CN109021948A - A kind of preparation method of novel heavy crude thinner - Google Patents

Abstract

The invention discloses a preparation method of a novel heavy oil viscosity reducer, which uses methyl methacrylate, styrene, acrylamide and maleic anhydride as raw materials to prepare the heavy oil viscosity reducer through aqueous solution polymerization and physical compounding methods , the raw materials used are in the following proportions by weight: 30-50 parts of methyl methacrylate, 9-15 parts of styrene, 5-11 parts of acrylamide, and 3-5 parts of maleic anhydride. The invention uses an initiator to initiate the polymerization reaction of monomers to obtain an oil-soluble polymer, which can effectively reduce the viscosity of crude oil and increase the recovery rate of heavy oil by adding a small amount of the product to crude oil, and is suitable for the development and utilization of heavy oil oilfields.

Description

A kind of preparation method of novel heavy oil viscosity reducer

technical field

The invention relates to the field of preparation of oilfield chemical additives, in particular to a preparation method of a novel heavy oil viscosity reducer.

Background technique

With the continuous decline of recoverable volume and output of conventional crude oil, its exploitation can no longer meet people's demand for resources, and the exploitation of heavy oil has received extensive attention at home and abroad. The composition of heavy oil is relatively complex, containing a large amount of macromolecular organic matter such as wax, colloid, asphaltene, and a small amount of heavy metals, making its density and viscosity much higher than that of light crude oil. It has poor fluidity at room temperature and is extremely difficult to mine and transport. , the industrial cost is expensive. Therefore, reducing the viscosity of heavy oil and enhancing the fluidity of heavy oil has become a hot and difficult issue in the research of oilfield chemistry in recent years.

At present, the commonly used viscosity reduction methods are mainly physical and chemical viscosity reduction methods. The physical viscosity reduction method has the disadvantages of large fixed investment, high energy consumption, and short effective period of viscosity reduction. The chemical viscosity reduction method has poor temperature resistance and salt resistance, and the heavy oil produced is difficult to demulsify and dehydrate, and the processing capacity is large, which is greatly restricted in application. However, ordinary polypropylene amine polymers have low surface activity, poor affinity between molecules and heavy oil, and poor emulsification and viscosity reduction effects. The present invention uses methyl methacrylate, styrene, acrylamide, and maleic anhydride as raw materials to prepare an oil-soluble heavy oil viscosity reducer through aqueous solution polymerization and physical compounding. Effectively reduce the viscosity of crude oil and increase the recovery rate of heavy oil.

Contents of the invention

The object of the present invention is to provide a preparation method of a novel heavy oil viscosity reducer. The viscosity reducer is an oil-soluble polymer. Adding a small amount of the product to crude oil can effectively reduce the viscosity of crude oil.

A kind of preparation method of novel heavy oil viscosity reducer is characterized in that the method comprises the following steps:

Weigh 100 parts by weight of toluene and place it in a reaction kettle, then add 30-50 parts of methyl methacrylate, 9-15 parts of styrene, ultrasonically disperse for 30 minutes, then add 5-11 parts of maleic anhydride, 3-5 parts For acrylamide, raise the temperature of the reactor to 60°C and stir at constant temperature for 1-2 hours. After the monomer is completely dissolved, fill the reactor with 60% nitrogen and 40% neon for 30 minutes, then raise the temperature to 75-80°C. Slowly add 0.8 parts of benzoyl peroxide to the medium, keep the temperature down to 65-70°C after 4 hours of heat preservation reaction, add 16 parts of nano-KH550-CMK-3 composite materials and continue heat preservation reaction for 2-3 hours, and discharge to obtain a new type of heavy oil adhesive. The preparation method of the nanometer KH550-CMK-3 composite material is as follows:

