CN114032117B - Demulsifier for treating oil-water transition layer rich in polymer and colloid asphaltene in crude oil dehydration system and preparation method thereof - Google Patents
Demulsifier for treating oil-water transition layer rich in polymer and colloid asphaltene in crude oil dehydration system and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000007704 transition Effects 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- 239000010779 crude oil Substances 0.000 title claims abstract description 14
- 239000000084 colloidal system Substances 0.000 title claims abstract description 12
- 230000018044 dehydration Effects 0.000 title claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 8
- -1 alkyl ether sulfate Chemical class 0.000 claims abstract description 23
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000001632 sodium acetate Substances 0.000 claims abstract description 15
- 235000017454 sodium diacetate Nutrition 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000004359 castor oil Substances 0.000 claims description 32
- 235000019438 castor oil Nutrition 0.000 claims description 32
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 230000005587 bubbling Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- MHIJVQDHTRBZKY-UHFFFAOYSA-N benzene-1,4-diol;ethanol Chemical compound CCO.OC1=CC=C(O)C=C1 MHIJVQDHTRBZKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 235000017858 Laurus nobilis Nutrition 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000005212 Terminalia tomentosa Nutrition 0.000 claims description 4
- 244000125380 Terminalia tomentosa Species 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 125000005011 alkyl ether group Chemical group 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000002893 slag Substances 0.000 abstract description 2
- 230000002457 bidirectional effect Effects 0.000 abstract 1
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 238000004581 coalescence Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 4
- 229930195725 Mannitol Natural products 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000594 mannitol Substances 0.000 description 4
- 235000010355 mannitol Nutrition 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 101100129750 Arabidopsis thaliana MDN1 gene Proteins 0.000 description 3
- 101100049029 Rattus norvegicus Atp6v0e1 gene Proteins 0.000 description 3
- 101100327317 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CDC1 gene Proteins 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical group C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KLYDBHUQNXKACI-UHFFFAOYSA-M sodium;2-[2-(2-tridecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O KLYDBHUQNXKACI-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- OPVLOHUACNWTQT-UHFFFAOYSA-N azane;2-dodecoxyethyl hydrogen sulfate Chemical compound N.CCCCCCCCCCCCOCCOS(O)(=O)=O OPVLOHUACNWTQT-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AOLMPVPUFVWGPN-UHFFFAOYSA-N diazanium;1-dodecoxydodecane;sulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC AOLMPVPUFVWGPN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002699 waste material Substances 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
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a demulsifier for an oil-water transition layer rich in polymers and colloid asphaltenes in a crude oil dehydration system and a preparation method thereof. The demulsifier DSR consists of three components, one is a star-tree triblock demulsifier SR with polyhydroxy ester as a core, the other is commercial sodium diacetate, and the third is commercial alkyl ether sulfate with the mass ratio of SR to sodium diacetate to alkyl ether sulfate=15-30:1-3:0.5-2. The demulsifier molecule has high spatial extension and bidirectional diffusion effects and excellent coalescence capacity, and can realize three-phase effective separation of oil-water-slag (including polymer) by aiming at rapid deep demulsification of an oil-water transition layer rich in polymer and colloid asphaltene in a crude oil dehydration system through a thermo-chemical process.
Description
Technical Field
The invention belongs to the technical field of oilfield chemical preparations, and particularly relates to a demulsifier for treating an oil-water layer rich in polymers and colloid asphaltenes in a crude oil dehydration system and a preparation method thereof.
Background
The problem to be solved is to demulsify the oil-water passing layer in the crude oil dehydration system, the cause of which is complex, is generally considered to be the result of a plurality of comprehensive factors such as the use of a large amount of non-compatible chemical agents, mechanical impurities and bacterial metabolites contained in oil products, and recovery of aging oil. The oil-water mixed emulsion is complex in components, a part of the oil-water mixed layer is in a W/O/W or O/W/O sleeve type state and the other part of the oil-water mixed layer is in an O/W state when being observed under a high-power microscope, the water content of the mixed layer is generally stabilized at about 45-85%, the mixed layer contains inorganic salt, metal oxide (such as FeS), colloid and asphaltene, paraffin, mechanical impurities and the like through chemical analysis, and some mixed layer oil products also contain very sticky high polymers, all the substances are scattered in the mixed layer in a disordered manner to form emulsion which is stable in the mixed layer, and a large number of experiments show that the mixed layer is difficult to effectively demulsify the mixed layer by singly using a conventional crude oil demulsifying agent.
