CN103193971B - The poly(propylene oxide) oil head being initiator with dihydrogenated tallow secondary amine and block polymer demulsifier and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of the poly(propylene oxide) oil head and block polymer demulsifier and preparation method thereof that are initiator with dihydrogenated tallow secondary amine of preparing technical field of block polymer demulsifier, the present invention with dihydrogenated tallow secondary amine for initiator, under high-temperature and high-pressure conditions, obtained a kind of with dihydrogenated tallow secondary amine be initiator oxyethane and propylene oxide block polyether demulsification agent by propylene oxide and epoxyethane ring-expansion polymerization.The emulsion splitter of this invention, gathers the O/W type emulsion of driving rear generation for oil field and has good demulsification.

Description

Polypropylene oxide oil head and block polyether demulsifier using dihydrogenated tallow-based secondary amine as initiator and preparation method thereof

technical field

The present invention relates to the preparation of a block polyether demulsifier, especially a polypropylene oxide oil head and ethylene oxide and propylene oxide block polyether with dihydrogenated tallow-based secondary amine as the initiator Demulsifier and method for its preparation.

Background technique

At present, many domestic oilfields have entered the stage of full-scale polymer injection, and the properties of polymer flooding fluids are quite different from those of water flooding fluids: (1) the degree of oil-water emulsification is high, and the stability of oil-water emulsions is strong; (2) with the With the increase of the water content of the produced fluid, the emulsion type of the produced fluid also changed significantly, and the emulsion type changed from the water-in-oil type (W/O) in the early stage of oilfield development to the oil-in-water type (O/W) and water-in-oil-in-water (W/O/W) multiple emulsions. These characteristics have brought many difficulties to the treatment of produced fluid, such as: the original demulsifier is not suitable for the treatment of polymer injection produced fluid, resulting in a significant increase in its consumption; the water content of crude oil after dehydration exceeds the standard and the oil content in separated produced water substantial improvement. So far, the demulsifiers used in various oilfields are mainly proposed for the W/O type crude oil emulsion after water flooding, and there is little work on demulsifiers for the O/W type crude oil emulsion produced after polymer flooding. Therefore, research on demulsifiers for O/W production fluid produced after polymer flooding is of great significance.

Contents of the invention

The object of the present invention is to provide polypropylene oxide oil head and ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow base secondary amine as initiator and its preparation method.

The present invention provides a polypropylene oxide oil head (DHCA-x) with dihydrogenated tallow-based secondary amine as the starting agent, and its structural formula is shown in formula (I):

Wherein R=C ₁₆ -C ₁₈ , x represents the mass ratio of propylene oxide to dihydrogenated tallow-based secondary amine, and x=34, 40, 45, 51 or 57.

The present invention provides a method for preparing polypropylene oxide oil head represented by the above formula (I) with dihydrogenated tallow-based secondary amine as a starting agent, which comprises the following steps: adding dihydrogenated tallow-based secondary amine and a catalyst to High-temperature and high-pressure reaction kettle, seal the reaction kettle well, use nitrogen purge replacement before heating up, and then vacuumize, first nitrogen purge replacement and then vacuumize the operation repeated at least twice, then start stirring and heat up to the reaction temperature, then add Propylene oxide is reacted under high temperature and high pressure until the pressure in the kettle is 0 MPa, and finally the temperature is lowered and the kettle is discharged to obtain a polypropylene oxide oil head with dihydrogenated tallow-based secondary amine as the initiator;

In the above preparation method, the reaction pressure should be controlled at 0-0.4 MPa; the reaction temperature is 120-150°C, preferably 130°C.

In the above preparation method, the mass ratio of propylene oxide to dihydrogenated tallow-based secondary amine may specifically be 34, 40, 45, 51 or 57.

In the above preparation method, the catalyst is potassium hydroxide, sodium hydroxide, barium hydroxide or calcium acetate.

In the above preparation method, the amount of the catalyst is 0.2%-0.6% of the sum of the mass of the reaction raw materials (dihydrogenated tallow-based secondary amine and propylene oxide), preferably 0.3%.

