CN115433352A - Modified polyamine demulsifier and preparation method and application thereof - Google Patents
Modified polyamine demulsifier and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of petroleum chemical additives for oilfield development, and discloses a modified polyamine demulsifier, and a preparation method and application thereof. The preparation method of the modified polyamine demulsifier comprises five steps: (1) Synthesizing modified polyamine polymer head by cross-linking reaction of tetraethylenepentamine and epichlorohydrin; (2) Polymerizing the modified polyamine headgroup and epoxypropane to synthesize an intermediate polymerization product; (3) The intermediate polymerization product and ethylene oxide are polymerized to synthesize a target macromolecular polymerization product; (4) preparing a mixed solvent; (5) And diluting the target macromolecular polymerization product by using a mixed solvent to obtain the modified polyamine demulsifier. The reaction process is mild, and the prepared modified polyamine demulsifier is of a linear multi-branched-chain structure, has long molecular chain and more branched chains, has better hydrophilic capacity, wetting property and permeation effect than the traditional demulsifier with a phenolic resin structure, can quickly destroy the interfacial energy of emulsion, and has the characteristics of high oil-water separation speed and low oil content in water.
Description
Technical Field
The invention relates to the field of petroleum chemical additives for oilfield development, and particularly relates to a modified polyamine demulsifier, and a preparation method and application thereof.
Background
With the popularization and use of polymer flooding, ternary complex flooding and other technologies in various domestic oil fields, the composition of crude oil produced liquid becomes more complex, the water content in crude oil emulsion is increased, the stability is enhanced, the crude oil demulsification difficulty is increased, and a large amount of various oil extraction auxiliaries are applied, so that the efficient and rapid demulsification of crude oil becomes a key technology influencing the oil extraction cost, the crude oil quality, the yield and controlling the environmental pollution of the oil fields.
At present, the demulsifier in China is most widely applied by using polyol polyether, phenolic resin polyether and phenolic amine resin polyether, wherein particularly, the phenolic amine resin polyether demulsifier has better effect and wider adaptability. However, because of the few active groups of the alkylphenol, the synthesized polyether has few branches and relatively low molecular weight, and the demulsification performance is damaged. As for the current situation of China, some oil fields enter a tertiary oil recovery stage, the water content of crude oil reaches 60% -90%, emulsion is more stable, the existing demulsifier is difficult to meet the requirements, and the demulsification dehydration rate and the water color become problems, so that the development of a novel crude oil demulsifier is required.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a modified polyamine demulsifier and a preparation method and application thereof, and the technical scheme is as follows:
a preparation method of a modified polyamine demulsifier comprises the following steps:
(1) Synthesis of modified polyamine polymer head by cross-linking reaction of tetraethylenepentamine and epichlorohydrin
Firstly, adding tetraethylenepentamine into a reaction kettle, and then dropwise adding epoxy chloropropane into the reaction kettle through a dropwise adding tank, wherein the molar ratio of the tetraethylenepentamine to the epoxy chloropropane is 1 (0.4-0.6); after the dropwise addition is finished, the temperature is raised, heat preservation is carried out, and a modified polyamine polymer head is obtained through a crosslinking reaction;
(2) Intermediate polymerization product synthesized by polymerization reaction of modified polyamine headings and epoxypropane
Polymerizing the modified polyamine polymer head synthesized in the step (1) with propylene oxide according to the mass ratio of 1 (169-229) to obtain an intermediate polymerization product; the polymerization reaction controls the reaction pressure to be less than or equal to 0.4Mpa, and the reaction temperature is kept between 90 and 100 ℃; the polymerization reaction is terminated at a point where the reaction pressure does not decrease any more;
(3) The intermediate polymerization product and ethylene oxide are polymerized to synthesize the target macromolecular polymerization product
Carrying out polymerization reaction on the intermediate polymerization product synthesized in the step (2) and ethylene oxide to synthesize a target macromolecular polymerization product; the dosage of the ethylene oxide is 1/3-1/2 of the mass of the propylene oxide in the step (2); the polymerization reaction controls the reaction pressure to be less than or equal to 0.4Mpa, and the reaction temperature is kept between 90 and 100 ℃; the polymerization reaction is terminated at a point where the reaction pressure does not decrease any more;
(4) Preparing mixed solvent
Preparing methanol and water into a mixed solvent;
(5) Diluting the target macromolecular polymerization product by using mixed solvent to obtain modified polyamine demulsifier
And (4) pumping the mixed solvent prepared in the step (4) into the target macromolecular polymerization product synthesized in the step (3), uniformly mixing, and discharging to obtain the modified polyamine demulsifier.