Add 75 parts of absolute ethanol and 30 parts of deionized water into the flask, stir magnetically for 30 minutes to make it evenly mixed, then add 8 parts of silane coupling agent 3-triethoxysilyl-1-propylamine, Under ultrasonic treatment for 2 hours, add 45 parts of nanometer CMK-3 nanopowder, stir vigorously to make it uniformly dispersed, stir and react in a constant temperature oil bath at 80°C under nitrogen atmosphere for 3 hours, then centrifuge the product, wash with ethanol 3 to 5 times, 65 ℃ vacuum drying for 12 hours to obtain the intermediate product nano KH550/CMK-3; weigh 20 parts of octadecanoic acid and dissolve it in 50 parts of xylene, and then uniformly disperse the intermediate product nano KH550/CMK-3 in it under stirring. ℃ for constant temperature reaction for 3 hours, after centrifugation, microwave treatment at 140 ℃ for 2 hours in a microwave digestion apparatus, and vacuum drying at 65 ℃ for 12 hours to obtain nano KH550-CMK-3 composite material.

Beneficial effects: the present invention provides a preparation method of a novel heavy oil viscosity reducer. The production process of the agent is simple, and the raw materials are relatively easy to obtain. During the preparation process, an amide group is introduced, which can form with asphaltenes and other polar substances Hydrogen bonds, the viscosity reducer molecules can form hydrogen bonds to penetrate and disperse into the sheet-like molecules of colloid and asphaltene, break up the aggregates formed by overlapping and stacking planes, reduce the structural viscosity of crude oil, and the viscosity reducer polymer Molecular chains can stretch well in oil, destroying the formed spatial network structure. The introduction of nano-KH550-CMK-3 composite material, the nano-particles can be used as nucleation points to adsorb wax crystallization and precipitation on the surface by using special surface effects, changing the crystallization behavior of wax and destroying the original H-dimensional network structure of wax crystals ; At the same time, the strong polar groups introduced on the surface of the nanoparticles adsorb colloids and equicyanins to form a solvation layer on the surface through nitrogen bonds. The existence of the solvation layer can prevent the wax crystals from connecting to form a network structure, It can also dismantle the planar overlapping stacking structure of colloids and pyrenes in the original heavy oil system, thereby greatly reducing the viscosity of the heavy oil.

Detailed ways

Example 1

Weigh 100 parts by weight of toluene and place it in the reactor, then add 30 parts of methyl methacrylate and 9 parts of styrene, ultrasonically disperse for 30 minutes, then add 5 parts of maleic anhydride and 3 parts of acrylamide, and heat the reactor to Stir at a constant temperature of 60°C for 1-2 hours. After the monomer is completely dissolved, fill the reactor with 60% nitrogen and 40% neon for 30 minutes, then raise the temperature to 75-80°C, and slowly add 0.8 parts of benzene peroxide into the reactor. Formyl, heat preservation reaction for 4 hours, lower the temperature to 65-70°C, add 16 parts of nano-KH550-CMK-3 composite material, continue heat preservation reaction for 2-3 hours, and discharge to obtain a new type of heavy oil viscosity reducer.

The preparation method of the above-mentioned nanometer KH550-CMK-3 composite material is as follows:

Add 75 parts of absolute ethanol and 30 parts of deionized water into the flask, stir magnetically for 30 minutes to make it evenly mixed, then add 8 parts of silane coupling agent 3-triethoxysilyl-1-propylamine, Under ultrasonic treatment for 2 hours, add 45 parts of nano CMK-3 nano powder, stir vigorously to make it uniformly dispersed, stir and react in a constant temperature oil bath at 80°C under nitrogen atmosphere for 3 hours, then centrifuge the product, wash with ethanol 3 to 5 times, 65 ℃ vacuum drying for 12 hours to obtain the intermediate product nano KH550/CMK-3; weigh 20 parts of octadecanoic acid and dissolve it in 50 parts of xylene, and then uniformly disperse the intermediate product nano KH550/CMK-3 in it under stirring. ℃ for constant temperature reaction for 3 hours, after centrifugation, microwave treatment at 140 ℃ for 2 hours in a microwave digestion apparatus, and vacuum drying at 65 ℃ for 12 hours to obtain nano KH550-CMK-3 composite material.