At present, the treatment of the transition layer is generally periodic physical removal, which causes secondary pollution to the environment. There are demulsification by a centrifuge and demulsification by distillation, but the cost is too high, and the treatment by microwaves is also useful, but the treatment effect is not ideal, and sometimes the emulsification degree of an excessive layer is even increased. There are reports in China that a composite medicament of sodium alkyl sulfonate, sulfuric acid, sulfate and conventional demulsifier is disclosed in "treatment of oil-water transition layer in crude oil dehydration" of volume 11 and phase 2 of the journal of petroleum planning and design, and satisfactory effect is obtained on demulsification of certain transition layers, but the demulsification effect on transition layers rich in polymers and in colloid asphaltenes is not ideal, and the main appearance is that no demulsification or the demulsification effect is very little.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an oil-water transition layer demulsifier which has a good demulsification effect on an oil-water transition layer rich in polymers and colloid asphaltenes, and realizes oil-water-slag three-phase separation after thermochemical demulsification. On one hand, the problem that the dewatering system is disordered and the water content of the oil product is out of standard caused by the continuous accumulation and thickening of the oil-water transition layer is solved, and on the other hand, the problem of environmental pollution caused by direct discharge because the transition layer cannot be effectively treated is solved.
In order to achieve the above object, the present invention provides the following technical solutions: a demulsifier for treating an oil-water transition layer rich in polymer and colloid asphaltene is composed of the following components in percentage by mass: demulsifier SR: sodium diacetate: alkyl ether sulfate = 15-30: 1 to 3:0.5 to 2.
Wherein the SR demulsifier has a structure as shown in a formula I:
M：-CH＝CH-，-CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -，
Ro：
R：
m=1, 2,3,4,5 or 6
x=1, 2,3,4,5,6,7,8,9 or 10
y=1, 2,3,4,5,6,7,8,9 or 10
z=1, 2,3,4,5,6,7,8,9 or 10
Wherein x, y, z represent the degree of polymerization.
Wherein the structural formula of the alkyl ether sulfate is as follows:
wherein R is dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or isoeicosyl, n represents the addition number of ethylene oxide, and n=an integer of 1 to 6.
A method for preparing a demulsifier for treating a polymer-rich and colloid asphaltene-rich oil-water transition layer in a crude oil dewatering system as described above, preferably, comprises the following steps:
1. preparation of oil head YPAE
According to the mass ratio, the initiator: propylene oxide = 1: 199-1: 499, firstly adding a specified amount of initiator into a reaction kettle, heating to 88-90 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content, then measuring water content once every half an hour of bubbling until the water content is less than 0.03%, vacuumizing, when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, firstly introducing propylene oxide with one third of the mass of the initiator, heating to 99-105 ℃, keeping the reaction pressure at 0.4-0.5 MPa, when the pressure is reduced to 0.02MPa, introducing the rest of the propylene oxide, keeping the pressure at 0.4-0.5 MPa, and when the pressure is reduced to 0.02MPa, keeping the temperature for half an hour, and then reducing the temperature to 80 ℃ to obtain the YPAE oil head.
Preferably, the initiator is tetraethylenepentamine, mannitol or ethyl hydrogen silicone oil.
Preferably, the initiator: propylene oxide = 1: 199-1: 399.
2. preparation of demulsifier DPAE
According to the mass ratio, YPAE: ethylene oxide: propylene oxide = 20-50: 6-24: 1-3, firstly adding a specified amount of YPAE and an alkaline catalyst into a reaction kettle, heating to 88-90 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour, until the water content is less than 0.03%, vacuumizing, introducing specified amount of ethylene oxide when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, heating to 105-110 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing specified amount of propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 0.4-0.5 MPa at 100-108 ℃, neutralizing with glacial acetic acid to the PH value at 5.5-6 when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain the DPAE.
