CN113509960B - Application of crown ether transition metal complex in underground in-situ modification of thickened oil and underground in-situ modification method of thickened oil - Google Patents
Application of crown ether transition metal complex in underground in-situ modification of thickened oil and underground in-situ modification method of thickened oil Download PDFInfo
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- -1 crown ether transition metal Chemical class 0.000 title claims abstract description 98
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 82
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 45
- 230000004048 modification Effects 0.000 title claims abstract description 45
- 238000012986 modification Methods 0.000 title claims abstract description 45
- 238000002715 modification method Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- 230000001603 reducing effect Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000000536 complexating effect Effects 0.000 claims abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 7
- 239000000295 fuel oil Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 10
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 150000003983 crown ethers Chemical class 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 4
- NBXKUSNBCPPKRA-UHFFFAOYSA-N 1,4,7,10,13-pentaoxa-16-azacyclooctadecane Chemical compound C1COCCOCCOCCOCCOCCN1 NBXKUSNBCPPKRA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 4
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 2
- 150000003993 24-crown-8 derivatives Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 238000010796 Steam-assisted gravity drainage Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The invention provides an application of crown ether transition metal complex in-situ modification of thick oil underground and a method for in-situ modification of thick oil underground. The application of crown ether transition metal complex as viscosity reducing catalyst in underground in-situ modification of thick oil is provided, wherein the crown ether transition metal complex is formed by complexing crown ether compound and transition metal ion. Injecting a viscosity-reducing catalyst crown ether transition metal complex into a target stratum, and raising the stratum temperature to a certain temperature after injecting the viscosity-reducing catalyst to perform a viscosity-reducing reaction of the thick oil; wherein the crown ether transition metal complex is formed by complexing crown ether compound and transition metal ion.
Description
Technical Field
The invention belongs to the technical field of thickened oil development and thermal recovery, and particularly relates to application of crown ether transition metal complex in underground in-situ modification of thickened oil and a method for underground in-situ modification of thickened oil.
Background
The thick oil reserves are rich in resources, account for nearly 70% of the residual recoverable reserves, have huge development potential and have been widely paid attention to. However, the conventional water flooding development is low-efficiency due to the high viscosity and poor flow property of the thick oil, and a high-efficiency development mode capable of reducing the viscosity of the thick oil and improving the performance of the thick oil is needed. The main development mode of thick oil at present is a thermal recovery technology mainly based on steam flooding and SAGD. However, with the development of thermal recovery entering the middle and later stages, the problems of high energy consumption, high pollution, low yield ratio and the like are increasingly remarkable, and the realization of the effective development of energy conservation and consumption reduction, economy and environmental protection of thickened oil becomes a hot spot of research in recent years.
The heavy oil in-situ modification technology is a technology for injecting a modification catalyst into an oil reservoir and realizing irreversible viscosity reduction of heavy oil in situ in the oil reservoir, and is a new generation of heavy oil development technology which is attractive. At present, the viscosity-reducing catalyst used in the thick oil in-situ modification technology mainly comprises three main types, namely a water-soluble catalyst, an oil-soluble catalyst and a nano catalyst. The nano catalyst has a plurality of problems in the construction and injection process of the ground liquid preparation, is easy to damage a reservoir and has higher cost. The water-soluble catalyst is cheap and easy to obtain, the process is simple, but the contact efficiency with crude oil in an oil reservoir is low, so that the catalytic effect is poor. The conventional oil-soluble catalyst can be well dispersed in oil to improve the contact and catalytic efficiency, but the oil-soluble catalyst cannot be dissolved in water, and a large amount of organic solvent is required to be carried into a stratum, so that the environment pollution is serious and the cost is high. The in-situ heavy oil modification viscosity-reducing catalyst has contradiction between injectability and contact catalytic efficiency, and needs a new generation of heavy oil modification viscosity-reducing agent which is more efficient and has both water-soluble injectability and oleophylic contact catalysis.
Disclosure of Invention
The invention aims to find a viscosity-reducing catalyst suitable for underground in-situ modification of thick oil, and the viscosity-reducing catalyst can be applied to underground in-situ modification of thick oil to effectively solve the contradiction between the injectability and the catalytic contact efficiency of the viscosity-reducing catalyst in the prior art, so as to realize the synergy of water-soluble injectability and efficient catalytic contact.
