Polyoxyethylene alkylphenol ether water-based wax inhibitor and preparation method and application thereof
Technical Field
The application relates to the technical field of oil field additives, in particular to a polyoxyethylene alkylphenol ether water-based wax inhibitor and a preparation method and application thereof.
Background
According to statistics, in oil fields in China, crude oil with the wax content higher than 10% accounts for about 90% of the total crude oil yield in China, and the mass fraction of the wax in most of the crude oil is more than 20%, and some crude oil even reaches 45% -50%. In the process of crude oil extraction, when crude oil flows into a well bottom from a stratum and then rises to a well head, the formation pressure and temperature are gradually reduced, and light components in the crude oil continuously escape, so that the solubility of the crude oil to wax is reduced, the wax is continuously separated out and deposited in a crystal form and is adsorbed on oil extraction equipment such as an oil well pipe wall, the oil well yield is continuously reduced, the wax is adsorbed on an oil layer part, and the oil reservoir is damaged.
At present, the paraffin removal and prevention technologies commonly used in oil fields mainly comprise a mechanical paraffin removal technology, a thermal paraffin removal technology, a surface energy paraffin prevention technology, a magnetic paraffin prevention technology, a microorganism paraffin removal and prevention technology, a chemical agent paraffin removal and prevention technology and the like, wherein the chemical agent paraffin removal and prevention technology is widely applied, and an oil-based paraffin removal and prevention agent, an emulsion paraffin removal and prevention agent and a water-based paraffin removal and prevention agent are most widely applied in the chemical agent paraffin removal and prevention agent.
However, the oil-based paraffin remover and inhibitor has strong capability of dissolving paraffin, but is flammable, explosive and high in toxicity, is easy to dilute by crude oil, is not suitable for crude oil with high water content, and is limited in application; the emulsion wax removing and preventing agent has no toxicity and is safe to use, but the stability of the emulsion wax removing and preventing agent needs to be improved; the water-based wax cleaning and preventing agent is safer to use and can be suitable for crude oil with high water content.
The water-based wax inhibitor provided in the prior art is mostly prepared by taking water as a carrier and compounding various conventional surfactants, and commonly used surfactants comprise sulfonate type, quaternary ammonium salt type, polyether type, Tween type and the like, but the traditional water-based wax inhibitor also has the problems of slow wax dissolution effect, low speed and poor wax dissolution effect, and the water-based wax inhibitor with a new molecular structure, which is designed for improving the wax dissolution speed and the wax prevention effect, cannot be provided in the prior art.
Disclosure of Invention
In order to solve the problems, the application designs a water-based wax inhibitor with a novel molecular structure aiming at improving the wax dissolution rate and the wax-proof effect of the wax inhibitor, and the water-based wax inhibitor is prepared by a specific preparation method.
In one aspect, the present application provides a polyoxyethylene alkylphenol ether water-based wax inhibitor having a structure represented by formula (I):
wherein R is1The group is a substituent with 12-18C atoms, R2The group is a C8-18 substituent, and the polymerization degree n of the polyoxyethylene ether is 3-10.
The paraffin inhibitor with the molecular structure introduces a substituted tertiary amine group structure and a glucose structure on the molecule of alkylphenol polyoxyethylene ether, wherein, besides the original alkylphenol polyoxyethylene ether part has oleophylic alkyl groups and hydrophilic polyoxyethylene groups, the paraffin inhibitor also has oleophylic R1 groups, hydrophilic amido and glucose groups.
The wax inhibitor with the molecular structure has both lipophilic groups and hydrophilic groups, so that certain surface activity can be shown, and after the wax inhibitor is added into an oil well, a layer of polar water film can be formed on the wall of an oil pipe and the surface of wax crystal particles respectively, and the existence of the polar water film can change the friction between fluid and a solid phase into the sliding between liquid phases, thereby greatly reducing the friction force, reducing the deposition probability of wax crystals, and on the other hand, the water wettability of the wall of the oil well pipe can be enhanced, so that the direct crystallization of paraffin on the surface of the pipe wall is prevented, and for the wax crystal particles, the non-polar wax crystal surface can be inverted into a polar surface, thereby inhibiting the adhesion of wax particles.