Preferably, YPAE: ethylene oxide: propylene oxide = 35-45: 12-16: 1 to 2.
Preferably, the basic catalyst is potassium hydroxide.
3. Preparation of demulsifier SR
Refined castor oil according to the mass ratio: DPAE: graft chain extender = 1:3 to 7: adding refined castor oil and a grafting chain extender into a reactor according to a proportion of 0.1-0.25, adding an esterification catalyst accounting for 0.4-0.6% of the refined castor oil according to a proportion, adding a hydroquinone ethanol solution accounting for 200-400 ppm and with a mass percentage concentration of 20-21% of the refined castor oil, stirring and mixing uniformly, heating to 75-80 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour, measuring until the water content is less than 0.03%, adding 50-100 ppm of laurel mercaptan accounting for the refined castor oil, adding DPAE according to a proportion, stirring and heating to 110-120 ℃ for 2 hours, sampling and measuring the dynamic viscosity of a material at 70 ℃ every half an hour, cooling to 80 ℃ when the material viscosity reaches 450-500 cP, adding triethanolamine, measuring and adjusting the PH value to 5.5-6.5, and stirring uniformly to obtain a demulsifier SR.
Preferably, the iodine value of the refined castor oil is 82-85 g/g, and the saponification value is 176-180 mgKOH/g.
Preferably, the refined castor oil: DPAE: graft chain extender = 1:4 to 6:0.15 to 0.2.
Preferably, the graft chain extender is 2, 3-pyrazinedicarboxylic acid anhydride, 2, 3-pyridinedicarboxylic acid anhydride, phthalic acid anhydride.
Preferably, the esterification catalyst is phosphoric acid, p-toluene sulfonic acid or dodecylbenzene sulfonic acid.
Preferably, the adding amount of the esterification catalyst is 0.45-0.5% of the mass of the refined castor oil.
Preferably, the amount of the alcoholic solution of the benzenediol added is 300 to 350ppm based on the refined castor oil.
Preferably, the added amount of laurylthiol is 60 to 80ppm based on the refined castor oil.
4. Preparation of demulsifier DSR of the present invention
Demulsifier SR: sodium diacetate: alkyl ether sulfate = 15-30: 1 to 3: and (2) heating the demulsifier SR to 65-75 ℃, sequentially adding sodium diacetate and alkyl ether sulfate while stirring, heating to 75-85 ℃ after the two materials are added, and preserving heat for half an hour to obtain the demulsifier DSR.
Preferably, demulsifier SR: sodium diacetate: alkyl ether sulfate = 18-21: 1-2: 0.5 to 1.
Preferably, in the alkyl ether sulfate, alkyl is dodecyl or tridecyl, and ethylene oxide is added to an integer of 3 to 5.
Preferably, the demulsifier SR is heated to a feed temperature of 70 ℃.
Preferably, the incubation temperature is 80 ℃.
Compared with the prior art, the invention has the following characteristics:
1. the demulsifier component of the invention comprises a novel star-tree structure, and long chain alkyl is introduced into castor oil molecules in component raw materials, so that the molecular structure can offset the blocking effect of intermolecular stress to a greater extent, is easy for molecules to diffuse to an oil-water interface, has sufficient space expansion effect and flocculation capability, and conventional demulsifier molecules block the diffusion behavior and the space expansion effect of the molecules due to the limitation of the structure.
2. The demulsifier components sodium diacetate and alkyl ether sulfate have excellent demulsification cooperativity, wettability and permeability, so that the one-way diffusion of demulsifier molecules is converted into two-way diffusion, and the demulsifier can effectively demulsifie oil products of O/W/O and W/O type snare type and single O/W or W/O type transition zone rich in polymer and colloid asphaltene, and the conventional demulsifier has no or very weak two-way diffusion behavior, so that the phenomenon of no demulsification or very low demulsification efficiency is often caused when the demulsification is conducted on oil products of complex transition zones.
3. The components of the demulsifier, namely the castor oil, the sodium diacetate and the alkyl ether sulfate are safe to use, the raw materials are easy to obtain, the preparation process is simple, the emission of three wastes is avoided, and the demulsifier is worthy of popularization.