Example 2

It is exactly the same as Example 1, except that 30 parts of methyl methacrylate, 12 parts of styrene, 11 parts of maleic anhydride and 4 parts of acrylamide are added.

Example 3

It is exactly the same as Example 1, except that 30 parts of methyl methacrylate, 15 parts of styrene, 8 parts of maleic anhydride and 5 parts of acrylamide are added.

Example 4

It is exactly the same as Example 1, except that 40 parts of methyl methacrylate, 12 parts of styrene, 8 parts of maleic anhydride and 3 parts of acrylamide are added.

Example 5

It is exactly the same as Example 1, except that 40 parts of methyl methacrylate, 9 parts of styrene, 11 parts of maleic anhydride, and 5 parts of acrylamide are added.

Example 6

It is exactly the same as Example 1, except that 40 parts of methyl methacrylate, 15 parts of styrene, 5 parts of maleic anhydride and 4 parts of acrylamide are added.

Example 7

It is exactly the same as Example 1, except that 50 parts of methyl methacrylate, 9 parts of styrene, 11 parts of maleic anhydride and 3 parts of acrylamide are added.

Example 8

It is exactly the same as Example 1, except that 50 parts of methyl methacrylate, 12 parts of styrene, 5 parts of maleic anhydride and 4 parts of acrylamide are added.

Example 9

It is exactly the same as Example 1, except that 50 parts of methyl methacrylate, 15 parts of styrene, 8 parts of maleic anhydride, and 5 parts of acrylamide are added.

Comparative example 1

Exactly the same as Example 1, the difference is: just do not add nanometer KH550-CMK-3 composite material.

Comparative example 2

It is exactly the same as Example 1, except that the nanometer KH550-CMK-3 composite material is replaced by nanometer CMK-3 nanopowder.

Comparative example 3

It is exactly the same as Example 1, except that absolute ethanol is not added when preparing the nanometer KH550-CMK-3 composite material.

Comparative example 4

It is exactly the same as Example 1, except that no ultrasonic treatment is carried out when preparing the nano KH550-CMK-3 composite material.

Comparative example 5

It is exactly the same as Example 1, except that the microwave treatment is not carried out under the microwave digestion apparatus when preparing the nanometer KH550-CMK-3 composite material.

Comparative example 6

It is exactly the same as Example 1, except that stearyl acrylate is used to replace methyl methacrylate when preparing the heavy oil viscosity reducer.

Comparative example 7

It is exactly the same as Example 1, except that maleic anhydride is not added when the heavy oil viscosity reducer is prepared.

Comparative example 8

It is exactly the same as Example 1, except that 60% nitrogen and 40% neon are not charged when the heavy oil viscosity reducer is prepared.

Comparative example 9

It is exactly the same as Example 1, except that the temperature is always kept at 65-70° C. when preparing the heavy oil viscosity reducer.

The heavy oil viscosity reducer prepared by Examples 1-9 of the present invention and Comparative Examples 1-9 is subjected to a performance test as follows:

Viscosity reduction performance test of heavy oil viscosity reducer

Take two 1000ml thick oils, one of which does not add a viscosity reducer, and the other adds a 50mg viscosity reducer, and puts it into a 50°C water bath for constant temperature stirring, and measures the viscosity of the two heavy oils respectively. Parallel measurement 3 times, take the average value, the calculation method of viscosity reduction rate is as follows.