The dropping temperature in the step (1) is controlled within 20 ℃, and the dropping time is 50-75 minutes; the temperature is raised to 90 ℃ and the reaction is kept for 4 hours.
The step (2) is carried out by the following two steps:
firstly, carrying out primary polymerization reaction on a modified polyamine head and propylene oxide according to the mass ratio of 1;
and secondly, carrying out secondary polymerization reaction on the product of the primary polymerization reaction in the first step and the rest propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, keeping the reaction temperature at 90-100 ℃, and taking the reaction pressure not to decrease as an end point.
The mass ratio of the methanol to the water in the step (4) is 3.
The mass ratio of the mixed solvent in the step (5) to the target macromolecular polymerization product is 1.
Triethylamine is added into the polymerization reaction in the step (2) and the polymerization reaction in the step (3) as a catalyst; the dosage of the catalyst in the step (2) is 3 per mill of the total mass of the modified polyamine polymerization head and the propylene oxide; the dosage of the catalyst in the step (3) is 3 per mill of the mass of the ethylene oxide.
Triethylamine is added into the primary polymerization reaction in the first step and the secondary polymerization reaction in the second step to serve as catalysts; the amount of the catalyst added in the primary polymerization reaction is 3 per mill of the total mass of the modified polyamine polymer head and the propylene oxide; the amount of the catalyst added in the secondary polymerization reaction is 3 per mill of the mass of the rest propylene oxide.
The polymerization reaction of the step (2) and the polymerization reaction of the step (3) are carried out in an oxygen-free and water-free environment; the anaerobic environment is obtained by nitrogen replacement; the anhydrous environment is obtained by a vacuum dehydration mode, the temperature of the vacuum dehydration is 90-100 ℃, and the pressure is-0.08 to-0.10 Mpa.
The modified polyamine demulsifier is prepared by adopting the preparation method of the modified polyamine demulsifier.
The modified polyamine demulsifier is applied to oilfield development.
Compared with the prior art, the invention mainly has the following beneficial technical effects:
1. the modified polyamine demulsifier prepared by the invention is of a linear multi-branched structure, has long molecular chain and more branched chains compared with the traditional demulsifier of a phenolic resin structure, has better hydrophilic capacity, wettability and osmotic effect, can quickly reach an oil-water interface and destroy the interface energy of an emulsion, and has the characteristics of high oil-water separation speed and low oil content in water.
2. The preparation method of the modified polyamine demulsifier provided by the invention uses a cross-linked product of tetraethylenepentamine and epichlorohydrin as a polymer head, the product is a linear multi-branched structure and contains a plurality of active groups, and a novel demulsifier with good demulsification and dehydration performance effects is obtained by adjusting the polymerization proportion of the polymer head to the block polymerization of propylene oxide and ethylene oxide.
3. The preparation method of the modified polyamine demulsifier provided by the invention has the advantages of reasonable operation steps, mild reaction process and strong feasibility.
4. The modified polyamine demulsifier provided by the invention can be widely popularized and applied in oil field development.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Example 1 Synthesis of demulsifier A
Polymerizing a modified polyamine polymer head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.4 with propylene oxide at a mass ratio of 1 to 169, and then polymerizing the modified polyamine polymer head with ethylene oxide (the mass is 1/3 of the mass of the propylene oxide) to obtain a demulsifier A, wherein the specific steps are as follows:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.4, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 50 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to a molar ratio of 1.4 and propylene oxide according to a mass ratio of 1.
300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths, (300kg) + 2700kg) multiplied by 3 thousandths =9kg of the total mass of the modified polyamine head and the epoxypropane) which are crosslinked by the mol ratio of tetraethylenepentamine to the epoxychloropropane of 1; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, the reaction temperature is maintained, the stirring, aging and absorption are continued until the pressure is not reduced, the reaction is finished, and the material is discharged for standby.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 14.4kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 4800kg multiplied by 3 per mill =14.4 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 4800kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and ending the reaction to obtain an intermediate polymerization product, wherein the product is left in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 5.07kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 1690kg multiplied by 3 per mill =5.07 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 1690kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier A.
