CN113278442A - Multi-branch silicon-containing polyether demulsifier, compound demulsifier and preparation method thereof - Google Patents
Multi-branch silicon-containing polyether demulsifier, compound demulsifier and preparation method thereof Download PDFInfo
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- CN113278442A CN113278442A CN202110388430.5A CN202110388430A CN113278442A CN 113278442 A CN113278442 A CN 113278442A CN 202110388430 A CN202110388430 A CN 202110388430A CN 113278442 A CN113278442 A CN 113278442A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 80
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 79
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 73
- 239000010703 silicon Substances 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 polyphenol amine Chemical class 0.000 claims abstract description 37
- 241001122767 Theaceae Species 0.000 claims abstract description 30
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 30
- 229960000583 acetic acid Drugs 0.000 claims abstract description 23
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 229920002545 silicone oil Polymers 0.000 claims abstract description 23
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical group O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/208—Sediments, e.g. bottom sediment and water or BSW
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a multi-branch type silicon-containing polyether demulsifier, a compound demulsifier and a preparation method thereof, wherein the preparation method of the multi-branch type silicon-containing polyether demulsifier comprises the following steps: step one, preparing a tea polyphenol amine type phenolic resin initiator; adding the tea polyphenol amine type phenolic resin initiator synthesized in the step one and an alkaline catalyst into a reaction kettle, and carrying out ring-opening polymerization with propylene oxide and ethylene oxide to obtain triblock polyether; step three, reacting the triblock polyether synthesized in the step two, silicone oil and glacial acetic acid, and introducing a polysiloxane chain segment to obtain organic silicon modified polyether; and step four, crosslinking and esterifying the organic silicon modified polyether demulsifier synthesized in the step three and a cross-linking agent to synthesize the green high-molecular multi-branched silicon-containing polyether demulsifier with higher branching degree. The multi-branch type silicon-containing demulsifier has the characteristics of large molecular weight, multiple branching and multiple aromatic rings, can replace a natural emulsifier in the emulsion, and can effectively reduce the strength of an oil-water interface, thereby improving the demulsification effect of crude oil.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a crude oil demulsifier, and particularly relates to a multi-branch silicon-containing polyether demulsifier, a compound demulsifier and a preparation method thereof.
Background
Most oil fields in China enter a tertiary oil recovery stage, and chemical agents such as polymers, alkali liquor, surfactants and the like are added in the oil recovery process to make the components of crude oil more complex, so that the water content and the demulsification difficulty of the crude oil are increased, the dehydration cost of the crude oil is increased, and energy is wasted. In particular, crude oil rich in colloid and asphaltene has the characteristics of large viscosity, small oil-water density difference and poor fluidity, and the formed multi-layer multi-emulsion is very stable, so that the demulsification temperature and the dosage are high. The natural surfactants such as colloid and asphaltene in the crude oil are adsorbed on the oil-water interface to form an interface film with certain strength, thereby increasing the difficulty of oil-water separation.
At present, the demulsifier used in China is mainly polyoxyethylene polyoxypropylene block polyether, and the methods for modifying the block polyether mainly comprise methods of head changing, tail changing, bone adding, grafting, chain extending, compounding and the like. However, most of the raw materials of the demulsifiers are petroleum alkyl phenols, which are expensive and pollute water resources, so that the development of a novel demulsifier with low cost, a green initiator and excellent performance is urgent.
The invention application with the application number of 201410756493.1 discloses a novel spectrum crude oil demulsifier, which is prepared by taking tea polyphenol amine type phenolic resin as an initiator, and performing ring-opening polymerization with propylene oxide and ethylene oxide to obtain a diblock polyether demulsifier. The demulsifier has the characteristics of good dehydration effect, small dosage, environmental protection, no pollution and strong spectrum type.
However, the above prior art still has the problems of poor permeability and poor dehydration effect on crude oil rich in colloid and asphaltene. Because the crude oil rich in colloid and asphaltene has high viscosity, low oil-water density and excessively high active components, the diffusion speed and the water drop aggregation speed of the demulsifier are slow, and further, the demulsifier has large dosage, low demulsification speed and poor demulsification effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the multi-branch type silicon-containing demulsifier which has the advantages of environment-friendly and easily-obtained raw materials and small using amount, and can effectively demulsify crude oil rich in colloid and asphaltene.