In order to achieve the above object, the present invention provides the use of crown ether transition metal complexes (also called crown ether transition metal complexes) formed by complexing crown ether compounds (having crown ether macrocyclic structures) with transition metal ions as viscosity reducing catalysts in the underground in situ upgrading of heavy oil.
The crown ether transition metal complex has crown ether macrocyclic structure, and is formed by complexing crown ether compound and transition metal, and the transition metal ion with catalytic activity is coated in crown ether molecule. The crown ether transition metal complex is a transition metal complex which can be dissolved in water, the hydrophilia of the crown ether group is influenced by temperature, and when the temperature is higher than the cloud point, the hydrophilia is greatly reduced, and the lipophilicity is improved. The crown ether transition metal complex has the function of catalyzing the cracking and viscosity reduction of thick oil, has good water-solubility at normal temperature, can be injected into a stratum along with water, has the characteristic of high-temperature oil solubility due to the fact that the hydrophilic property of the crown ether transition metal complex can be reduced along with the temperature, and after an oil layer is heated, the oil solubility of the crown ether transition metal complex is improved to spontaneously enter an oil phase for catalytic modification reaction.
The crown ether transition metal complex is used as a viscosity-reducing catalyst in the underground in-situ modification process of the thickened oil, so that the viscosity-reducing catalyst can be injected into a stratum along with water, and the viscosity-reducing catalyst spontaneously diffuses to an oil phase to catalyze the thickened oil to perform a modification viscosity-reducing reaction, thereby achieving the synergy of water-soluble injectability and high-efficiency contact catalysis. The crown ether transition metal complex is used for the first time in the technical field of underground in-situ modification of thick oil.
In the above application, preferably, the crown ether compound includes one of a peroxy crown ether compound, an aza crown ether compound, a thiacrown ether compound and derivatives thereof; more preferably, the lipophilic alkyl group of the derivative includes one or a combination of two or more of a linear alkane, a branched alkane-containing hydrocarbon, a benzene ring, and the like.
In the above application, preferably, the crown ether main structure of the crown ether compound includes one of 12 crown 4 ether, 15 crown 5 ether, 18 crown 6 ether, 24 crown 8 ether and derivatives thereof.
In the above application, preferably, the transition metal includes one of Co, ni, mn, cu, mo and Ag.
In one embodiment, the crown ether compound includes 18-crown-6 (CAS: 17455-13-9), benzo-15-crown-5 (CAS: 14098-44-3), dibenzo-15-crown-5 (CAS: 14262-60-3), dibenzo-18-crown-6 (CAS: 14187-32-7), dibenzo-24-crown-8 (CAS: 14174-09-5), 1-aza-18-crown-6 (CAS: 33941-15-0), 1, 10-diaza-18-crown-6 (CAS: 23978-55-4), dibenzo-aza-15-crown-5, dibenzo-aza-18-crown-6.
In the above application, preferably, the crown ether transition metal complex has the structure:
wherein n=1, 2, 3 or 5; i= … … n; x is X 1 、X 2 、X 3 、X 3+i Independently selected from one of O, N-H, S; r is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 5+2i 、R 6+2i Independently selected from one of hydrogen, linear alkane, branched alkane-containing hydrocarbon, benzene ring, etc.; m is selected from one of transition metals (preferably one of Co, ni, mn, cu, mo and Ag);
in one embodiment, the crown ether transition metal complex has the structure:wherein M is selected from one of transition metals (preferably one of Co, ni, mn, cu, mo and Ag);
in one embodiment, the crown ether transition metal complex has the structure:wherein M is selected from one of transition metals (preferably one of Co, ni, mn, cu, mo and Ag).
In the above application, preferably, the cloud point temperature of the crown ether transition metal complex is 80 ℃ or lower.
The invention also provides a method for modifying the thick oil underground in situ, wherein the method comprises the steps of injecting a viscosity-reducing catalyst crown ether transition metal complex (also called crown ether transition metal complex) into a target stratum, and raising the stratum temperature to a certain temperature after injecting the viscosity-reducing catalyst to carry out a thick oil modification viscosity-reducing reaction; wherein the crown ether transition metal complex is formed by complexing crown ether compound (with crown ether macrocyclic structure) and transition metal ion.
The crown ether transition metal complex used in the method for underground in-situ modification of the thickened oil is the same as the crown ether transition metal complex (also called crown ether transition metal complex) in the application of the crown ether transition metal complex as a viscosity reducing catalyst in underground in-situ modification of the thickened oil.