Example 2 Synthesis of demulsifier B
Polymerizing a modified polyamine polymer head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.5 with propylene oxide at a mass ratio of 1 to 169, and then polymerizing the modified polyamine polymer head with ethylene oxide (the mass is 1/3 of the mass of the propylene oxide) to obtain a demulsifier B, wherein the specific steps are as follows:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.5, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 60 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.
Adding 300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths of the total mass of the modified polyamine head and the epoxypropane, (300kg +2700 kg) multiplied by 3 thousandths =9 kg) of the crosslinked modified polyamine head and the epoxychloropropane into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, and carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, the reaction temperature is maintained, the stirring, aging and absorption are continued until the pressure is not reduced, the reaction is finished, and the material is discharged for standby.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 14.4kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 4800kg multiplied by 3 per mill =14.4 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 4800kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and ending the reaction to obtain an intermediate polymerization product, wherein the product is left in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 5.07kg of catalyst triethylamine (namely 3 per mill of the mass of ethylene oxide, 1690kg multiplied by 3 per mill =5.07 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 1690kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
Step four, compounding solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier B.
Example 3 Synthesis of demulsifier C
Polymerizing a modified polyamine polymer head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 with propylene oxide at a mass ratio of 1 to 169, and then polymerizing the modified polyamine polymer head with ethylene oxide (the mass is 1/3 of the mass of the propylene oxide) to obtain a demulsifier C, wherein the specific steps are as follows:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.6, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 75 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.
Adding 300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths of the total mass of the modified polyamine head and the epoxypropane, (300kg +2700 kg) multiplied by 3 thousandths =9 kg) of the crosslinked modified polyamine head of tetraethylenepentamine and the epoxychloropropane into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, and carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, the reaction temperature is maintained, the stirring, aging and absorption are continued until the pressure is not reduced, the reaction is finished, and the material is discharged for standby.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 14.4kg of triethylamine (namely 3 per mill of the mass of the rest propylene oxide, 4800kg multiplied by 3 per mill =14.4 kg) as a catalyst into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 4800kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
The third step of polymerizing the intermediate polymerization product with ethylene oxide
Adding 5.07kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 1690kg multiplied by 3 per mill =5.07 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 1690kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3:2, pumping in the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier C.
Example 4 Synthesis of demulsifier D
Polymerizing a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.4 to 169 of propylene oxide, and polymerizing the modified polyamine head with ethylene oxide (the mass of the modified polyamine head is 1/2 of that of the propylene oxide) to obtain a demulsifier D, wherein the specific steps are as follows:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to a molar ratio of 1.4 and propylene oxide according to a mass ratio of 1.
300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths, (300kg) + 2700kg) multiplied by 3 thousandths =9kg of the total mass of the modified polyamine head and the epoxypropane) which are crosslinked by the mol ratio of tetraethylenepentamine to the epoxychloropropane of 1; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, finishing the reaction, and discharging for later use.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 14.4kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 4800kg multiplied by 3 per mill =14.4 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 4800kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and ending the reaction to obtain an intermediate polymerization product, wherein the product is left in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 7.6kg of catalyst triethylamine (namely 3 per mill of the mass of ethylene oxide, 2535kg multiplied by 3 per mill =7.6 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08- -0.10Mpa, and closing a vacuum valve; then slowly introducing 2535kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier D.
Example 5 Synthesis of demulsifier E
Polymerizing a modified polyamine polymer head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 with propylene oxide at a mass ratio of 1 to 169, and then polymerizing the modified polyamine polymer head with ethylene oxide (the mass is 1/2 of the mass of the propylene oxide) to obtain a demulsifier E, wherein the specific steps are as follows:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.6, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 75 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 and propylene oxide according to the mass ratio of 1.