ε _μ = (μ ₁ -μ ₂ )/μ ₁ ×100%

In the formula, ε _μ —viscosity reduction rate, %;

μ ₁ - is the viscosity of crude oil, mPa·s;

μ ₂ - is the viscosity of crude oil after adding viscosity reducer, mPa·s;

Table 1 Viscosity reduction performance test of heavy oil viscosity reducer

Embodiment 1-9 can find, when being in the proportioning environment in embodiment 1, the thick oil viscosity reducer effect of making is the best, has reached 79.2, and the heavy oil viscosity reducer prepared in embodiment 2-9 is not It is particularly ideal, only between 20-60%. It can be seen that the ratio of raw materials has a huge impact on the viscosity reduction rate of the entire product. The ratio of Example 1 has produced an unexpected viscosity reduction effect, as can be seen in the embodiment. The heavy oil viscosity reducer prepared under the raw material ratio described in 1 has a moderate molecular weight and the best solubility in crude oil. At this time, the viscosity reducer polymer and the nano KH550-CMK-3 composite material have the best synergy. The resulting heavy oil viscosity reducer has the best viscosity reduction performance. In addition, comparative examples 1 to 5 show that adding nano KH550-CMK-3 composite materials to the viscosity reducer polymer can significantly improve the viscosity reduction performance of the viscosity reducer. It shows that nano KH550 - The CMK-3 composite material and the synthesized polymer can reduce viscosity synergistically. Comparative examples 6 to 9 show that the conditions and raw material selection for the preparation of heavy oil viscosity reducer have a prominent impact on its viscosity reduction performance.

Claims (4)

1. a kind of preparation method of novel heavy crude thinner, it is characterised in that method includes the following steps:

It weighs 100 parts by weight of toluene to be placed in reaction kettle, then 30 ~ 50 parts of methyl methacrylates of addition, 9 ~ 15 parts of styrene, 5 ~ 11 parts of maleic anhydrides are sequentially added after ultrasonic disperse 30min, reaction kettle is warming up to 60 DEG C of constant temperature by 3 ~ 5 parts of acrylamides 1 ~ 2h of stirring is filled with 60% nitrogen and 40% neon 30min after monomer is completely dissolved into reaction kettle, then temperature is risen to 75 ~ 80 DEG C, it is slowly added to 0.8 part of benzoyl peroxide into reaction kettle, 65 ~ 70 DEG C are cooled the temperature to after insulation reaction 4h, is added 16 parts Nanometer KH550-CMK-3 composite material continues 2 ~ 3h of insulation reaction, and discharging obtains novel heavy crude thinner.

2. a kind of preparation method of novel heavy crude thinner according to claim 1, it is characterised in that reaction kettle in step 1) For ceramic electric heating reaction kettle.

3. a kind of preparation method of novel heavy crude thinner according to claim 1, it is characterised in that stir speed in step 2 Degree is about 300 ~ 400r/min.

4. a kind of preparation method of novel heavy crude thinner according to claim 1, it is characterised in that the nanometer KH550- CMK-3 composite material and preparation method thereof is as follows:

75 parts of dehydrated alcohols, 30 parts of deionized waters are added in flask, magnetic agitation 30min is uniformly mixed it, adds 8 parts Silane coupling agent 3- triethoxysilyl -1- propylamine, is ultrasonically treated 2h under ultrasonic oscillation instrument, 45 parts of nanometers is added CMK-3 nano powder, being vigorously stirred makes it be uniformly dispersed, and constant temperature oil bath is stirred to react product after 3h under 80 DEG C, nitrogen atmosphere Centrifuge separation, with ethanol washing 3 ~ 5 times, 65 DEG C of vacuum drying 12h obtain intermediate product nanometer KH550/CMK-3；Weigh 20 part ten Eight acid are dissolved in 50 parts of dimethylbenzene, and then intermediate product nanometer KH550/CMK-3 is dispersed under stiring wherein, 60 Isothermal reaction 3h at DEG C, 140 DEG C of microwave treatment 2h, 65 DEG C of vacuum drying 12h are received under microwave dissolver after centrifuge separation Rice KH550-CMK-3 composite material.