The underground in-situ modifying process of heavy oil is one technology of irreversible modification and viscosity reduction of heavy oil in stratum developed for heavy oil reservoir with viscosity over 50 mPa.s, and belongs to the field of heavy oil heat recovery technology in tertiary oil recovery.
Crown ether transition metal complexes are used as viscosity-reducing catalysts in the underground in-situ modification process of the thickened oil, so that the viscosity-reducing catalysts can be injected into a stratum along with water (namely, water-based efficient injection of the thickened oil modifying catalysts can be realized), and the viscosity-reducing catalysts spontaneously diffuse into an oil phase to catalyze the thickened oil to undergo a modifying viscosity-reducing reaction, so that the synergy of water-soluble injectability and efficient contact catalysis is achieved. The on-site liquid preparation of the viscosity-reducing catalyst solution in the underground in-situ modification process of the thickened oil can be realized, and the injection process is simple. The method for in-situ modification of oil underground provided by the invention uses crown ether transition metal complex as a viscosity reducing catalyst for the first time.
In the above method for underground in-situ modification of heavy oil, preferably, the crown ether compound includes one of a total oxygen crown ether compound, an aza crown ether compound, a thiacrown ether compound and derivatives thereof; more preferably, the lipophilic alkyl group of the derivative includes one or a combination of two or more of a linear alkane, a branched alkane-containing hydrocarbon, a benzene ring, and the like.
In the above method for underground in-situ modification of heavy oil, preferably, the crown ether main structure of crown ether compound includes one of 12 crown 4 ether, 15 crown 5 ether, 18 crown 6 ether, 24 crown 8 ether and derivatives thereof.
In one embodiment, the crown ether compound includes 18-crown-6 (CAS: 17455-13-9), benzo-15-crown-5 (CAS: 14098-44-3), dibenzo-15-crown-5 (CAS: 14262-60-3), dibenzo-18-crown-6 (CAS: 14187-32-7), dibenzo-24-crown-8 (CAS: 14174-09-5), 1-aza-18-crown-6 (CAS: 33941-15-0), 1, 10-diaza-18-crown-6 (CAS: 23978-55-4), dibenzo-aza-15-crown-5, dibenzo-aza-18-crown-6.
In the above-described method for underground in-situ upgrading of heavy oil, preferably, the transition metal comprises one of Co, ni, mn, cu, mo and Ag.
In the above-described method for underground in-situ upgrading of a heavy oil, preferably, the cloud point temperature of the crown ether transition metal complex is 80 ℃ or lower.
In the above method for underground in-situ modification of heavy oil, preferably, the crown ether transition metal complex has the structure:
wherein n=1, 2, 3 or 5; i= … … n; x is X 1 、X 2 、X 3 、X 3+i Independently selected from one of O, N-H, S; r is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 5+2i 、R 6+2i Independently selected from one of hydrogen, linear alkane, branched alkane-containing hydrocarbon, benzene ring, etc.; m is selected from one of transition metals (preferably one of Co, ni, mn, cu, mo and Ag);
in one embodiment, the crown ether transition metal complex has the structure:
in one embodiment, the crown ether transition metal complex has the structure:
in the above-described method for in-situ upgrading of a heavy oil underground, the method preferably comprises: injecting crown ether transition metal complex aqueous solution into a target stratum, and then raising the stratum temperature to more than 200 ℃ to perform thickened oil modification viscosity reduction reaction; more preferably, the formation temperature is raised to 250-350 ℃; more preferably, the soaking is performed after the formation temperature is raised to the target temperature; more preferably, the formation temperature elevation is performed by injecting high temperature superheated steam and/or using electrical heating;
the formation temperature is raised to be more than 200 ℃ so as to be more conducive to the heavy oil modification viscosity reduction reaction, and the cloud point temperature of the crown ether transition metal complex is far beyond 200 ℃, so that the lipophilicity can be greatly improved and can be efficiently diffused into crude oil; therefore, the underground in-situ modification of the thick oil can be better realized by increasing the stratum temperature to more than 200 ℃.
In one embodiment, after injection of the crown ether transition metal complex aqueous solution into the target formation, high temperature superheated steam is injected and/or the formation is heated to above 200 ℃ by using an electric heating mode to perform a thickened oil modification viscosity reduction reaction.