The present invention provides an ethylene oxide and propylene oxide block polyether demulsifier (DHCA-x-mnp) with dihydrogenated tallow-based secondary amine as the initiator, and its structural formula is shown in formula (II):

Among them, m, n and p respectively represent the quality of polypropylene oxide oil head, ethylene oxide block and propylene oxide block with dihydrogenated tallow base secondary amine as the initiator in the demulsifier, m: n : p represents the mass ratio of polypropylene oxide oil head, ethylene oxide block and propylene oxide block in the demulsifier with dihydrogenated tallow-based secondary amine as the initiator, R=C ₁₆ -C ₁₈ , x represents the mass ratio of propylene oxide to dihydrogenated tallow-based secondary amine, x=34, 40, 45, 51 or 57.

In the ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow base secondary amine as initiator of the present invention, polypropylene oxide oil with dihydrogenated tallow base secondary amine as initiator The mass ratio of the head, the ethylene oxide block and the propylene oxide block may specifically be 1:6:3, 1:6:6, 1:6:9 or 1:6:12.

The above-mentioned ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow-based secondary amine as the initiator has a molecular weight of 1107-3155 g/mol.

The cloud point of the above-mentioned ethylene oxide and propylene oxide block polyether demulsifier using dihydrogenated tallow-based secondary amine as an initiator is 24.2-32.3°C.

The present invention provides a preparation method of an ethylene oxide and propylene oxide block polyether demulsifier represented by the above formula (II) using dihydrogenated tallow-based secondary amine as an initiator, which comprises the following steps: Add polypropylene oxide oil head and catalyst with dihydrogenated tallow-based secondary amine as the initiator in the reaction kettle, seal the reaction kettle well, use nitrogen purge replacement before heating up, then vacuumize, nitrogen purge replacement first Repeat the vacuuming operation at least twice, then start stirring and heat up to the reaction temperature, then add ethylene oxide, and react under high temperature and high pressure until the pressure in the kettle is 0 MPa; then add propylene oxide, and react to the kettle under high temperature and high pressure The internal pressure is 0 MPa, that is, the reaction is over, and finally the temperature is lowered and the kettle is discharged to obtain an ethylene oxide and propylene oxide block polyether demulsifier using dihydrogenated tallow-based secondary amine as an initiator;

In the preparation method of the above block polyether demulsifier, the pressure during the reaction should be controlled at 0-0.4 MPa, and the temperature during the reaction should be controlled at 120-150°C, preferably 130°C.

In the preparation method of the above-mentioned block polyether demulsifier, the mass ratio of polypropylene oxide oil head, ethylene oxide and propylene oxide added with dihydrogenated tallow-based secondary amine as the initiator can be specifically 1:6 :3, 1:6:6, 1:6:9 or 1:6:12.

In the above method for preparing the block polyether demulsifier, the catalyst is selected from potassium hydroxide, sodium hydroxide, barium hydroxide or calcium acetate.

In the preparation method of the above-mentioned block polyether demulsifier, the amount of catalyst used is the sum of the mass of the reaction raw materials (polypropylene oxide oil head, ethylene oxide and propylene oxide with dihydrogenated tallow base secondary amine as initiator) 0.2%-0.6%, preferably 0.3%.

The present invention uses dihydrogenated tallow-based secondary amine as the initiator, and obtains a ring-opening polymerization of dihydrogenated tallow-based secondary amine through the ring-opening polymerization of propylene oxide and ethylene oxide under high temperature and high pressure conditions. Ethylene oxide and propylene oxide block polyether demulsifier. The demulsifier of the invention has a good demulsification effect on the O/W emulsion produced after polymer flooding in oilfields.

Detailed ways

The following examples can enable those skilled in the art to understand the present invention more comprehensively, but do not limit the present invention in any way.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.