Detailed Description
The following detailed description of the invention is of the embodiments, and is intended to be exemplary and explanatory only and should not be construed as limiting the scope of the invention.
Embodiment 1
1. Preparation of oil head YPAE1
Tetraethylenepentamine in mass ratio: propylene oxide = 1:199, firstly adding a prescribed amount of tetraethylenepentamine into a reaction kettle, heating to 88-90 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content, then measuring water content once every half an hour, until the water content is less than 0.03%, vacuumizing, when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, firstly introducing one third of the mass of propylene oxide of the tetraethylenepentamine, heating to 99-105 ℃, keeping the reaction pressure at 0.4-0.5 MPa, when the pressure is reduced to 0.02MPa, introducing the rest of the propylene oxide, keeping the reaction pressure at 0.4-0.5 MPa, and the reaction temperature at 125-135 ℃, when the pressure is reduced to 0.02MPa, preserving heat for half an hour, and then cooling to 80 ℃ to obtain the YPAE1 oil head.
2. Preparation of demulsifier DPAE1
YPAE1: ethylene oxide: propylene oxide = 35:12:1, firstly adding a specified amount of YPAE1 and potassium hydroxide into a reaction kettle, wherein the catalyst potassium hydroxide is added into 0.3 percent of the total mass of materials according to the proportion, heating to 88-90 ℃, bubbling for 1 hour from the bottom of the reaction kettle by using nitrogen, measuring water content every half an hour, measuring water content until the water content is less than 0.03 percent, vacuumizing, introducing specified amount of ethylene oxide when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, heating to 105-110 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing specified amount of propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 100-108 ℃, keeping the reaction pressure at 0.4-0.5 MPa, neutralizing to a PH value of 5.5-6 by using glacial acetic acid when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain the DPAE1.
3. Preparation of demulsifier SR1
Refined castor oil according to the mass ratio: DPAE1:2,3 pyrazinedicarboxylic anhydride=1: 4: adding refined castor oil and 2, 3-pyrazine dianhydride into a reactor according to a proportion, adding phosphoric acid with the mass of 0.45% of the refined castor oil according to a proportion, adding a hydroquinone ethanol solution with the mass percentage concentration of 20-21% and 300ppm calculated by the refined castor oil, stirring and mixing uniformly, heating to 75-80 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour until the water content is less than 0.03%, adding laurel mercaptan with the mass percentage of 60ppm calculated by the refined castor oil, adding DPEA1 according to a proportion, stirring and heating to 110-120 ℃, preserving heat for 2 hours, sampling and measuring the dynamic viscosity of a material at 70 ℃ every half an hour, cooling to 80 ℃, adding triethanolamine when the viscosity of the material reaches 450-500 cP, measuring and adjusting the PH value to 5.5-6.5 by a PH meter, and stirring uniformly to obtain the demulsifier SR1.
4. Preparation of demulsifier DSR1 of the present invention
Demulsifier SR1: SDA (serial digital access card): sodium dodecyl ether sulfate with an ethylene oxide addition number of 3 = 18:1:0.5, firstly adding a demulsifier SR1 into a mixing kettle, then heating to 70 ℃, sequentially adding sodium diacetate and sodium dodecyl ether sulfate while stirring, heating to 80 ℃ after the two materials are added, and preserving heat for half an hour to obtain the demulsifier DSR1.
5. The physical and chemical indexes of the demulsifier DSR1 are as follows:
1. appearance: amber semitransparent viscous liquid
2. Density (20 ℃): 0.912g/cm 3
3、RSN＝13.5
4、PH＝5.8
5. Dynamic viscosity (70 ℃): 455cP
All the indexes meet the requirements of the general technical condition and the use specification of the SY/T5280-2018 crude oil demulsifier in the Chinese petroleum and natural gas industry standard.