In order to achieve the above object, the present invention provides a preparation method of a multi-branched silicon-containing polyether demulsifier, which has the following characteristics: the method comprises the following steps:
mixing tea polyphenol and polyethylene polyamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding 37-40 wt% of formaldehyde solution, keeping the temperature for 3 hours after dropwise adding, and carrying out reduced pressure distillation to remove redundant water and impurities to obtain viscous liquid, namely the tea polyphenol amine type phenolic resin initiator; the mol ratio of the tea polyphenol, the formaldehyde and the polyethylene polyamine is 1: 3: 5;
step two, adding the tea polyphenol amine type phenolic resin initiator synthesized in the step one and an alkaline catalyst into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen; stirring and continuously heating to 130-140 ℃, slowly introducing the propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure falls back, cooling to 120-130 ℃, slowly introducing the ethylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure falls back, heating to 130-140 ℃, slowly introducing the propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and triblock polyether with an initiator-PO-EO-PO structure is obtained; the dosage of the alkaline catalyst is 0.3 percent of the total mass of the tea polyphenol amine type phenolic resin initiator, the alkaline catalyst, the propylene oxide and the ethylene oxide;
step three, mixing the triblock polyether synthesized in the step two, silicone oil and glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, neutralizing glacial acetic acid by using triethanolamine, standing for layering, and removing impurities and unreacted substances to obtain an organic silicon modified polyether demulsifier; the dosage of the glacial acetic acid is 0.3 percent of the total mass of the triblock polyether, the silicone oil and the glacial acetic acid; the mass ratio of the triblock polyether to the silicone oil is 1: 0.1-0.5;
step four, mixing the organic silicon modified polyether demulsifier synthesized in the step three with a cross-linking agent, maintaining the temperature at 110-120 ℃, and stirring for 1.5 hours at normal temperature and normal pressure to obtain a cross-linked product, namely the multi-branched silicon-containing polyether demulsifier; the dosage of the cross-linking agent is 1.5 percent of the mass of the organic silicon modified polyether demulsifier.
Further, the invention provides a preparation method of the multi-branch type silicon-containing polyether demulsifier, which can also have the following characteristics: in the first step, the polyethylene polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
Further, the invention provides a preparation method of the multi-branch type silicon-containing polyether demulsifier, which can also have the following characteristics: in the second step, the alkaline catalyst is potassium hydroxide, sodium hydroxide or sodium ethoxide.
Further, the invention provides a preparation method of the multi-branch type silicon-containing polyether demulsifier, which can also have the following characteristics: in the second step, the mass ratio of the tea polyphenol amine type phenolic resin initiator to the propylene oxide, the ethylene oxide and the propylene oxide which are introduced for the first time to the second time is 1 to (49-249) to (16-249) to (49-249).
Further, the invention provides a preparation method of the multi-branch type silicon-containing polyether demulsifier, which can also have the following characteristics: in the third step, the silicone oil is methyl silicone oil, hydrogen-containing silicone oil, hydroxyl silicone oil or methyl ethoxy silicone oil.
Further, the invention provides a preparation method of the multi-branch type silicon-containing polyether demulsifier, which can also have the following characteristics: in the fourth step, the cross-linking agent is phenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate or trimesoyl chloride.
The invention also protects the multi-branch type silicon-containing polyether demulsifier prepared by the preparation method.
The preparation method of the multi-branched silicon-containing polyether demulsifier can change the hydrophilic and oleophilic capacity of the triblock polyether demulsifier by adjusting the PO/EO ratio. Only when PO/EO is in a proper range, the molecules can be paved on the oil-water interface as well as possible to replace the emulsified substances on the oil-water interface, and the effect of breaking the interface membrane and dehydrating is generated. The triblock polyether demulsifier belongs to a multi-branch type, has more branched chains, and emulsion molecules can extend all around, so that the surface energy is reduced, and the wetting and permeation speeds are increased. The hydroxyl polyether is introduced into a polysiloxane chain segment, so that the surface activity is high, and the good performance can be realized at low temperature. The molecular weight and the branched chain of the demulsifier after crosslinking are increased sharply, the intermolecular gap is reduced, and the oil-water interface strength is further reduced.
