (D-DMSO,400MHz), δ:4.52(4H, b),4.41(4H, m),3.91(4H, s),3.76(4H, t, J ═ 7.6Hz),2.32(4H, t, J ═ 7.6Hz),1.71(8H, t, J ═ 7.6Hz),1.58(8H, t, J ═ 7.6Hz),1.26-1.31(56H, m),0.88(4H, t, J ═ 7.6 Hz). From the above analysis results, it was confirmed that the obtained product was the spiro compound of example 3.
Example 15
The preparation method of the viscosity-reducing pour-point depressant for crude oil in this example is described in example 10, and specifically includes the following steps:
1) dispersing single-long-chain fatty glyceride into an organic solvent of which the weight is 8 times that of the single-long-chain fatty glyceride at normal temperature in a reaction container, and uniformly stirring, wherein the single-long-chain fatty glyceride is industrial grade glycerol monoricinoleate, and the organic solvent is industrial grade coal tar;
2) adding cyclohexanedione accounting for 52% of the amount of the monoglyceride of the single-long-chain fatty acid into the reaction vessel, adding a catalyst accounting for 7% of the mass of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for 4 hours (the reaction temperature is 195 ℃) while stirring, and cooling to room temperature, wherein the cyclohexanedione is 1, 3-cyclohexanedione, and the catalyst is industrial anhydrous ferric chloride;
3) adding polyoxyethylene ether accounting for 20% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 5% of the mass of the single long-chain fatty glyceride into the reaction container, and uniformly stirring, wherein the polyoxyethylene ether is industrial-grade eicosanol polyoxyethylene ether, and the polyethylene glycol is a product with the industrial-grade molecular weight of 2000; the weight ratio of the spiro compound to the eicosanol polyoxyethylene ether to the polyethylene glycol is 5: 4: 1;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain spiro compound derived from natural oil for nuclear magnetic resonance analysis.
The analysis result is as follows:1h NMR (D-DMSO,400MHz), δ:5.46(4H, b),4.47(2H, m),4.07(2H, s),3.78(4H, t, J ═ 7.6Hz),3.58(2H, t, J ═ 7.6Hz),2.33(8H, t, J ═ 7.6Hz),2.91(2H, t, J ═ 7.6Hz),1.26-1.31(32H, m),0.86(4H, t, J ═ 7.6 Hz). From the above analysis results, it was confirmed that the obtained product was the spiro compound of example 4.
Example 16
The preparation method of the viscosity-reducing pour-point depressant for crude oil in this example is described in example 11, and specifically includes the following steps:
1) dispersing single-long-chain fatty glyceride into an organic solvent with the weight ratio of 9 times at normal temperature in a reaction vessel, and uniformly stirring, wherein the single-long-chain fatty glyceride is monocaprylic glyceride with the chemical purity mass ratio of 1:3, and the organic solvent is a composition of toluene and xylene with the chemical purity volume ratio of 1: 1;
2) adding cyclohexanedione with the amount of 60% of that of the monoglyceride of the single-long-chain fatty acid into the reaction vessel, adding a catalyst with the mass of 6% of that of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for reaction for 3 hours (reaction temperature is 195 ℃) under stirring, and cooling to room temperature, wherein the cyclohexanedione is analytically pure 1, 2-cyclohexanedione, and the catalyst is anhydrous sodium bisulfate and anhydrous potassium bisulfate with the analytically pure mass ratio of 1: 1;
3) adding polyoxyethylene ether accounting for 25% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 5% of the mass of the single long-chain fatty glyceride into the reaction container, uniformly stirring, wherein the polyoxyethylene ether is a composition of octadecanol polyoxyethylene ether and nonylphenol polyoxyethylene ether with an industrial mass ratio of 1:2, and the polyethylene glycol is a product with an industrial molecular weight of 10000; the weight ratio of the spiro compound to the dispersant is 4: 6, the dispersing agent consists of polyoxyethylene ether and polyethylene glycol (with the molecular weight of 10000) according to the mass ratio of 5:1, wherein the polyoxyethylene ether is a composition of octadecanol polyoxyethylene ether and nonylphenol polyoxyethylene ether with the mass ratio of 1: 2;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain spiro compound derived from natural oil for nuclear magnetic resonance analysis.
And (3) analysis results:1h NMR (D-DMSO,400MHz), δ:4.46(2H, b),4.30(4H, m),4.07(4H, s),3.71(4H, t, J ═ 7.6Hz),3.75(4H, t, J ═ 7.6Hz),2.29(4H, t, J ═ 7.6Hz),1.70(4H, t, J ═ 7.6Hz),1.62(4H, s),1.59(4H, s),1.26-1.33(16H, m),0.86(4H, t, J ═ 7.6 Hz). From the above analysis results, it was confirmed that the obtained product was the spiro compound of example 5.