Embodiment 2
1. Preparation of oil head YPAE2
Mannitol according to mass ratio: propylene oxide = 1:299, firstly, putting a prescribed amount of mannitol into a reaction kettle, heating to 88-90 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content every half an hour, vacuumizing until the water content is less than 0.03%, when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, firstly introducing propylene oxide with one third of the mass of mannitol, heating to 99-105 ℃, keeping the reaction pressure at 0.4-0.5 MPa, when the pressure is reduced to 0.02MPa, introducing the rest amount of propylene oxide, and when the reaction pressure is reduced to 0.4-0.5 MPa, the reaction temperature is 125-135 ℃, and when the pressure is reduced to 0.02MPa, preserving heat for half an hour, and then reducing the temperature to 80 ℃ to obtain the YPAE2 oil head.
2. Preparation of demulsifier DPAE2
YPAE2: ethylene oxide: propylene oxide = 40:15:1.5, firstly adding a specified amount of YPAE2 and potassium hydroxide into a reaction kettle, wherein the catalyst potassium hydroxide is added into 0.3 percent of the total mass of materials according to the proportion, heating to 88-90 ℃, bubbling with nitrogen from the bottom of the reaction kettle for 1 hour, measuring the water content once every half hour until the water content is less than 0.03 percent, vacuumizing, introducing specified amount of ethylene oxide when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, heating to 105-110 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing specified amount of propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 100-108 ℃, keeping the reaction pressure at 0.4-0.5 MPa, neutralizing to the PH value at 5.5-6 with glacial acetic acid when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain the DPAE2.
3. Preparation of demulsifier SR2
Refined castor oil according to the mass ratio: DPAE2:2,3 pyridine dianhydride = 1:4.5: adding refined castor oil and 2,3 pyridine dianhydride into a reactor according to a proportion, adding p-toluenesulfonic acid accounting for 0.5% of the mass of the refined castor oil according to a proportion, adding hydroquinone ethanol solution accounting for 320ppm and with the mass percentage concentration of 20-21% of the refined castor oil, stirring and mixing uniformly, heating to 75-80 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour until the water content is less than 0.03%, adding laurel mercaptan accounting for 70ppm of the refined castor oil, adding DPAE2 according to a proportion, stirring and heating to 110-120 ℃, preserving heat for 2 hours, sampling and measuring dynamic viscosity of a material at 70 ℃ every half an hour, cooling to 80 ℃, adding triethanolamine when the material viscosity reaches 450-500 cP, measuring and adjusting the PH value to 5.5-6.5 by a PH meter, and stirring uniformly to obtain the demulsifier SR2.
4. Preparation of demulsifier DSR2 of the present invention
Demulsifier SR2: sodium diacetate: ammonium lauryl ether sulfate with an ethylene oxide addition number of 4 = 19:1.5: and 0.8, firstly adding a demulsifier SR2 into the mixing kettle, then heating to 70 ℃, sequentially adding SDA and dodecyl ether sulfate ammonium while stirring, heating to 80 ℃ after the two materials are added, and preserving heat for half an hour to obtain the demulsifier DSR2.
5. The physical and chemical indexes of the demulsifier DSR2 are as follows:
1. appearance: amber semitransparent viscous liquid
2. Density (20 ℃): 0.915g/cm 3
3、RSN＝14.2
4、PH＝6.1
5. Dynamic viscosity (70 ℃): 460cP
All the indexes meet the requirements of the general technical condition and the use specification of the SY/T5280-2018 crude oil demulsifier in the Chinese petroleum and natural gas industry standard.
Embodiment 3
1. Preparation of oil head YPAE3
According to the mass ratio, ethyl hydrogen silicone oil: propylene oxide = 1:399, firstly adding a prescribed amount of ethyl hydrogen-containing silicone oil into a reaction kettle, heating to 88-90 ℃, bubbling for 1 hour from the bottom of the reaction kettle by using nitrogen, measuring water content, then measuring water content once every half an hour of bubbling until the water content is less than 0.03%, vacuumizing, when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, firstly introducing propylene oxide with one third of the mass of the ethyl hydrogen-containing silicone oil, heating to 99-105 ℃, keeping the reaction pressure at 0.4-0.5 MPa, when the pressure is reduced to 0.02MPa, introducing the rest of the propylene oxide, keeping the pressure at 0.4-0.5 MPa, and the reaction temperature at 125-135 ℃, when the pressure is reduced to 0.02MPa, preserving heat for half an hour, and then cooling to 80 ℃ to obtain the YPAE3 oil head.