The invention also provides a compound demulsifier, which has the following characteristics: the multi-branch type silicon-containing polyether demulsifier is compounded with a solvent, a viscosity reducer and a flocculating agent; the compound components are calculated according to the following parts by weight: 40-60 parts of multi-branch silicon-containing demulsifier, 20 parts of solvent, 10-20 parts of viscosity reducer and 10-20 parts of flocculant.
Further, the invention provides a compound demulsifier, which can also have the following characteristics: wherein the solvent is isopropanol; the viscosity reducer is DM-5513 type, DM-5522 type or X-217 type; the flocculant is NPAM-6640 type, GC-309 type or APAM-8470 type.
The invention also provides a preparation method of the compound demulsifier, which is characterized in that: and adding the multi-branch type silicon-containing demulsifier, the solvent, the viscosity reducer and the flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2 hours, and reacting to obtain the compound demulsifier.
In the compound demulsifier, the isopropanol is beneficial to the dissolution of high-molecular polyether, the viscosity reducer reduces the viscosity of crude oil, and the groups in the polyacrylamide flocculant attract particles in water, thereby being beneficial to the diffusion of the demulsifier in the crude oil and the coalescence and sedimentation of water drops.
The invention has the beneficial effects that: the invention provides a multi-branch type silicon-containing polyether demulsifier, which firstly takes tea polyphenol as a raw material to synthesize tea polyphenol amine type phenolic resin. The tea polyphenol raw material is green and environment-friendly, has more active groups, and can increase molecular weight and branched chain number by modification. The novel initiator is used for ring-opening polymerization to obtain triblock polyethers with different molecular weights, and the novel initiator can be used for demulsifying crude oils of different types. The silicone modified triblock polyether is used for introducing the polysiloxane chain segment, and the demulsifier has high surface activity. Crosslinking by using a crosslinking agent to synthesize the green high-molecular silicon-containing demulsifier with higher branching degree. The silicon-containing demulsifier with higher branching degree can replace the natural emulsifier in the emulsion, is suitable for the rapid demulsification of crude oil rich in colloid and asphaltene, and has the advantage of low consumption.
Compared with the prior art, the method has the advantages of green and natural raw materials, simple preparation process and mild reaction conditions, greatly increases the molecular weight and the number of branched chains by modifying and crosslinking the triblock polyether, can rapidly demulsify at low consumption, and is suitable for demulsification of different types of crude oil.
In addition, the invention also provides a compound demulsifier, which is added with the viscosity reducer and the flocculating agent to promote the diffusion of the demulsifier and the coalescence and sedimentation of water drops, can quickly demulsify the crude oil with high asphaltene and colloid contents and greatly improve the dehydration effect of the crude oil.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a preparation method of a multi-branch silicon-containing polyether demulsifier, which comprises the following steps:
mixing 14.068g of tea polyphenol and 25.79g of diethylenetriamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding 4.5g of 37-40 wt% formaldehyde solution, keeping the temperature for 3 hours after the dropwise adding is finished, carrying out reduced pressure distillation, and removing redundant water and impurities to obtain a viscous liquid, namely the tea polyphenol amine type phenolic resin initiator.
Step two, adding 0.1g of the tea polyphenol amine type phenolic resin initiator synthesized in the step one and 0.09g of KOH into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen; stirring and continuously heating to 130-140 ℃, slowly introducing 6.63g of propylene oxide into the reaction kettle in a small amount by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure falls back, the temperature is reduced to 120-130 ℃, 9.95g of ethylene oxide is slowly and slightly introduced into the reaction kettle by nitrogen, and the polymerization pressure is controlled to be 0.25 +/-0.05 MPa; after the pressure falls back, heating to 130-140 ℃, slowly introducing 13.27g of propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and the triblock polyether with the structure of 'initiator-PO-EO-PO' is obtained.