Therefore, based on the above principle, the molecules of the compound having surface activity are required to have a branched structure and good hydrophilicity when used for wax removal and prevention. Compared with the conventional alkylphenol polyoxyethylene ether, the paraffin inhibitor provided by the application has R on the tertiary amine group2The branched structure is added to the group, and the length of the branched structure is similar to that of a hydrocarbon chain of dissolved paraffin wax crystal particles, so that the molecule is easier to adsorb on a solid-liquid interface due to the similarity and intermiscibility principle, and the effects of better wetting the pipe wall and reversing the polarity of the wax crystal surface are achieved; and the introduced glucosyl group is a hydrophilic group with larger volume, has strong hydrophilicity, is more beneficial to forming a water film on the solid-liquid surface, finally improves the wax-dissolving effect rate, and obviously improves the wax-proofing effect.
In addition, the paraffin inhibitor with the molecular structure provided by the application also has good biodegradability. In the prior art, the polyoxyethylene group in the alkylphenol polyoxyethylene ether is generally considered to be hydrophilic, so that the higher the polymerization degree of the polyoxyethylene group is, the stronger the hydrophilicity is, and therefore, the polymerization degree of the conventional commercial alkylphenol polyoxyethylene ether is mostly 15-20, but the biodegradation efficiency at the polymerization degree is obviously reduced. The wax inhibitor provided by the application can still keep strong hydrophilicity under the condition that the polymerization degree of polyoxyethylene is small (n is 3-10), the biodegradation rate is high, short-chain oxyethyl groups generated after degradation are few, and the biodegradability of a glucose alkylamine part is good and the degradation rate is high. Therefore, the wax inhibitor has little pollution to the environment and better green, safe and environment-friendly properties.
In one embodiment, R1Group and R2The substituent group can be saturated hydrocarbyl, such as alkyl, unsaturated hydrocarbyl, such as alkylene, substituted alkyl phenyl, etc., and hydroxyl-OH, carboxyl-COOH, etc. can be connected on a certain carbon atom of the substituent group, wherein, R1Group and R2The group is preferably a hydrocarbon group, more preferably a saturated alkyl hydrocarbon.
Further, said R1The group is selected from-C12H25、-C14H29、-C16H33、-C18H37One of (1); the R is2The group is selected from saturated alkyl with 8-18C atoms.
Furthermore, the appearance of the polyoxyethylene alkylphenol ether water-based wax inhibitor is yellow liquid, the freezing point is less than or equal to minus 30 ℃, the density is 1.06-1.08 g/ml, the viscosity is 500-800 mPa.s, and the solid content is more than or equal to 98%.
In another aspect, the present application provides a method for preparing the above polyoxyethylene alkylphenol ether-based wax control agent, the method comprising the steps of:
the method comprises the following steps: dissolving substituted primary amine and glucose in n-butyl alcohol, reacting for 5-8 h at 40-50 ℃, cooling to room temperature, and separating out white floccule to obtain an intermediate A;
step two: dissolving the intermediate A and alkylphenol in ethanol, heating to 50-60 ℃, uniformly stirring, adding formaldehyde, heating to 75-80 ℃, performing reflux dehydration reaction for 10-12 hours, and performing vacuum dehydration and solvent removal after the reaction is finished to obtain an intermediate B;
step three: adding alkali powder into the xylene solution of the intermediate B, stirring and heating to 130-140 ℃, carrying out vacuum dehydration for 1-2 h, adding ethylene oxide, carrying out dehydration reaction for 6-8h at the temperature of 120-140 ℃ and under the pressure of less than or equal to 0.2MPa, cooling, and thus obtaining the polyoxyethylene alkylphenol ether water-based wax inhibitor.
Further, in the first step, the molar ratio of the substituted primary amine to the glucose is 1.1-1.5: 1.
Further, in the second step, the molar ratio of the intermediate A, the alkylphenol and the formaldehyde is (1.3-1.5): 1, (2-4); the formaldehyde is 37% formaldehyde solution or paraformaldehyde.
Furthermore, in the third step, the molar ratio of the intermediate B to the ethylene oxide is 1: 3-10.
Wherein, the chemical reaction process involved in the preparation process is as follows:
wherein R is1The group is C12-18 alkyl group, R2The group is C8-18 alkyl, and n is 3-10.
On the other hand, the application also provides the application of the polyoxyethylene alkylphenol ether water-based wax inhibitor and/or the polyoxyethylene alkylphenol ether water-based wax inhibitor prepared by the method in oil-gas well operation.
Further, the polyoxyethylene alkylphenol ether water-based wax inhibitor is independently prepared into an aqueous solution with the concentration of 0.05 wt% -5 wt% for use, or is compounded with a cosolvent and water to form a composition for use.