2. Preparation of demulsifier DPAE3
YPAE3: ethylene oxide: propylene oxide = 45:15:1, firstly adding a specified amount of YPAE3 and potassium hydroxide into a reaction kettle, wherein the catalyst potassium hydroxide is added into 0.3 percent of the total mass of materials according to the proportion, heating to 88-90 ℃, bubbling with nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour until the water content is less than 0.03 percent, vacuumizing, introducing specified amount of ethylene oxide when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, heating to 105-110 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing specified amount of propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 100-108 ℃, keeping the reaction pressure at 0.4-0.5 MPa, neutralizing with glacial acetic acid to a PH value of 5.5-6 when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain DPAE3.
3. Preparation of demulsifier SR3
Refined castor oil according to the mass ratio: DPAE3: phthalic anhydride=1: 5.5: adding refined castor oil and phthalic anhydride into a reactor according to a proportion, adding boric acid accounting for 0.45% of the mass of the refined castor oil, adding hydroquinone ethanol solution accounting for 310ppm and accounting for 20-21% of the mass percent of the refined castor oil, stirring and mixing uniformly, heating to 75-80 ℃, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every half an hour until the water content is less than 0.03%, adding lauryl mercaptan accounting for 65ppm of the refined castor oil, adding DPAE3 according to a proportion, stirring and heating to 110-120 ℃, preserving heat for 2 hours, sampling and measuring dynamic viscosity of a material at 70 ℃ every half an hour, cooling to 80 ℃ when the material viscosity reaches 450-500 cP, adding triethanolamine, measuring and adjusting the pH value to 5.5-6.5 by a PH meter, and stirring uniformly to obtain the demulsifier SR3.
4. Preparation of demulsifier DSR3 of the present invention
Demulsifier SR3: sodium diacetate: sodium tridecyl ether sulfate with an ethylene oxide addition number of 5 = 20:1.8:0.7, firstly adding a demulsifier SR3 into a mixing kettle, then heating to 70 ℃, sequentially adding SDA and sodium tridecyl ether sulfate while stirring, heating to 80 ℃ after the two materials are added, and preserving heat for half an hour to obtain the demulsifier DSR3.
5. The physical and chemical indexes of the demulsifier DSR3 are as follows:
1. appearance: amber semitransparent viscous liquid
2. Density (20 ℃): 0.913g/cm 3
3、RSN＝13.7
4、PH＝5.9
5. Dynamic viscosity (70 ℃): 470cP
All the indexes meet the requirements of the general technical condition and the use specification of the SY/T5280-2018 crude oil demulsifier in the Chinese petroleum and natural gas industry standard.
The following emulsion breaking experiment comparison is performed on an oil-water transition layer, wherein the oil-water transition layer is respectively taken from Daqing oil field and Liaohe oil field, and the emulsion breaking effect pair is shown in tables 1 and 2. The evaluation standard adopts the general technical condition of the SY/T5280-2018 crude oil demulsifier in the China petroleum and natural gas industry standard.
Table 1 comparison of demulsification Effect of demulsifiers of different models (oil-water transition layer was taken from Daqing oilfield)
TABLE 2 demulsification Effect comparison of demulsifiers of different models (transition layer was taken from Liaohe oilfield)
Remarks: deslagging is the mass percentage of the total solids (including polymers and the like) contained in the total mass of the oil-water transition layer. The numerical calculation method of the solid (including polymer and the like) executes national standard GB/T6533-2012.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. A demulsifier for treating an oil-water transition layer rich in polymers and colloid asphaltenes in a crude oil dehydration system is composed of three components, wherein one component is a star-tree triblock demulsifier SR taking polyhydroxy ester as a core, the second component is sodium diacetate, the third component is alkyl ether sulfate, and the weight ratio of SR is as follows: sodium diacetate: alkyl ether sulfate = 15-30: 1 to 3:0.5 to 2;
wherein, the SR demulsifier has a structure as shown in a formula I:
wherein x, y, z represent the degree of polymerization;
wherein the structural formula of the alkyl ether sulfate is as follows:
wherein R is dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or isoeicosyl, and n=an integer of 1 to 6.