Step three, mixing 20g of triblock polyether synthesized in the step two, 4g of methyl ethoxy silicone oil and 0.066g of glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, neutralizing glacial acetic acid by using triethanolamine, standing for layering, and removing impurities and unreacted substances to obtain the organic silicon modified polyether demulsifier.
And step four, crosslinking 10g of the organic silicon modified polyether demulsifier synthesized in the step three with 0.15g of toluene diisocyanate, maintaining the temperature at 110-120 ℃, and stirring for 1.5h at normal temperature and normal pressure to obtain a crosslinked product, namely the multi-branched silicon-containing polyether demulsifier, wherein the serial number of the crosslinked product is GTP-01.
In this embodiment, diethylenetriamine may also be replaced with triethylenetetramine, tetraethylenepentamine, or pentaethylenehexamine; KOH may also be replaced with sodium hydroxide or sodium ethoxide; the methyl ethoxy silicone oil can also be replaced by methyl silicone oil, hydrogen-containing silicone oil and hydroxyl silicone oil; toluene diisocyanate may also be replaced by phenyl isocyanate, hexamethylene diisocyanate or trimesoyl chloride.
The embodiment also provides a compound demulsifier, which comprises the following components in parts by weight: 50 parts of the synthesized multi-branch silicon-containing demulsifier, 20 parts of solvent isopropanol, 20 parts of viscosity reducer and 10 parts of flocculant.
The preparation method of the compound demulsifier comprises the following steps: adding a multi-branch silicon-containing demulsifier, isopropanol, a viscosity reducer and a flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2h, and obtaining a product after the reaction, namely a compound demulsifier, which is numbered as FP-01.
Wherein the viscosity reducer is selected from DM-5513 type viscosity reducer, and the flocculant is selected from GC-309 type flocculant.
In the embodiment, the viscosity reducer can be replaced by DM-5522 type or X-217 type; the flocculant may also be replaced by NPAM-6640 or APAM-8470 types.
Example 2
The embodiment provides a preparation method of a multi-branch silicon-containing polyether demulsifier, which comprises the following steps:
mixing 14.068g of tea polyphenol and 25.79g of diethylenetriamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding 4.5g of 37-40 wt% formaldehyde solution, keeping the temperature for 3 hours after the dropwise adding is finished, carrying out reduced pressure distillation, and removing redundant water and impurities to obtain a viscous liquid, namely the tea polyphenol amine type phenolic resin initiator.
Step two, adding 0.1g of the tea polyphenol amine type phenolic resin initiator synthesized in the step one and 0.09g of KOH into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen; stirring and continuously heating to 130-140 ℃, slowly introducing 9.95g of propylene oxide into the reaction kettle in a small amount by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure falls back, the temperature is reduced to 120-130 ℃, 9.95g of ethylene oxide is slowly and slightly introduced into the reaction kettle by nitrogen, and the polymerization pressure is controlled to be 0.25 +/-0.05 MPa; after the pressure falls back, heating to 130-140 ℃, slowly introducing 9.95g of propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and the triblock polyether with the structure of 'initiator-PO-EO-PO' is obtained.
Step three, mixing 20g of triblock polyether synthesized in the step two, 4g of methyl ethoxy silicone oil and 0.066g of glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, neutralizing glacial acetic acid by using triethanolamine, standing for layering, and removing impurities and unreacted substances to obtain the organic silicon modified polyether demulsifier.
And step four, crosslinking 10g of the organic silicon modified polyether demulsifier synthesized in the step three with 0.15g of toluene diisocyanate, maintaining the temperature at 110-120 ℃, and stirring for 1.5h at normal temperature and normal pressure to obtain a crosslinked product, namely the multi-branched silicon-containing polyether demulsifier, wherein the number of the crosslinked product is represented as GTP-02.
The embodiment also provides a compound demulsifier, which comprises the following components in parts by weight: 40 parts of the synthesized multi-branch silicon-containing demulsifier, 20 parts of solvent isopropanol, 20 parts of viscosity reducer and 20 parts of flocculant.