Embodiment 1, the preparation of the polypropylene oxide oil head that dihydrogenated tallow base secondary amine is starter

Add 10 g of dihydrogenated tallow-based secondary amine and 1.38 g of potassium hydroxide into a high-temperature and high-pressure reactor, and seal the reactor well. Before heating up, use nitrogen to blow and replace, then use a vacuum pump to evacuate, repeat twice, then start stirring and heat up, stop heating when the temperature rises to 120°C, open the feed valve, drop 450g of propylene oxide, and control the reaction The temperature does not exceed 140°C and the pressure is controlled below 0.4MPa. After the reaction of the material is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa. Finally, the temperature is lowered and the kettle is discharged to obtain dihydrogenated tallow-based secondary amine as the initiator. Polypropylene oxide oil head, marked DHCA-45.

Embodiment 2, the preparation of the polypropylene oxide oil head that dihydrogenated tallow base secondary amine is initiator

Add 10 g of dihydrogenated tallow-based secondary amine and 1.16 g of potassium hydroxide into a high-temperature and high-pressure reactor, and seal the reactor well. Before heating up, use nitrogen to blow and replace, then use a vacuum pump to evacuate, repeat twice, then start stirring and raise the temperature, stop heating when the temperature rises to 120°C, open the feed valve, add 570g of propylene oxide dropwise, and control the reaction The temperature does not exceed 140°C and the pressure is controlled below 0.4MPa. After the reaction of the material is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa. Finally, the temperature is lowered and the kettle is discharged to obtain dihydrogenated tallow-based secondary amine as the initiator. Polypropylene oxide oil head, marked DHCA-57.

Example 3

The method of Example 1 is adopted, but the amount of propylene oxide is changed to 340g, 400g, 510g respectively, and the obtained polypropylene oxide oil head with dihydrogenated tallow base secondary amine as the initiator is respectively marked as DHCA-34, DHCA-40, DHCA-51.

Embodiment 4, the preparation of ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow base secondary amine as initiator

Add 40g of DHCA-45 oil head and 2.08g of potassium hydroxide to the high temperature and high pressure reactor, and seal the reactor well. Before heating up, use nitrogen to blow and replace, then use a vacuum pump to evacuate, repeat twice, then start stirring and heat up, stop heating when the temperature rises to 120°C, open the feed valve, add 240g of ethylene oxide dropwise, control The reaction temperature does not exceed 140°C and the pressure is controlled below 0.4MPa. After the reaction of the material is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa; then, heat to 130°C and then add 240g of propylene oxide, and control the reaction temperature not to exceed 150°C and the pressure is controlled below 0.4MPa. After the reaction of the material is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa. Finally, the temperature is lowered and the kettle is discharged to obtain the epoxy resin with dihydrogenated tallow-based secondary amine as the initiator. Ethane and propylene oxide block polyether demulsifier, designated DHCA-45-166.

Embodiment 5,

The method of Example 4 is adopted, but the DHCA-45 oil head is changed to DHCA-34, DHCA-40, DHCA-51 and DHCA-57 respectively, and the obtained dihydrogenated tallow base secondary amine is the epoxy resin of the initiator Ethane and propylene oxide block polyether demulsifiers, designated DHCA-34-166, DHCA-40-166, DHCA-51-166 and DHCA-57-166, respectively.

The molecular weight and cloud point of DHCA-x-166 series demulsifiers are shown in Table 1 and Table 2 respectively.

The molecular weight of table 1DHCA-x-166 series demulsifier

sample DHCA-34-166 DHCA-40-166 DHCA-45-166 DHCA-51-166 DHCA-57-166 Molecular weight (g/mol) 2091 3084 2784 3134 3073

Cloud point of table 2DHCA-x-166 series demulsifiers

sample DHCA-34-166 DHCA-40-166 DHCA-45-166 DHCA-51-166 DHCA-57-166 Cloud point (°C) 28.9 32.3 29.0 29.0 32.0

Example 6, Preparation of ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow base secondary amine as initiator