2. The method for preparing the demulsifier as claimed in claim 1, wherein the method comprises the following steps:
2.1 preparation of oil header YPAE
According to the mass ratio of the initiator to the propylene oxide=1:199-1:499, firstly adding a specified amount of the initiator polyethylene polyamine into a reaction kettle, heating to 88-90 ℃, bubbling for 1 hour from the bottom of the reaction kettle by using nitrogen, measuring water content once every half hour until the water content is less than 0.03%, vacuumizing, introducing one third of the mass of the initiator when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, heating to 99-105 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing the residual amount of the propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 0.4-0.5 MPa, keeping the temperature for half an hour when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain the YPAE oil head;
2.2 preparation of demulsifier DPAE
According to the mass ratio of YPAE to ethylene oxide to propylene oxide=20-50:6-24:1-3, firstly adding a specified amount of YPAE and an alkaline catalyst into a reaction kettle, wherein the alkaline catalyst is added into 0.3% of the total mass of materials according to the proportion, heating to 88-90 ℃, bubbling for 1 hour from the bottom of the reaction kettle with nitrogen, measuring water once every half hour of bubbling until the water content is less than 0.03%, vacuumizing, introducing the specified amount of ethylene oxide when the pressure in the reaction kettle is minus 0.09-minus 0.08MPa, then heating to 105-110 ℃, keeping the reaction pressure at 0.4-0.5 MPa, introducing the specified amount of propylene oxide when the pressure is reduced to 0.02MPa, keeping the reaction pressure at 100-108 ℃, keeping the reaction pressure at 0.4-0.5 MPa, neutralizing to the PH value at 5.5-6 with glacial acetic acid when the pressure is reduced to 0.02MPa, and cooling to 80 ℃ to obtain the demulsifier DPAE;
2.3 preparation of demulsifier SR
According to the mass ratio of refined castor oil to DPAE to graft chain extender=1:3-7:0.1-0.25, adding refined castor oil and graft chain extender into a reactor according to the proportion, adding esterification catalyst with the mass of 0.4-0.6% of refined castor oil according to the proportion, adding hydroquinone ethanol solution with the mass concentration of 20-21% and 200-400 ppm calculated by the refined castor oil, heating to 75-80 ℃ after stirring and mixing uniformly, bubbling nitrogen from the bottom of the reaction kettle for 1 hour, measuring water content once every bubbling for half an hour until the water content is less than 0.03%, adding laurel mercaptan with the mass of 50-100 ppm calculated by the refined castor oil, adding DPAE according to the proportion, stirring and heating to 110-120 ℃ for 2 hours, sampling and measuring the dynamic viscosity of materials in the kettle at 70 ℃ every half an hour, cooling to 80 ℃ when the material viscosity reaches 450-500 cP, adding triethanolamine, measuring and adjusting the PH value to 5.5-6.5 after stirring uniformly, and obtaining the demulsifier SR;
2.4 preparation of demulsifier DSR
According to the mass ratio, the demulsifier SR is heated to 65-70 ℃ according to the mass ratio of the demulsifier SR to the sodium diacetate to the sodium alkyl ether sulfate salt=15-30:1-3:0.5-2, then the sodium diacetate and the alkyl ether sulfate salt are sequentially added while stirring, and the temperature is raised to 80 ℃ for half an hour after the two materials are added, so as to obtain the demulsifier DSR.
3. The method for preparing the demulsifier as claimed in claim 2, wherein: the basic catalyst used in step 2.2 comprises potassium hydroxide, sodium hydroxide or calcium hydroxide.
4. The method for preparing the demulsifier as claimed in claim 2, wherein: the esterification catalyst used in step 2.3 comprises sulfuric acid, phosphoric acid, p-toluene sulfonic acid, hydrochloric acid or boric acid.
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| CN105504306A (en) * | 2016-01-15 | 2016-04-20 | 浙江大学 | Application of polyether hyperbranched polymers as demulsifier |
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