The preparation method of the compound demulsifier comprises the following steps: adding a multi-branch silicon-containing demulsifier, isopropanol, a viscosity reducer and a flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2h, and obtaining a product after the reaction, namely a compound demulsifier, which is numbered as FP-02.
Wherein the viscosity reducer is selected from DM-5513 type viscosity reducer, and the flocculant is selected from GC-309 type flocculant.
Example 3
The embodiment provides a preparation method of a multi-branch silicon-containing polyether demulsifier, which comprises the following steps:
mixing 14.068g of tea polyphenol and 25.79g of diethylenetriamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding 4.5g of 37-40 wt% formaldehyde solution, keeping the temperature for 3 hours after the dropwise adding is finished, carrying out reduced pressure distillation, and removing redundant water and impurities to obtain a viscous liquid, namely the tea polyphenol amine type phenolic resin initiator.
Step two, adding 0.1g of the tea polyphenol amine type phenolic resin initiator synthesized in the step one and 0.09g of KOH into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen; stirring and continuously heating to 130-140 ℃, slowly introducing 6.63g of propylene oxide into the reaction kettle in a small amount by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure falls back, the temperature is reduced to 120-130 ℃, 9.95g of ethylene oxide is slowly and slightly introduced into the reaction kettle by nitrogen, and the polymerization pressure is controlled to be 0.25 +/-0.05 MPa; after the pressure falls back, heating to 130-140 ℃, slowly introducing 13.27g of propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and the triblock polyether with the structure of 'initiator-PO-EO-PO' is obtained.
Step three, mixing 20g of triblock polyether synthesized in the step two, 2g of methyl ethoxy silicone oil and 0.066g of glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, neutralizing glacial acetic acid by using triethanolamine, standing for layering, and removing impurities and unreacted substances to obtain the organic silicon modified polyether demulsifier.
And step four, crosslinking 10g of the organic silicon modified polyether demulsifier synthesized in the step three with 0.15g of toluene diisocyanate, maintaining the temperature at 110-120 ℃, and stirring for 1.5h at normal temperature and normal pressure to obtain a crosslinked product, namely the multi-branched silicon-containing polyether demulsifier, wherein the serial number of the crosslinked product is GTP-03.
The embodiment also provides a compound demulsifier, which comprises the following components in parts by weight: 60 parts of the synthesized multi-branch type silicon-containing demulsifier, 20 parts of solvent isopropanol, 10 parts of viscosity reducer and 10 parts of flocculant.
The preparation method of the compound demulsifier comprises the following steps: adding a multi-branch silicon-containing demulsifier, isopropanol, a viscosity reducer and a flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2h, and obtaining a product after the reaction, namely a compound demulsifier, which is numbered as FP-03.
Wherein the viscosity reducer is selected from DM-5513 type viscosity reducer, and the flocculant is selected from GC-309 type flocculant.
Example 4
The embodiment provides a preparation method of a multi-branch silicon-containing polyether demulsifier, which comprises the following steps:
mixing 14.068g of tea polyphenol and 25.79g of diethylenetriamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding 4.5g of 37-40 wt% formaldehyde solution, keeping the temperature for 3 hours after the dropwise adding is finished, carrying out reduced pressure distillation, and removing redundant water and impurities to obtain a viscous liquid, namely the tea polyphenol amine type phenolic resin initiator.
Step two, adding 0.1g of the tea polyphenol amine type phenolic resin initiator synthesized in the step one and 0.09g of KOH into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen; stirring and continuously heating to 130-140 ℃, slowly introducing 9.95 propylene oxide into the reaction kettle in a small amount by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the pressure drops, the temperature is reduced to 120-130 ℃, 19.9g of ethylene oxide is slowly introduced into the reaction kettle in a small amount by using nitrogen, and the polymerization pressure is controlled to be 0.25 +/-0.05 MPa; after the pressure falls back, heating to 130-140 ℃, slowly introducing 9.95g of propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa; after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and the triblock polyether with the structure of 'initiator-PO-EO-PO' is obtained.
