CN106701050B - A kind of heavy oil viscosity reducer, preparation method and application - Google Patents

Abstract

The invention discloses a thick oil viscosity reducer, which is obtained by reacting compounds represented by formula I, formula II and formula III; wherein n=13-17. The invention also provides a preparation method of the heavy oil viscosity reducer and an application of the heavy oil viscosity reducer. The heavy oil viscosity reducer provided by the application has good viscosity reduction effect and good solubility, and can be directly used for heavy oil gathering and transportation, and the preparation method of the heavy oil viscosity reducer provided by the application is simple;

Description

A kind of heavy oil viscosity reducer, preparation method and application

technical field

The invention relates to the technical field of oil gathering and transportation, in particular to a heavy oil viscosity reducer.

Background technique

With the continuous exploitation of oil, the proportion of heavy oil in the proven oil resources is increasing. In the situation of shortage of thin oil resources in the world, heavy oil will become an important substitute for oil resources. In the process of gathering and transportation, with the increase of heavy oil production, its characteristics of high density, high viscosity and poor fluidity have brought great difficulties to its development and application. Therefore, the advancement and economy of heavy oil gathering and transportation technology directly affect the comprehensive economic and technical indicators of crude oil production.

For a long time, the traditional ways of heating and emulsifying viscosity-reducing transportation for heavy oil have been mainly used at home and abroad. The former has high fuel consumption and high cost; the latter has post-processing problems and is not suitable for heavy oil with low water content. The commonly used viscosity reduction method in the heavy oil transportation process is mixed with thin oil for viscosity reduction transportation. Thin oil-mixed viscosity-reducing transportation is limited by the source of thin oil, and the price of thin oil is relatively expensive, so there is a problem of high cost.

In addition, after studying the structure of heavy oil, a viscosity-reducing method of viscosity-reducing agent was obtained. In the composition of heavy oil in my country, the high content of colloid and asphaltene is the main reason for the high viscosity of heavy oil. The colloid and asphaltene molecules are in a state of accumulation, which makes them "loose" in the accumulation layer under the action of high temperature or solvent specialty. Thick oil viscosity reducer is added to make the viscosity reducer molecules "infiltrate" between the colloid or asphaltene molecular layers to reduce the viscosity of heavy oil, so as to reduce the freezing point and viscosity of crude oil and make it easy to flow. However, the research time on viscosity reducing agents for heavy oil viscosity reduction is relatively short, and most of them are limited to laboratory research and field tests, and the viscosity reducing effect is not significant, and the viscosity reducing effect in high temperature areas is poor.

Contents of the invention

In view of this, the application provides a thick oil viscosity reducer. The heavy oil viscosity reducer has good viscosity reduction effect and good solubility, and has good universality for different oil fields, can be directly used in the heavy oil gathering and transportation process, and has a simple synthesis process.

In order to solve the above-mentioned technical problems, the present invention provides a heavy oil viscosity reducer, which is characterized in that the heavy oil viscosity reducer is obtained by reacting compounds represented by formula I, formula II and formula III;

Where n=13-17.

Preferably, said n=13, 15, 17.

Preferably, the n=17.

The invention provides a kind of preparation method of described heavy oil viscosity reducer, comprising:

a) mixing and dissolving the compounds shown in formula I, formula II and formula III to obtain a mixed solution;

Among them, n=13～17;

b) heating the mixed solution in step a) to obtain the thick oil viscosity reducer.

Preferably, the molar ratio of the compounds represented by the formula I, the formula II and the formula III is 1:(1-6):(1-6).

Preferably, the molar ratio of the compounds represented by the formula I, the formula II and the formula III is 1: (1-4): (1-4)

Preferably, the molar ratio of the compounds represented by the formula I, the formula II and the formula III is 1:2:2

Preferably, the solvent selected for dissolving in step a) is one or more of toluene, xylene or benzene.

Preferably, the solution is toluene.

Preferably, the step a) specifically includes: firstly mixing and dissolving the compound represented by the formula I and the formula II, and reacting, and then adding the compound represented by the formula III for reaction to obtain the mixture.

Preferably, the step b) is specifically: heating the mixed solution obtained in the step a), cooling and solidifying to obtain the thick oil viscosity reducer.

Preferably, the step b) specifically includes: adding a catalyst into the mixed solution and heating the mixed solution to obtain the thick oil viscosity reducer, and the catalyst accounts for 0.5% to 1.5% by weight of the mixture .