In one embodiment, an aqueous solution of crown ether transition metal complex is injected into the target formation, followed by injection of high temperature superheated steam and/or heating of the formation to 250-350 ℃ using electrical heating, shut-in for 5-25 days, and open-hole production.
In the above method for underground in-situ modification of a thickened oil, preferably, the concentration of the crown ether transition metal complex in the crown ether transition metal complex aqueous solution is 10 based on the total volume of the crown ether transition metal complex aqueous solution -3 mmol/L-1mmol/L。
According to the technical scheme provided by the invention, the crown ether transition metal complex is used as a viscosity reducing catalyst in a method for underground in-situ modification of thick oil, the crown ether transition metal complex has temperature-sensitive property, the cloud point temperature of the crown ether transition metal complex is generally below 80 ℃, the crown ether transition metal complex has strong water solubility at low temperature and can be directly dispersed in a water phase, and the lipophilicity is greatly improved along with the temperature rise; therefore, the following excellent effects are obtained: the crown ether transition metal complex is used as the viscosity reducing catalyst in the method of underground in-situ modification of the thick oil, so that the viscosity reducing catalyst is injected into the deep part of an oil reservoir along with water in the underground in-situ modification process of the thick oil, then the bottom layer is heated to a certain temperature (the requirement of the viscosity reducing catalyst for catalyzing the thick oil to carry out the viscosity reducing reaction of modification of the thick oil is met), the viscosity reducing reaction of the thick oil is carried out, at the moment, the stratum temperature is the cloud point temperature of the original super crown ether transition metal complex, the lipophilicity of the crown ether transition metal complex is greatly improved, and is diffused into crude oil to catalyze the crude oil to carry out the viscosity reducing reaction of modification, the water-based injection of the thick oil underground modification catalyst and the efficient catalysis of the oil phase are synergistically realized, the complex injection process (without adding surfactants, organic solvents, cosolvents and the like) of the common oil soluble catalyst is greatly simplified, and the catalytic contact efficiency and the catalytic viscosity reducing effect of the common water soluble catalyst are enhanced.
Drawings
FIG. 1A is a schematic distribution diagram of a mixture of crown ether transition metal complex aqueous solution and kerosene at room temperature in example 1 of the present invention.
FIG. 1B is a schematic diagram showing the distribution of an aqueous crown ether transition metal complex and kerosene mixture at 60℃in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The present example provides a demonstration of the potential of crown ether transition metal complexes for use as viscosity reducing catalysts in underground in situ upgrading of heavy oil.
Preparation of crown ether transition metal complex used as viscosity reducing catalyst in underground in-situ modification of heavy oil, wherein the crown ether transition metal complex is N 3 O 2 The specific synthesis method and structure verification of the aza crown ether cobalt complex are shown in the literature: wang Yan, liu Yi, liu, etc. N 3 O 2 Synthesis of aza crown ether and solid phase Synthesis of cobalt Complex thereof [ C]Chinese medicineInorganic chemistry and chemical chemistry academy of sciences meeting, discussion of the western region of the chemical society 2008:173-174.
Dissolving the prepared crown ether transition metal complex in water with the concentration of 0.4mmol/L, mixing and fully dissolving to prepare crown ether transition metal complex aqueous solution;
kerosene is added into the crown ether transition metal complex aqueous solution, the temperature is gradually increased to 60 ℃, and the crown ether transition metal complex prepared (see fig. 1A-1B) can be observed to spontaneously expand into an upper oil phase, so that the crown ether transition metal complex has excellent water solubility at normal temperature and has temperature-sensitive characteristics of increasing oil solubility along with the increase of the temperature;
adding crown ether transition metal complex aqueous solution and a certain oilfield super-thick oil sample (the viscosity of crude oil is 23586 mPa.s at 50 ℃) in northwest area into a high-temperature high-pressure reaction kettle, and replacing air in the reaction kettle with nitrogen; setting the initial pressure of the reaction kettle to be 1MPa, setting the reaction temperature to be 300 ℃, maintaining for 8 hours, cooling the reaction kettle to room temperature, and ending the reaction; the rotation speed of the stirring paddle is always controlled at 400r/min in the reaction process; the viscosity of the modified dehydrated crude oil is reduced to 2777 mPa.s at 50 ℃, and the viscosity reduction rate reaches 88.2%.
From this, it is known that crown ether transition metal complexes have the potential to be used as viscosity-reducing catalysts in underground in-situ upgrading of heavy oil, which can be used as viscosity-reducing catalysts in underground in-situ upgrading of heavy oil.