Adding 300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths of the total mass of the modified polyamine head and the epoxypropane, (300kg +2700 kg) multiplied by 3 thousandths =9 kg) of the crosslinked modified polyamine head of tetraethylenepentamine and the epoxychloropropane into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, and carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, finishing the reaction, and discharging for later use.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 14.4kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 4800kg multiplied by 3 per mill =14.4 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 4800kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 7.6kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 2535kg multiplied by 3 per mill =7.6 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to make the pressure in the kettle approach-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2535kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
Step four, compounding solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3:2, pumping in the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier E.
Example 6 Synthesis of demulsifier F
Polymerizing a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.4 with propylene oxide of 1:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.4, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 50 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to a molar ratio of 1.4 and propylene oxide according to a mass ratio of 1.
Adding 300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths of the total mass of the modified polyamine head and the epoxypropane, (300kg +2700 kg) multiplied by 3 thousandths =9 kg) of the crosslinked modified polyamine head of tetraethylenepentamine and the epoxychloropropane into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, and carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, the reaction temperature is maintained, the stirring, aging and absorption are continued until the pressure is not reduced, the reaction is finished, and the material is discharged for standby.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 19.8kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 6600kg multiplied by 3 per mill =19.8 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 6600kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 6.87kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 2290kg multiplied by 3 per mill =6.87 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to make the pressure in the kettle approach-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2290kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier F.
Example 7 Synthesis of demulsifier G
Polymerizing a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 with propylene oxide at a mass ratio of 1:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1.6, wherein the tetraethylenepentamine is added into a reaction kettle, the epoxy chloropropane is added into a dripping tank, stirring is started, a valve of the dripping tank is started, the dripping temperature is controlled within 20 ℃, and the dripping time is 75 minutes; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 and propylene oxide according to the mass ratio of 1.
300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 ‰, (300kg) +2700 kg) multiplied by 3 ‰ =9kg of the total mass of the modified polyamine head and the epoxypropane) after tetraethylenepentamine and the epoxychloropropane are crosslinked according to the mol ratio of 1; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, finishing the reaction, and discharging for later use.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 19.8kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 6600kg multiplied by 3 per mill =19.8 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 6600kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 6.87kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 2290kg multiplied by 3 per mill =6.87 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2290kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier G.
Example 8 Synthesis of demulsifier H
Polymerizing a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.4 with propylene oxide of 1:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.
Adding 300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 thousandths of the total mass of the modified polyamine head and the epoxypropane, (300kg +2700 kg) multiplied by 3 thousandths =9 kg) of the crosslinked modified polyamine head of tetraethylenepentamine and the epoxychloropropane into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, and carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, the reaction temperature is maintained, the stirring, aging and absorption are continued until the pressure is not reduced, the reaction is finished, and the material is discharged for standby.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 19.8kg of catalyst triethylamine (namely 3 per mill of the mass of the rest propylene oxide, 6600kg multiplied by 3 per mill =19.8 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 6600kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 10.3kg of catalyst triethylamine (namely 3 per mill of the mass of the ethylene oxide, 3435kg multiplied by 3 per mill =10.3 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to make the pressure in the kettle approach-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 3435kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
Step four, compounding solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier H.
Example 9 Synthesis of demulsifier I
Polymerizing a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 with propylene oxide at a mass ratio of 1:
first step synthesis of modified polyamine headings
Feeding tetraethylenepentamine and epoxy chloropropane according to a molar ratio of 1; after the dripping is finished, the temperature is raised to 90 ℃, the reaction is carried out for 4 hours under the condition of heat preservation, and the materials are cooled and discharged for standby.
Second step polymerization of modified polyamine headings with propylene oxide
a. Carrying out primary polymerization reaction on a modified polyamine head obtained by crosslinking tetraethylenepentamine and epichlorohydrin according to the molar ratio of 1.6 and propylene oxide according to the mass ratio of 1.
300kg of modified polyamine head and 9kg of catalyst triethylamine (namely 3 ‰, (300kg) +2700 kg) multiplied by 3 ‰ =9kg of the total mass of the modified polyamine head and the epoxypropane) after tetraethylenepentamine and the epoxychloropropane are crosslinked according to the mol ratio of 1; then slowly introducing 2700kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuing stirring, aging and absorbing until the pressure is not reduced, finishing the reaction, and discharging for later use.
b. The product of the primary polymerization and the remaining propylene oxide are subjected to secondary polymerization
Adding 300kg of products of the primary polymerization reaction and 19.8kg of catalyst triethylamine (namely 3 per mill of the mass of the residual propylene oxide, 6600kg multiplied by 3 per mill =19.8 kg) into a polyether reaction kettle, starting stirring, heating the materials to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 6600kg of propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature to be 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, finishing the reaction to obtain an intermediate polymerization product, and keeping the product in the kettle for later use.