Preferably, the catalyst accounts for 1.0% by weight of the mixture.

Preferably, the catalyst is one or more of sulfuric acid or p-toluenesulfonic acid.

Preferably, the catalyst is p-toluenesulfonic acid.

Preferably, the heating temperature in step b) is 80-140°C.

Preferably, the heating temperature in step b) is 90-120°C.

The invention provides the application of the heavy oil viscosity reducer, which is used for reducing the viscosity of heavy oil with a viscosity of 10000-50000 mPa·s.

Preferably, the viscosity is 20000-45000 mPa·s.

Preferably, the viscosity is 20000-40000 mPa·s.

The application is compared with the prior art, and its detailed description is as follows:

The heavy oil viscosity reducer provided by the invention contains C18 long chain alkyl and benzene ring. On the one hand, the long-chain alkyl group makes it form a comb polymer, which co-crystallizes with the wax in the heavy oil, thereby changing the state of the wax crystal, making it difficult to form and expand the three-dimensional network structure in space. On the other hand, the long-chain alkyl group increases the steric hindrance of the viscosity reducer. When the viscosity reducer breaks up the asphaltene and colloidal structure and prevents the heavy oil from changing in temperature and other conditions, the asphaltene in the heavy oil , Reconstruction of colloid molecules to form new hydrogen bonds, inhibit the aggregation of asphaltenes and colloids and reduce the adsorption and growth of paraffin on the surface, thereby effectively reducing the viscosity of heavy oil. The viscosity reducer provided by the invention also has a benzene ring, which is beneficial to the interaction between the viscosity reducer and the colloid with a ring structure, and can reduce the viscosity of heavy oil more effectively. For ultra-heavy oil, the viscosity reduction rate can reach up to 60%, which reduces the viscosity of heavy oil from 30000mPa·s to 12000mPa·s, significantly improves the low-temperature fluidity of heavy oil, and has a better viscosity reduction effect than common viscosity reducers on the market .

The heavy oil viscosity reducer provided by the invention contains C18 hydrophobic groups in its molecular structure, has good solubility and does not need to be dissolved in a solvent, and can be directly used in the process of oil and gas gathering and transportation.

The raw materials used in the present invention have wide sources and low cost, and will not cause corrosion to subsequent oil refining equipment, and are energy-saving and environment-friendly.

The preparation method provided by the invention has simple production process, convenient operation method, short reaction time, automatic continuous production can be realized, high degree of mechanization, and is suitable for popularization and industrial production.

Description of drawings

Fig. 1 is the infrared spectrogram of the heavy oil viscosity reducer provided by the present invention.

Detailed ways

In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with specific examples.

The invention provides a heavy oil viscosity reducer, which is obtained by reacting compounds represented by formula I, formula II and formula III;

Where n=13-17.

Preferably, n=13, 15, 17, more preferably n=17. In some embodiments provided by the present invention, the n=13; in some embodiments provided by the present invention, the n=15; in other embodiments provided by the present invention, the n= 17.

The invention provides a kind of preparation method of described heavy oil viscosity reducer, comprising:

a) mixing and dissolving the compounds shown in the formula I, the formula II and the formula III to obtain a mixed solution;

b) heating the mixed solution in step a) to obtain the thick oil viscosity reducer.

Preferably, the molar ratio of the compounds represented by the formula I, the formula II and the formula III is 1:(1-6):(1-6), more preferably 1:(1-4):(1 ~4), optimally 1:2:2; in some embodiments provided by the present invention, the molar ratio is preferably 1:1:1; in some embodiments provided by the present invention, the molar ratio The ratio is preferably 1:1.5:2.5; in some embodiments provided by the present invention, the molar ratio is preferably 1:2:2; in some embodiments provided by the present invention, the molar ratio is preferably 1 : 2:4; in some embodiments provided by the present invention, the molar ratio is preferably 1:2.5:2.5; in some embodiments provided by the present invention, the molar ratio is preferably 1:4:2 ; In some embodiments provided by the present invention, the molar ratio is preferably 1:4:4; in some embodiments provided by the present invention, the molar ratio is preferably 1:4:6; in the present invention In other examples provided, the molar ratio is preferably 1:6:4.

Preferably, the solvent selected for dissolving in step a) is one or more of toluene, xylene or benzene. More preferred is toluene.

Preferably, the step a) specifically includes: firstly mixing and dissolving the compound represented by the formula I and the formula II, and reacting, and then adding the compound represented by the formula III for reaction to obtain the mixture.