In one embodiment, the wax inhibitor provided by the application can obtain a fast wax dissolving rate and a remarkably improved wax dissolving effect when used alone; in another embodiment, to meet the requirements of different field conditions and oil fields, the wax inhibitor provided by the present application can be used as the main active ingredient of the water-based wax inhibitor composition and compounded with other additives, such as solubilizer, reversal agent, dispersant, stabilizer, etc., wherein the conventional additives can be selected and need not be described in detail herein.
In another aspect, the present application also provides a wax-proofing composition comprising the above polyoxyethylene alkylphenol ether water-based wax-proofing agent, and/or the polyoxyethylene alkylphenol ether water-based wax-proofing agent prepared by the above method, wherein the wax-proofing composition is composed of the following components: 0.05 wt% -5 wt% of polyoxyethylene alkylphenol ether water-based wax inhibitor, 15 wt% -25 wt% of ethanol and the balance of water.
The following beneficial effects can be brought through the application:
according to the water-based wax inhibitor, a substituted tertiary amine group structure and a glucose structure are introduced into molecules of alkylphenol ethoxylates, a series of novel polyoxyethylene ether alkylphenol water-based wax inhibitors are designed aiming at a wax-proofing mechanism and prepared by adopting a specific method, the molecular structure of the water-based wax inhibitor is provided with more branch structures and hydrophilic group glucosamine with larger volume, the wax-dissolving effect efficiency and the wax-proofing effect can be obviously improved, and the water-based wax inhibitor also has good biodegradability, is small in environmental pollution after degradation, and is a safe and environment-friendly green water-based wax inhibitor.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description of the overall scheme of the present invention is made by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
Unless otherwise specified, the starting components in the examples below are commercially available, and the laboratory instruments used are laboratory conventional laboratory instruments and the performance testing methods are those known in the art.
Example 1
The embodiment provides a polyoxyethylene ether alkylphenol water-based wax inhibitor, which is prepared by the following method:
the method comprises the following steps: 4.810g (26mmol) of dodecyl primary amine is dissolved in 50ml of n-butyl alcohol, 3.637g (20mmol) of anhydrous glucose is added, the mixture is uniformly mixed by magnetic stirring, the mixture is heated to 50 ℃ under the condition of water bath and reacts for 5 to 8 hours, the mixture is cooled after the reaction is finished, and the mixture is placed at the low temperature of 4 ℃ and stands for 12 hours, and a large amount of white floccules are separated out, namely an intermediate A;
step two: dissolving 0.05mol of nonylphenol in 100ml of ethanol, adding 0.07mol of intermediate A, magnetically stirring to mix and dissolve the nonylphenol, heating to 55 ℃, keeping the temperature for 30min, dropwise adding 37% formaldehyde solution, wherein the dropwise adding amount is 3 times of the molar amount of the nonylphenol, after the dropwise adding is finished, continuously heating to 79 ℃, performing reflux dehydration reaction for 10-12 h, and after the reaction is finished, performing dehydration and solvent removal under a vacuum condition to obtain an intermediate B;
step three: dissolving 1mmol of intermediate B in 50ml of dimethylbenzene, adding potassium hydroxide powder with twice molar amount based on the intermediate B, stirring and dissolving, heating to 130 ℃, performing vacuum dehydration for 1h, introducing ethylene oxide with 3.1 times molar amount based on the intermediate B, performing dehydration reaction for 5h at 120 ℃ and 0.2MPa, heating to 130 ℃, performing dehydration reaction for 2h at-0.3 MPa, cooling to about 30 ℃, and discharging to obtain the polyoxyethylene ether alkylphenol water-based wax inhibitor.
The polyoxyethylene ether alkylphenol water-based wax inhibitor obtained by the method has the following chemical formula:
the appearance of the polyoxyethylene ether alkylphenol water-based wax inhibitor is yellow transparent liquid, and the polyoxyethylene ether alkylphenol water-based wax inhibitor has the density of 1.08g/ml, the freezing point of less than or equal to-30 ℃, the flash point of 95 ℃, the viscosity of about 700mPa.s and the solid content of more than or equal to 98 percent according to the relevant standards of liquid petrochemical products.