Step three, mixing 20g of triblock polyether synthesized in the step two, 2g of methyl ethoxy silicone oil and 0.066g of glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, neutralizing glacial acetic acid by using triethanolamine, standing for layering, and removing impurities and unreacted substances to obtain the organic silicon modified polyether demulsifier.
And step four, crosslinking 10g of the organic silicon modified polyether demulsifier synthesized in the step three with 0.15g of toluene diisocyanate, maintaining the temperature at 110-120 ℃, and stirring for 1.5h at normal temperature and normal pressure to obtain a crosslinked product, namely the multi-branched silicon-containing polyether demulsifier, wherein the number of the crosslinked product is represented as GTP-04.
The embodiment also provides a compound demulsifier, which comprises the following components in parts by weight: 40 parts of the synthesized multi-branch silicon-containing demulsifier, 20 parts of solvent isopropanol, 10 parts of viscosity reducer and 20 parts of flocculant.
The preparation method of the compound demulsifier comprises the following steps: adding a multi-branch silicon-containing demulsifier, isopropanol, a viscosity reducer and a flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2h, wherein the product after the reaction is a compound demulsifier, and the product is numbered as FP-04.
Wherein the viscosity reducer is selected from DM-5513 type viscosity reducer, and the flocculant is selected from GC-309 type flocculant.
Performance testing
The multi-branch type silicon-containing demulsifier, the compound demulsifier and the market demulsifier synthesized by the above embodiments are respectively subjected to demulsification performance test according to the technical requirements of Q/SHCG 66-2013 crude oil demulsifier. Demulsifying conditions are as follows: the dehydration temperature is 50 ℃, and the medicine adding amount is 100 mg/L. The crude oil used in the test was experimental oil having a wax content of 17.3%, a gum content of 33.8%, and asphaltenes content of 0.25%, and the crude oil had a water content (V/V) of 40%.
TABLE 1 results of demulsification Performance of different multi-branched silicon-containing demulsifiers
The test results in Table 1 show that the demulsification effect of GTP-01 is better, and 92.1% of water can be dehydrated in 90 min. The triblock polyether demulsifier with different molecular weights can be synthesized by controlling the proportion of the initiator, the head PO, the EO and the tail PO, and can be used for different types of crude oil. The proportion of PO and EO has a large influence on the demulsification effect of the demulsifier, and the dosage of the silicone oil has an influence on the demulsification effect of the modified demulsifier.
TABLE 2 demulsification Performance Effect of different compounded demulsifiers
The test result in Table 2 shows that the compound demulsifier FP-01 has better demulsification effect. The demulsifying effect of the compounded demulsifier is partially better than that of the silicon-containing demulsifier which is used alone, but the demulsifying effect is poorer when the content of the silicon-containing demulsifier is too low. The demulsifying effect of the silicon-containing demulsifier prepared by the technical scheme is better than that of the AE type polyether demulsifier.
The dosage of the demulsifiers is the same, the dosage of the multi-branch type silicon-containing demulsifier in the compound demulsifier is far lower than that of the single multi-branch type silicon-containing demulsifier, and the compound demulsifier has better demulsification effect and lower cost, which is not possessed by the prior art.