Third step the intermediate polymerization product is polymerized with ethylene oxide
Adding 10.3kg of catalyst triethylamine (namely 3 per mill of the mass of ethylene oxide, 3435kg multiplied by 3 per mill =10.3 kg), heating the intermediate polymerization product reserved in the kettle to 90-l 00 ℃, carrying out vacuum dehydration to ensure that the pressure in the kettle is close to-0.08 to-0.10 Mpa, and closing a vacuum valve; then slowly introducing 3435kg of ethylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, and keeping the reaction temperature at 90-100 ℃; after the reaction is finished, maintaining the reaction temperature, continuously stirring, aging and absorbing until the pressure is not reduced, and finishing the reaction to obtain the target macromolecular polymer.
The fourth step is a compound solvent
Preparing a mixed solvent according to the mass ratio of methanol to water =3, pumping the mixed solvent with the same mass as the target macromolecular polymer, uniformly mixing, and discharging to obtain the demulsifier I.
Example 10 crude oil demulsification experiment
The demulsifier synthesized in the examples 1-9 was subjected to demulsification experiments on crude oil produced liquid at the site temperature of the islanding combined-site station of the victory oil field island oil production plant by adopting the standard Q/SH CG0066-2021 technical requirement for crude oil demulsifier of the national petrochemical group company Limited corporation, and demulsifiers of normal crude oil used on site were selected as a reference, the dosage of the demulsifier was 125mg/L, and the demulsification data thereof is shown in Table 1.
Demulsification Effect of the demulsifiers synthesized in Table 1 and examples 1 to 9
As can be seen from Table 1, the demulsifier prepared by the invention can realize demulsification of crude oil produced liquid in an lone-tetrad united station of a victory oil field island oil production plant, meets the technical requirements that the dehydration rate of heavy crude oil is more than or equal to 90% in 90 minutes and the continuous dehydration rate is more than or equal to 96% in 24 hours, and meanwhile, the early-stage dehydration speed is obviously superior to that of a field agent, and the demulsification effect is outstanding. In terms of 30-minute dehydration rate, the dehydration rate of the on-site demulsifier is 36.2 percent, while the dehydration rate of the demulsifier of 9 embodiments of the invention is 42.8 to 51.4 percent, which is 6.6 to 15.2 percent higher than that of the on-site demulsifier; for a 60 minute dehydration rate, the on-site demulsifier dehydration rate was 67.6%, whereas the demulsifier dehydration rate of 9 embodiments of the present invention was 77.9% to 82.2%, which was 10.3% to 14.6% higher than the on-site demulsifier dehydration rate. With respect to the demulsifiers of 9 examples of the invention, the demulsifier B of example 2 has the best dehydration effect, and the 30-minute dehydration rate is 51.4 percent which is 15.2 percent higher than that of the on-site demulsifier; the dehydration rate in 60 minutes is 82.2 percent, which is 14.6 percent higher than that of the field demulsifier; the dehydration rate in 90 minutes is 93.4 percent, which is 2.8 percent higher than that of the field demulsifier; the dehydration rate in 24 hours is 98.5 percent, which is 2.3 percent higher than that of the on-site demulsifier.
The foregoing are merely exemplary of the invention; and tests prove that the demulsifier products similar to the demulsifier products of the 9 embodiments can be prepared by selecting other ratios and control parameters of the materials within the protection range of the invention, and the demulsification effect is basically equivalent, which is not repeated herein.