Examples 2 to 12
Examples 2 to 12 each provide a polyoxyethylene ether alkylphenol-based wax inhibitor, which is prepared in substantially the same manner as in example 1, except that the type of alkyl primary amine used in the first step is different from that of alkyl phenol used in the second step, and both satisfy the following general formula:
wherein the polymerization degree of the polyoxyethylene group is 3, R1The group is selected from C12-18 saturated hydrocarbon alkyl, R2The group is selected from saturated hydrocarbon alkyl with 8-18 carbon atoms. Moreover, the appearance of the polyoxyethylene ether alkylphenol water-based paraffin inhibitor prepared in the embodiments 2 to 12 is yellow liquid, and according to the relevant standards of liquid petrochemical products, the freezing point of the water-based paraffin inhibitor in each embodiment is measured to be less than or equal to-30 ℃, the density is measured to be 1.06-1.08 g/ml, the flash point is measured to be 90-120 ℃, the viscosity is measured to be about 500-800 mPa.s, the solid content is greater than or equal to 98%, and the yield is measured to be 75-92%.
Comparative example 1
The comparative example adopts alkylphenol polyoxyethylene TX-10 which is commercially available and has better reaction effect and is purchased from a certain chemical company in Shandong.
Comparative example 2
This comparative example differs from example 1 in that, instead of carrying out step one, the intermediate A was directly replaced with primary dodecylamine and reacted with nonylphenol and formaldehyde, the remaining steps being identical, to obtain a paraffin inhibitor containing no glucosyl groups.
Comparative example 3
This comparative example differs from example 1 in that, without carrying out step one and step two, nonylphenol was directly reacted under alkaline conditions with 3.1 times the molar amount of ethylene oxide based on nonylphenol to obtain nonylphenol polyoxyethylene (3) ether.
Comparative example 4
This comparative example differs from example 1 in that only step one and step two, and not step three, are carried out, i.e., N-dodecylglucosamine is obtained.
The wax inhibitor of each example and each comparative example, ethanol and water are prepared into a field medicament, wherein the mass concentration of the wax inhibitor is 1 wt%, the wax inhibitor is dissolved by using 20 wt% of ethanol, and the balance is water. Testing the wax dissolving rate according to an operation method in SY/T6300-2009 paraffin removal and prevention agent technical conditions for oil extraction, and testing the wax prevention rate of crude oil on site aiming at a certain oil field area in the east China, wherein the detection method of the wax prevention rate comprises the following steps: and the mode of a vehicle-mounted high-pressure pump is adopted, so that pressurized impact type dosing is realized under the condition of no pumping stop. The impact type medicine adding can enable the medicine adding concentration to reach the maximum value instantly, so that deposited wax is removed efficiently, the pressure (bearing pressure) of a high-pressure pump is 2.5MPa, and the medicine adding period is once every 10 days.
Wherein, the wax content of the crude oil is 38.93%, and the oil temperature is 40 ℃. In the specific examples R1Group and R2The choice of groups, as well as the measured wax dissolution rate and wax control results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1, when paraffin control is performed on crude oil with high wax content under low temperature conditions, the water-based paraffin inhibitor provided in each example shows a significantly faster wax dissolution rate and a significantly improved paraffin control effect compared to the conventional common paraffin inhibitor on the market. As can be seen from comparison of each example and comparative examples 2-4, the wax control effect is significantly reduced by removing any group in the molecular structure, even inferior to that of the common wax control agent sold in the market, which indicates that each part of the group structure in the molecule provided by the present application has a large influence on the final wax control effect. At the same time, R is a fixed glucose group and a polymerization degree of a polyoxyethylene group of 31Group and R2The final wax control effect of the alkyl group selectivity of the group also has a certain influence, and is shown in R1The group is selected from saturated alkyl with 12-18 carbon atoms, R2When the group is selected from saturated alkyl with 8-18 carbon atoms, the wax-proof effect of the compound is optimal.
The water-based wax inhibitor obtained in the preferred embodiment is subjected to biodegradation tests by referring to national standard GB/T15818-2006, and the biodegradation rate is over 95%, the residual ethylene oxide chains after degradation are few, and the rest small molecules are pollution-free, safe and environment-friendly.
In addition, in the above performance tests, the compositions formulated with the water-based wax inhibitor provided herein are also examples provided herein and will not be described herein.
In conclusion, the novel polyoxyethylene ether alkylphenol water-based wax inhibitor which is designed aiming at the wax-proofing mechanism and prepared by adopting a specific method can show remarkably improved wax-dissolving effect efficiency and wax-proofing effect, and meanwhile, the novel polyoxyethylene ether alkylphenol water-based wax inhibitor has good biodegradability, has small environmental pollution after being degraded, and is a safe and environment-friendly green water-based wax inhibitor.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.