Add 40g of DHCA-45 oil head and 2.40g of potassium hydroxide to the high temperature and high pressure reactor, and seal the reactor well. Before heating up, use nitrogen to blow and replace, then use a vacuum pump to evacuate, repeat twice, then start stirring and heat up, stop heating when the temperature rises to 120°C, open the feed valve, add 240g of ethylene oxide dropwise, control The reaction temperature does not exceed 140°C and the pressure is controlled below 0.4MPa. After the reaction of the materials is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa; then, heat to 130°C and then add 360g of propylene oxide to control the reaction temperature. When the temperature exceeds 150°C and the pressure is controlled below 0.4MPa, after the reaction of the material is completed, the pressure drops and then reacts for 30 minutes to reduce the pressure to 0MPa. Finally, the temperature is lowered and the kettle is discharged to obtain a cyclic compound with dihydrogenated tallow-based secondary amine as the initiator. Ethylene oxide and propylene oxide block polyether demulsifier, designated DHCA-45-169.

Embodiment 7,

The method of Example 6 is adopted, but the DHCA-45 oil head is changed to DHCA-34, DHCA-40, DHCA-51 and DHCA-57 respectively, the catalyst is changed to calcium acetate, and the consumption is changed to 3.84g, and the obtained dihydrogenate Ethylene oxide and propylene oxide block polyether demulsifiers with tallow-based secondary amine as initiator, marked as DHCA-34-169, DHCA-40-169, DHCA-51-169 and DHCA-57- 169.

The molecular weight and cloud point of DHCA-x-169 series demulsifiers are shown in Table 3 and Table 4 respectively.

The molecular weight of table 3DHCA-x-169 series demulsifier

sample DHCA-34-169 DHCA-40-169 DHCA-45-169 DHCA-51-169 DHCA-57-169 Molecular weight (g/mol) 1624 1691 2817 2137 3155

Cloud point of table 4DHCA-x-169 series demulsifiers

sample DHCA-34-169 DHCA-40-169 DHCA-45-169 DHCA-51-169 DHCA-57-169 Cloud point (°C) 27.5 28.0 23.8 24.4 26.3

Example 8. Research on the performance of the ethylene oxide and propylene oxide block polyether demulsifier using dihydrogenated tallow-based secondary amine as the initiator

Taking the produced fluid after polymer flooding in an oilfield as the treatment object, the amount of demulsifier is 200mg/L, and the temperature is 65°C, the ethylene oxide and propylene oxide block polymer with dihydrogenated tallow-based secondary amine as the initiator The dehydration rate of ether demulsifier 1h is shown in Table 5 and Table 6.

Table 5 Performance evaluation 1 of DHCA series demulsifiers (65% water content in produced fluid)

sample DHCA-34-166 DHCA-40-166 DHCA-45-166 DHCA-51-166 DHCA-57-166 serial number 1 2 3 4 5 Dehydration rate (%) 85.0 86.6 78.3 81.6 81.6 sample DHCA-34-169 DHCA-40-169 DHCA-45-169 DHCA-51-169 DHCA-59-169 serial number 6 7 8 9 10 Dehydration rate (%) 86.6 85.0 96.6 86.6 86.6

Table 6 Performance evaluation 2 of DHCA series demulsifiers (75% water content in produced fluid)

sample DHCA-34-166 DHCA-40-166 DHCA-45-166 DHCA-51-166 DHCA-57-166 serial number 1 2 3 4 5 Dehydration rate (%) 85.2 81.7 95.5 73.1 95.5 sample DHCA-34-169 DHCA-40-169 DHCA-45-169 DHCA-51-169 DHCA-57-169 serial number 6 7 8 9 10 Dehydration rate (%) 98.9 98.9 92.6 98.9 95.5

Based on the performance evaluation results of the ethylene oxide and propylene oxide block polyether demulsifier with dihydrogenated tallow-based secondary amine as the initiator, it can be found that it has a good effect on the O/W emulsion produced after polymerization flooding. The demulsification effect can meet the basic requirements of oilfield production.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (6)

1., with dihydrogenated tallow secondary amine be initiator oxyethane and a propylene oxide block polyether demulsification agent, its structural formula is as shown in formula II:

Wherein, m, n and p represent the quality of oil head in emulsion splitter, ethylene oxide block and propylene oxide block respectively, the poly(propylene oxide) oil head of described oil head to be dihydrogenated tallow secondary amine be initiator, and its structural formula is as shown in formula I:

R=C ₁₆-C ₁₈, the mass ratio of x representative ring Ethylene Oxide and dihydrogenated tallow secondary amine, x=34,40,45,51 or 57.