Example 17
The preparation method of the viscosity-reducing pour point depressant for crude oil provided by the embodiment specifically comprises the following steps:
1) dispersing single-long-chain fatty glyceride into an organic solvent with the volume 6 times that of the single-long-chain fatty glyceride at normal temperature in a reaction container, and uniformly stirring, wherein the single-long-chain fatty glyceride is industrial monopalmitin, and the organic solvent is industrial benzene;
2) adding cyclohexanedione with the content of 52% of the mono-long-chain fatty glyceride substances into the reaction container, adding a catalyst with the mass of 7% of the cyclohexanedione, adding a water separator and a condensation reflux device on the reactor, heating and refluxing for reaction for 8 hours under stirring, and cooling to room temperature, wherein the cyclohexanedione is industrial grade 1, 3-cyclohexanedione, and the catalyst is industrial grade anhydrous ferric chloride;
3) adding polyoxyethylene ether accounting for 20% of the mass of the single long-chain fatty glyceride and polyethylene glycol accounting for 10% of the mass of the single long-chain fatty glyceride into the reaction container, and uniformly stirring, wherein the polyoxyethylene ether is industrial-grade cetyl alcohol polyoxyethylene ether, and the polyethylene glycol is an industrial-grade product with the molecular weight of 20000; the weight ratio of the spiro compound to the cetyl alcohol polyoxyethylene ether to the polyethylene glycol is 7: 2: 1;
4) filtering and removing insoluble substances in the mixture obtained in the step 3), concentrating the filtrate, and evaporating the organic solvent to obtain the crude oil viscosity-reducing pour point depressant.
Adding 4g of column chromatography silica gel into 2g of the product obtained in the step 2), and uniformly stirring until the solvent is completely volatilized to obtain the column chromatography silica gel loaded with the corresponding spiro compound. Loading 50g column chromatography silica gel into glass chromatography column with diameter of 3cm and length of 1.2m, uniformly spreading column chromatography silica gel loaded with corresponding spiro compound on the upper part, spreading column chromatography silica gel with thickness of 2cm, and adding absorbent cotton with height of 3cm on the upper part for buffering. After elution with 100ml of acetone, the column was washed with 100ml of acetone: eluting with chloroform-1: 1 (volume ratio), collecting the eluate, and evaporating to remove solvent to obtain natural oil surfactant for nuclear magnetic resonance analysis.
The analysis result is as follows:1H NMR(D-DMSO,400MHz),δ:7.31(2H,b),7.05(2H,m),6.86(4H,s),4.41(2H,t,J＝7.6Hz),4.20(4H,t,J＝7.6Hz),3.98(4H,t,J＝7.6Hz),2.61(4H,t,J＝7.6Hz),1.58(10H,s),1.59(4H,s),1.29-1.33(48H,m),0.86(4H,t,J＝7.6Hz)。
fourth, example of experiment
Crude oil viscosity reduction pour point depressants corresponding to examples 12-17 were subjected to crude oil viscosity reduction pour point depressants tests. The measurement of the viscosity and the condensation point of the crude oil is carried out by adopting a SY/T0520-2008 crude oil viscosity measurement rotational viscometer equilibrium method and a SY/T0541-2009 crude oil condensation point measurement method. The crude oil was tested as a thick oil with an initial viscosity of 46200mpa.s at 35 ℃ and a congealing point of 30.2 ℃.
The crude oil viscosity-reducing pour point depressant of example 12 is dissolved in benzene, and the mass ratio of the crude oil viscosity-reducing pour point depressant to the benzene is 1: 9, then adding the mixture into crude oil according to 100mg/L, uniformly stirring, measuring the solidifying point to be 26.7 ℃, measuring the viscosity of the crude oil to be 15708mPa.s at 35 ℃, and measuring the viscosity reduction rate to be 66% and the pour point to be 3.5 ℃.
The crude oil viscosity-reducing pour point depressant of example 13 is dissolved in toluene at a crude oil viscosity-reducing pour point depressant to toluene mass ratio of 1: 7, adding the mixture into crude oil according to 1000mg/L, uniformly stirring, measuring the condensation point to be 21.3 ℃, measuring the viscosity of the crude oil to be 11088mPa.s at the temperature of 35 ℃, and measuring the viscosity reduction rate to be 76% and the pour point to be 8.9 ℃.
The crude oil viscosity reducing pour point depressant of example 14 is dissolved in xylene with a mass ratio of the crude oil viscosity reducing pour point depressant to xylene of 1: 4, adding the mixture into crude oil according to the proportion of 300mg/L, uniformly stirring, measuring the solidifying point to be 26.7 ℃, measuring the viscosity of the crude oil to be 8778mPa.s at the temperature of 35 ℃, and measuring the viscosity reduction rate to be 81 percent and the pour point to be 3.5 ℃.