Preferably, the step b) is specifically: heating the mixed solution obtained in the step a), cooling and solidifying to obtain the thick oil viscosity reducer.

Preferably, the step b) specifically includes: adding a catalyst into the mixed solution and heating, and after the mixed solution is completely reacted, the thick oil viscosity reducer is obtained, and the catalyst accounts for 0.5% by weight of the mixture ~1.5%. More preferably, it is 1.0%.

Preferably, the catalyst is one or more of p-toluenesulfonic acid or sulfuric acid; more preferably, p-toluenesulfonic acid.

Preferably, the heating temperature in step c) is 80-140°C; more preferably, 90-120°C.

The present invention also provides the application of the heavy oil viscosity reducer, the heavy oil viscosity reducer is used to reduce the viscosity of heavy oil with a viscosity of 10000-50000mPa·s, preferably, the viscosity is 20000-45000mPa·s ; More preferably, the viscosity is 20000-40000mPa·s.

The structural formula of the compound described in formula I is So the thick oil viscosity reducer provided by the invention is by the compound described in formula I as crosslinking agent, has Repeating units, wherein R ₁ to R ₄ can be substituents of formula IV to formula VIII in Table 1.

Table 1 R ₁ ~ R ₄ substituents

-OH

Formula IV

-OC ₁₈ H ₃₇

Formula V

The scheme of the present invention is described in detail below with specific examples.

Embodiment 1-5

Add the compound shown in formula I, formula II and formula III in the reactor successively, n=17; In mass percentage, add the toluene of 30%～50% mass of total mass in the above-mentioned reactant as solvent and the total amount of reaction raw materials Use 1% p-toluenesulfonic acid as a catalyst, stir evenly, and react at 100°C for 2 hours to obtain a liquid product, and place it at room temperature for 5 hours. After the liquid solidifies, a thick oil viscosity reducer is obtained.

To evaluate the viscosity-reducing effect of heavy oil viscosity reducer, first take 1000ml of heavy oil and place it at 50°C to stir evenly. After two hours, take 100ml of the heavy oil and use NDJB-8S digital display viscometer to measure its viscosity, which is Viscosity of heavy oil.

Select heavy oil with a viscosity of 30000mPa·s. Add 50 mg of the product 1 obtained in Example 1 to 100 ml of heavy oil, and then stir evenly at 50°C for two hours, then measure its viscosity with a NDJB-8S digital display viscometer, and obtain the thick oil after adding product 1 Viscosity, and calculate the viscosity reduction rate; With the embodiment 1～9 that only reaction raw material molar ratio is different with embodiment 1, thick oil viscosity reduction agent is made, according to the above-mentioned method adding viscosity is in the obtained heavy oil of 30000mPa s, Measure the viscosity of heavy oil after viscosity reduction respectively, and calculate the viscosity reduction rate. The results are shown in Table 2.

Table 2

Examples 10-12

Add the compounds shown in the formula I, the formula II and the formula III respectively in the reactor successively, n is 13, 15, 17 respectively, and the compounds shown in the formula I, the formula II and the formula III The molar ratio of the compounds is 1:2:2; take 0.68g of the compound shown in Formula I, take the compound shown in Formula II according to Table 3, take 1.48g of the compound shown in Formula III, and add 30% xylene as a solvent and 1% p-toluenesulfonic acid as a catalyst of the total mass of the reaction raw materials, stirred evenly and reacted at a temperature of 100°C for 2 hours to obtain a liquid product, placed at room temperature for 5 hours, and after the liquid solidified, obtained Thick oil viscosity reducer.

According to the evaluation method of Example 1, the viscosity of the obtained heavy oil with a viscosity of 30000 mPa·s was reduced by adding the product prepared above to reduce the viscosity, and the viscosity reduction rate was calculated. The measurement results are shown in Table 3.

table 3

In summary, in the preparation method of the heavy oil viscosity reducer provided by the present invention, the heavy oil viscosity reducer prepared by the compound shown in the formula I, the formula II and the formula III, the compound shown in the formula II n=13-17 can effectively reduce the viscosity of heavy oil; the compound represented by the formula II with n=15-17 has the best viscosity-reducing effect. Wherein the compound n=17 shown in the formula II has the best viscosity-reducing effect, because the compound n=17 shown in the formula II is stearyl alcohol, and the normal paraffin content of 18 carbon atoms is relatively more in crude oil , the viscosity reducer has the best dissolution effect at this time, and it is easier to play a role.