Claims (10)
1. The preparation method of the modified polyamine demulsifier is characterized by comprising the following steps:
(1) Synthesis of modified polyamine poly head by cross-linking reaction of tetraethylenepentamine and epichlorohydrin
Firstly, adding tetraethylenepentamine into a reaction kettle, and then dropwise adding epoxy chloropropane into the reaction kettle through a dropwise adding tank, wherein the molar ratio of the tetraethylenepentamine to the epoxy chloropropane is 1 (0.4-0.6); after the dropwise addition is finished, the temperature is raised, heat preservation is carried out, and a modified polyamine polymer head is obtained through a crosslinking reaction;
(2) Intermediate polymerization product synthesized by polymerization reaction of modified polyamine headings and epoxypropane
Polymerizing the modified polyamine polymer head synthesized in the step (1) with propylene oxide according to the mass ratio of 1 (169-229) to obtain an intermediate polymerization product; the polymerization reaction controls the reaction pressure to be less than or equal to 0.4Mpa, and the reaction temperature is kept between 90 and 100 ℃; the polymerization reaction is terminated at a point where the reaction pressure does not decrease any more;
(3) The intermediate polymerization product and ethylene oxide are polymerized to synthesize the target macromolecular polymerization product
Carrying out polymerization reaction on the intermediate polymerization product synthesized in the step (2) and ethylene oxide to synthesize a target macromolecular polymerization product; the dosage of the ethylene oxide is 1/3-1/2 of the mass of the propylene oxide in the step (2); the polymerization reaction controls the reaction pressure to be less than or equal to 0.4Mpa, and the reaction temperature is kept between 90 and 100 ℃; the polymerization reaction is terminated at a point where the reaction pressure does not decrease any more;
(4) Preparing mixed solvent
Preparing methanol and water into a mixed solvent;
(5) Diluting the target macromolecule polymerization product by a mixed solvent to obtain a modified polyamine demulsifier
And (4) pumping the mixed solvent prepared in the step (4) into the target macromolecular polymerization product synthesized in the step (3), uniformly mixing, and discharging to obtain the modified polyamine demulsifier.
2. The preparation method of the modified polyamine demulsifier according to claim 1, wherein the dropping temperature in step (1) is controlled within 20 ℃ and the dropping time is 50-75 minutes; the temperature is raised to 90 ℃ and the reaction is kept for 4 hours.
3. The method for preparing the modified polyamine demulsifier according to claim 1, wherein the step (2) is performed in two steps:
firstly, carrying out primary polymerization reaction on a modified polyamine polymerization head and propylene oxide according to the mass ratio of 1;
and secondly, carrying out secondary polymerization reaction on the product of the primary polymerization reaction in the first step and the rest propylene oxide, controlling the reaction pressure to be less than or equal to 0.4Mpa, keeping the reaction temperature at 90-100 ℃, and taking the reaction pressure as the terminal point without reducing any more.
4. The method for preparing the modified polyamine demulsifier according to claim 1, wherein the mass ratio of methanol to water in step (4) is 3.
5. The method for preparing the modified polyamine demulsifier according to claim 1, wherein the mass ratio of the mixed solvent to the target macromolecular polymerization product in the step (5) is 1.
6. The method for preparing the modified polyamine demulsifier according to claim 1, wherein triethylamine is added as a catalyst in the polymerization reaction in the step (2) and the polymerization reaction in the step (3); the dosage of the catalyst in the step (2) is 3 per mill of the total mass of the modified polyamine polymer head and the propylene oxide; the dosage of the catalyst in the step (3) is 3 per mill of the mass of the ethylene oxide.
7. The method for preparing the modified polyamine demulsifier according to claim 3, wherein triethylamine is added as a catalyst in both the primary polymerization reaction in the first step and the secondary polymerization reaction in the second step; the amount of the catalyst added in the primary polymerization reaction is 3 per mill of the total mass of the modified polyamine polymer head and the propylene oxide; the amount of the catalyst added in the secondary polymerization reaction is 3 per mill of the mass of the rest propylene oxide.
8. The method for preparing the modified polyamine demulsifier according to claim 1, wherein the polymerization reaction in step (2) and step (3) is carried out in an oxygen-free and water-free environment; the anaerobic environment is obtained by a nitrogen replacement mode; the anhydrous environment is obtained by a vacuum dehydration mode, the temperature of the vacuum dehydration is 90-100 ℃, and the pressure is-0.08 to-0.10 Mpa.
9. A modified polyamine demulsifier, characterized in that the modified polyamine demulsifier is prepared by the method for preparing the modified polyamine demulsifier according to any one of claims 1 to 8.
10. Use of a modified polyamine demulsifier according to claim 9 in oil field development.
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