2. according to claim 1 with dihydrogenated tallow secondary amine be initiator oxyethane and propylene oxide block polyether demulsification agent, it is characterized in that: the mass ratio of oil head, ethylene oxide block and propylene oxide block is specially 1:6:3,1:6:6,1:6:9 or 1:6:12.

3. according to claim 1 with dihydrogenated tallow secondary amine be initiator oxyethane and propylene oxide block polyether demulsification agent, it is characterized in that: the oxyethane being initiator with dihydrogenated tallow secondary amine and propylene oxide block polyether demulsification agent, its molecular weight is 1107-3155g/mol, and cloud point is 24.2-32.3 DEG C.

4. described in any one claim of claims 1 to 3 with the preparation method of the dihydrogenated tallow secondary amine oxyethane that is initiator and propylene oxide block polyether demulsification agent, it is characterized in that comprising the following steps: add with dihydrogenated tallow secondary amine be initiator poly(propylene oxide) oil head and catalyzer in high-temperature high-pressure reaction kettle, airtight good reactor, first replace with nitrogen purging before intensification, then vacuumize, first nitrogen purging replaces the operation that vacuumizes again repeatedly at least twice, then start and stir and be warming up to temperature of reaction, add oxyethane again, react under High Temperature High Pressure to still internal pressure be 0MPa, add propylene oxide more afterwards, reacting to still internal pressure under High Temperature High Pressure is 0MPa, namely reacts end, and still discharging is opened in finally cooling, obtains with dihydrogenated tallow secondary amine be initiator oxyethane and propylene oxide block polyether demulsification agent,

Wherein, in reaction process, pressure should control at 0-0.4MPa, and in reaction process, temperature should control at 120-150 DEG C;

Described with the preparation method of the dihydrogenated tallow secondary amine poly(propylene oxide) oil head that is initiator, comprise the following steps: dihydrogenated tallow secondary amine and catalyzer are joined high-temperature high-pressure reaction kettle, airtight good reactor, first replace with nitrogen purging before intensification, then vacuumize, first nitrogen purging replaces the operation that vacuumizes again repeatedly at least twice, then start and stir and be warming up to temperature of reaction, add propylene oxide again, react under High Temperature High Pressure to still internal pressure be 0MPa, the still discharging poly(propylene oxide) oil head that to obtain with dihydrogenated tallow secondary amine be initiator is opened in finally cooling, wherein, described reaction pressure should control at 0-0.4MPa, described temperature of reaction is 120-150 DEG C, and the mass ratio of propylene oxide and dihydrogenated tallow secondary amine is specially 34,40,45,51 or 57.

5. according to claim 4 with the preparation method of the dihydrogenated tallow secondary amine oxyethane that is initiator and propylene oxide block polyether demulsification agent, it is characterized in that: in emulsion splitter preparation process, what add is specially 1:6:3,1:6:6,1:6:9 or 1:6:12 with the mass ratio of dihydrogenated tallow secondary amine be initiator poly(propylene oxide) oil head, oxyethane and propylene oxide.

6. according to claim 4 with the preparation method of the dihydrogenated tallow secondary amine oxyethane that is initiator and propylene oxide block polyether demulsification agent, it is characterized in that: described catalyzer is selected from potassium hydroxide, sodium hydroxide, hydrated barta or lime acetate, catalyst levels is the 0.2%-0.6% of reaction raw materials quality sum, described reaction raw materials refers in emulsion splitter preparation process, the poly(propylene oxide) oil head, oxyethane and the propylene oxide that are initiator with dihydrogenated tallow secondary amine that add.