Examples 13-19

Add 1.36g of the compound shown in the formula I, 2.70g of the compound shown in the formula II n=17 and 1.48g of the compound shown in the formula III in the reactor successively; add 30% of the total mass of the reaction raw materials in the above-mentioned reactant Toluene was used as solvent and 1.5% p-toluenesulfonic acid of the total mass of the reaction raw materials was used as catalyst, stirred evenly and reacted at different temperatures for 2 hours, the reaction temperatures were 80°C, 90°C, 100°C, 110°C, 80°C, 120°C °C, a liquid product was obtained, and it was placed at room temperature for 5 hours. After the liquid solidified, a thick oil viscosity reducer was obtained.

According to the evaluation method of Example 1, the viscosity of the heavy oil with a viscosity of 30000 mPa·s was reduced by adding the product prepared above to reduce the viscosity, and the viscosity reduction rate was calculated. The measured structure is shown in Table 4.

Table 4

In summary, the heating temperature in the preparation method of the heavy oil viscosity reducer provided by the present invention is 80-140°C; more preferably, 90-120°C; most preferably, 100°C, and the prepared heavy oil viscosity reducer , can effectively reduce the viscosity of heavy oil.

Examples 20-24

In the reactor, add the compound shown in 1.36g formula I, 2.70g compound shown in formula II n=17 and 1.48g compound shown in formula III in succession; Add 30% of the total mass of reaction raw materials in the above-mentioned reactant Toluene as a solvent and 1% p-toluenesulfonic acid as a catalyst of the total mass of the reaction raw materials, stirred evenly and reacted at 100°C for 2 hours to obtain a liquid product, placed at room temperature for 5 hours, after the liquid solidified, a thick oil with reduced viscosity was obtained agent.

According to the evaluation method of Example 1, the viscosities of the heavy oil after adding the product prepared above to reduce the viscosity of the heavy oil of different viscosities are measured, and the selected heavy oil viscosities are respectively 10000mPa s, 20000mPa s, 30000mPa s, 40000mPa s, 50000mPa·s, and calculate the viscosity reduction rate. The measured structure is shown in Table 5.

table 5

To sum up, the viscosity reduction rate of ultra-heavy oil with a viscosity of 10,000-50,000 mPa·s can reach up to 60%, which can significantly reduce the flow viscosity of heavy oil in pipeline transportation, and the viscosity reduction effect is good.

The above are only preferred implementations of the present invention. It should be noted that the above preferred implementations should not be regarded as limiting the present invention, and the scope of protection of the present invention should be based on the scope defined in the claims. For those skilled in the art, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (9)

1. A heavy oil viscosity reducer, characterized in that, the heavy oil viscosity reducer is obtained by reacting compounds shown in formula I, formula II and formula III; said formula I, said formula II and said formula The molar ratio of the compound shown in III is 1:(1～6):(1～6); Where n=13-17. 2. The heavy oil viscosity reducer according to claim 1, characterized in that, said n=13, 15, 17. 3. a kind of preparation method of heavy oil viscosity reducer, it is characterized in that, comprising: a) Mix and dissolve the compounds shown in formula I, formula II and formula III to obtain a mixed solution; the molar ratio of the compounds shown in formula I, formula II and formula III is 1: (1-6) :(1~6); Among them, n=13～17; b) heating the mixed solution in a) to obtain the viscous oil of the thick oil. 4. The preparation method according to claim 3, characterized in that, the selected solvent for dissolving in the step a) is one or more of toluene, xylene or benzene. 5. The preparation method according to claim 3, wherein the step b) is specifically: heating the mixed solution obtained in the step a) to obtain the thick oil viscosity reducer. 6. according to the described preparation method of claim 3, it is characterized in that, described step b) is specifically: add catalyst in described mixed solution, heat, obtain described thick oil viscosity reducer; Described catalyst occupies described mixture The weight percentage is 0.5%-1.5%. 7. according to the described preparation method of claim 6, it is characterized in that, described catalyst is one or more in sulfuric acid or p-toluenesulfonic acid. 8. The preparation method according to claim 3, characterized in that, the heating temperature in the step c) is 80-140°C. 9. The application of the heavy oil viscosity reducer according to claim 1, characterized in that the heavy oil viscosity reducer is used to reduce the heavy oil with a viscosity of 10000-50000 mPa·s.