Dissolving the crude oil viscosity-reducing pour-point depressant of example 15 in n-butanol, wherein the mass ratio of the crude oil viscosity-reducing pour-point depressant to the n-butanol is 1: 19, then adding the mixture into crude oil according to 500mg/L, uniformly stirring, measuring the solidifying point to be 23.2 ℃, measuring the viscosity of the crude oil to be 14784mPa.s at 35 ℃, and measuring the viscosity reduction rate to be 68% and the pour point to be 7.0 ℃.
The crude oil viscosity-reducing pour point depressant of example 16 is dissolved in coal tar, and the mass ratio of the crude oil viscosity-reducing pour point depressant to the coal tar is 1: 11, then adding the mixture into crude oil according to 600mg/L, uniformly stirring, measuring the solidifying point to be 19.4 ℃, measuring the viscosity of the crude oil to be 18942mPa.s at 35 ℃, and enabling the viscosity reduction rate to reach more than 59 percent and the pour point to reach 10.8 ℃.
The crude oil viscosity reduction pour point depressant of example 17 is dissolved in coal tar, and the mass ratio of the crude oil viscosity reduction pour point depressant to the coal tar is 1: 14, adding the mixture into crude oil according to 800mg/L, uniformly stirring, measuring the condensation point to be 22 ℃, measuring the viscosity of the crude oil to be 15708mPa.s at 35 ℃, and measuring the viscosity reduction rate to be 66% and the viscosity reduction rate to be 8.2 ℃.
Claims (10)
1. The spiro compound for reducing viscosity and pour point of crude oil is characterized by having the structures shown as formula (1), formula (2) and formula (3):
in the formula (1) -formula (3), R1、R2Each independently selected from: an aliphatic hydrocarbon group or a hydroxyaliphatic hydrocarbon group having 7 or more carbon atoms; the aliphatic hydrocarbon group is selected from saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group; the hydroxyl aliphatic hydrocarbon group is a hydroxyl group connected to at least one carbon of the carbon chain of the aliphatic hydrocarbon group.
2. The spiro compound for viscosity reduction and pour point depression of crude oil according to claim 1, wherein the saturated aliphatic hydrocarbon group has a general structural formula of CnH2n+1The structural general formula of the unsaturated aliphatic hydrocarbon group is CnH2n-1Wherein n is more than or equal to 7 and less than or equal to 22.
3. The spiro compound for viscosity reduction and pour point depression of crude oil according to claim 1 or 2, wherein the hydroxy aliphatic hydrocarbon group has a general structural formula of CnH2n-1O, wherein n is more than or equal to 7 and less than or equal to 22.
4. A viscosity reducing pour point depressant for crude oil comprising the spiro compound according to any one of claims 1 to 3 and a dispersant.
5. The viscosity-reducing pour-point depressant for crude oil of claim 4, wherein the dispersant comprises polyoxyethylene ether and polyethylene glycol, and the mass ratio of the polyoxyethylene ether to the polyethylene glycol is (10-30) to (5-10); the polyoxyethylene ether is selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.
6. A method for preparing the viscosity-reducing pour point depressant for crude oil according to claim 4 or 5, which comprises the following steps: performing condensation reaction on cyclohexanedione and a dihydroxy compound in a solvent in the presence of a catalyst to generate a spiro compound, wherein the dihydroxy compound is selected from fatty acid monoglyceride and/or monohydroxy fatty acid glyceride; and then mixing with the dispersant.
7. The method for preparing the viscosity-reducing and pour-point-reducing agent for crude oil according to claim 6, wherein the catalyst is one or more selected from sodium bisulfate, potassium bisulfate, aluminum chloride, ferric chloride and zinc chloride, and the amount of the catalyst is 5-10% of the mass of cyclohexanedione.
8. The method for preparing the viscosity-reducing and pour-point-reducing agent for crude oil according to claim 6, wherein the condensation reaction is a heating reflux reaction for 2 to 8 hours.
9. The method for preparing the viscosity-reducing pour point depressant for crude oil according to claim 6, wherein the molar ratio of the dihydroxy compound to the cyclohexanedione is 100 (50-60).
10. The method for preparing the viscosity-reducing and pour-point-reducing agent for crude oil according to any one of claims 6 to 9, wherein the dispersing agent comprises polyoxyethylene ether and polyethylene glycol, and the polyoxyethylene ether is selected from fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether; the dosage of the polyoxyethylene ether is 10-30% of the mass of the dihydroxy compound, and the dosage of the polyethylene glycol is 5-10% of the mass of the dihydroxy compound.
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| CN116426259B (en) * | 2022-01-04 | 2024-04-30 | 唐山冀油瑞丰化工有限公司 | Crude oil viscosity-reducing pour point depressant and preparation method thereof |
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