Claims (10)
1. A preparation method of a multi-branch type silicon-containing polyether demulsifier is characterized by comprising the following steps:
the method comprises the following steps:
mixing tea polyphenol and polyethylene polyamine, heating to 70-80 ℃ under the protection of nitrogen, stirring until the mixture is completely dissolved, slowly dropwise adding a formaldehyde solution with the concentration of 37-40 wt%, and keeping the temperature constant for 3 hours after dropwise adding is finished to obtain a tea polyphenol amine type phenolic resin initiator;
the mol ratio of the tea polyphenol, the formaldehyde and the polyethylene polyamine is 1: 3: 5;
step two, adding the tea polyphenol amine type phenolic resin initiator synthesized in the step one and an alkaline catalyst into a reaction kettle, closing the reaction kettle, heating to 100-110 ℃, vacuumizing, and replacing for 2-3 times by using dry nitrogen;
stirring and continuously heating to 130-140 ℃, slowly introducing the propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa;
after the pressure falls back, cooling to 120-130 ℃, slowly introducing the ethylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa;
after the pressure falls back, heating to 130-140 ℃, slowly introducing the propylene oxide into the reaction kettle by using nitrogen, and controlling the polymerization pressure to be 0.25 +/-0.05 MPa;
after the reaction is finished, glacial acetic acid is added to neutralize the alkaline catalyst, and triblock polyether with an initiator-PO-EO-PO structure is obtained;
the dosage of the alkaline catalyst is 0.3 percent of the total mass of the tea polyphenol amine type phenolic resin initiator, the alkaline catalyst, the propylene oxide and the ethylene oxide;
step three, mixing the triblock polyether synthesized in the step two, silicone oil and glacial acetic acid, stirring and slowly heating to 70-80 ℃; vacuumizing, slowly heating to 120-130 ℃, keeping the temperature for 2 hours, then finishing the reaction, and neutralizing glacial acetic acid by using triethanolamine to obtain an organic silicon modified polyether demulsifier;
the dosage of the glacial acetic acid is 0.3 percent of the total mass of the triblock polyether, the silicone oil and the glacial acetic acid; the mass ratio of the triblock polyether to the silicone oil is 1: 0.1-0.5;
step four, mixing the organic silicon modified polyether demulsifier synthesized in the step three with a cross-linking agent, maintaining the temperature at 110-120 ℃, and stirring for 1.5 hours at normal temperature and normal pressure to obtain a multi-branched silicon-containing polyether demulsifier;
the dosage of the cross-linking agent is 1.5 percent of the mass of the organic silicon modified polyether demulsifier.
2. The method for preparing the multi-branch type silicon-containing polyether demulsifier according to claim 1, wherein the method comprises the following steps:
in the first step, the polyethylene polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
3. The method for preparing the multi-branch type silicon-containing polyether demulsifier according to claim 1, wherein the method comprises the following steps:
in the second step, the alkaline catalyst is potassium hydroxide, sodium hydroxide or sodium ethoxide.
4. The method for preparing the multi-branch type silicon-containing polyether demulsifier according to claim 1, wherein the method comprises the following steps:
in the second step, the mass ratio of the tea polyphenol amine type phenolic resin initiator to the propylene oxide, the ethylene oxide and the propylene oxide which are introduced for the first time to the second time is 1 to (49-249) to (16-249) to (49-249).
5. The method for preparing the multi-branch type silicon-containing polyether demulsifier according to claim 1, wherein the method comprises the following steps:
in the third step, the silicone oil is methyl silicone oil, hydrogen-containing silicone oil, hydroxyl silicone oil or methyl ethoxy silicone oil.
6. The method for preparing the multi-branch type silicon-containing polyether demulsifier according to claim 1, wherein the method comprises the following steps:
in the fourth step, the cross-linking agent is phenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate or trimesoyl chloride.
7. The multi-branch type silicon-containing polyether demulsifier prepared by the preparation method of any one of claims 1 to 6.
8. A compound demulsifier is characterized in that: the multi-branch type silicon-containing polyether demulsifier of claim 7 is compounded with solvent, viscosity reducer and flocculant;
the compound components are calculated according to the following parts by weight: 40-60 parts of multi-branch silicon-containing demulsifier, 20 parts of solvent, 10-20 parts of viscosity reducer and 10-20 parts of flocculant.
9. The compounded demulsifier of claim 8, wherein:
wherein the solvent is isopropanol;
the viscosity reducer is DM-5513 type, DM-5522 type or X-217 type;
the flocculant is NPAM-6640 type, GC-309 type or APAM-8470 type.
10. The preparation method of the compound demulsifier of claim 8, which is characterized in that:
and adding the multi-branch type silicon-containing demulsifier, the solvent, the viscosity reducer and the flocculant into a reaction kettle, heating to 60-70 ℃, stirring for 2 hours, and reacting to obtain the compound demulsifier.
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