Example 2
The embodiment provides a method for underground in-situ modification of thick oil.
Selecting a certain thick oil field in northwest China as a single well small test block, and selecting a 1# well with better sealing property as a test well; the test well depth was about 500m and the formation pressure was 4.96MPa.
The invention provides an underground in-situ modification of thick oil, which uses crown ether transition metal complex as viscosity reduction catalyst, specifically uses nickel 18-crown-6 aza crown ether complex as viscosity reduction catalyst, and specific synthetic process and ligand structure verification are shown in documents Wang Genglin, yan Shiping, liao Daizheng, etc. Co (II), ni (II) is as large as tetraoxy dinitrogenStudy of the Ring ligand Complex I. NiCl 2 Ni(ClO 4 ) 2 Synthesis and Properties of CotetraOxodiazene macrocyclic ligand Complex [ J]Instructions on chemistry, 1986 (02): 196-199).
The specific synthesis method comprises the following steps: equimolar Ni (ClO) 4 ) 2 ·5H 2 O and tetraoxadiazine macrocyclic ligand are respectively dissolved in absolute ethyl alcohol, the ethanol solution of the ligand is slowly dripped into the ethanol solution of the refluxing nickel salt, and the mixture is continuously stirred and refluxed for 4 hours, a green solid product is separated out, cooled, filtered and washed three times by the absolute ethyl alcohol, and vacuum drying is carried out at room temperature, thus obtaining the required nickel 18-crown-6 aza crown ether complex.
The method for underground in-situ modification of the thick oil provided by the embodiment comprises the following steps:
dissolving the nickel 18-crown-6 aza crown ether complex in 6 tons of injection water to prepare a viscosity reducing catalyst aqueous solution with the concentration of 0.8mmol/L (based on the total volume of the viscosity reducing catalyst aqueous solution);
injecting the viscosity-reducing catalyst aqueous solution into a test well;
subsequently, 1200m was injected into the test well 3 Superheated steam, the formation temperature near the well reaches about 280 ℃, and the well is closed for 10 days; and (5) well opening and oil extraction.
Single well test results: the average dehydration viscosity of crude oil produced by the round of well opening is 759 mPa.s at 50 ℃, and the viscosity reduction rate reaches 98.0%. The exploitation effect is good.
The dewatering viscosity of the heavy oil produced by the test well in the huff and puff round before the heavy oil underground in-situ modification is carried out is 37664 mPa.s at 50 ℃, the number of days of self-injection of the last round of well opening is 8 days, and the wellhead temperature of the last 8 days of well opening is only 80 ℃. After the viscosity-reducing catalyst aqueous solution is injected, the test well is self-injected for 27 days after being opened, and the wellhead temperature is still higher than 100 ℃ after the test well is opened for 32 days.
Claims (11)
1. The application of crown ether transition metal complex as a viscosity reducing catalyst in underground in-situ modification of heavy oil, wherein the crown ether transition metal complex is formed by complexing crown ether compound and transition metal ion;
wherein the crown ether compound comprises one of 18-crown ether-6, benzo-15-crown ether-5, dibenzo-18-crown ether-6), dibenzo-24-crown ether-8, 1-aza-18-crown ether-6,1,10-diaza-18-crown ether-6, dibenzo-aza-15-crown ether-5 and dibenzo-aza-18-crown ether-6.
2. The use of claim 1, wherein the transition metal comprises one of Co, ni, mn, cu, mo and Ag.
3. The use according to claim 1, wherein the cloud point temperature of the crown ether transition metal complex is below 80 ℃.
4. The method comprises injecting a viscosity-reducing catalyst crown ether transition metal complex into a target stratum, and raising the stratum temperature to a certain temperature to perform a viscosity-reducing reaction; wherein the crown ether transition metal complex is formed by complexing crown ether compounds with transition metal ions;
wherein the crown ether compound comprises one of 18-crown ether-6, benzo-15-crown ether-5, dibenzo-18-crown ether-6, dibenzo-24-crown ether-8, 1-aza-18-crown ether-6,1,10-diaza-18-crown ether-6, dibenzo-aza-15-crown ether-5 and dibenzo-aza-18-crown ether-6.
5. The method of claim 4, wherein the transition metal comprises one of Co, ni, mn, cu, mo and Ag.
6. The method of claim 4, wherein the crown ether transition metal complex has a cloud point temperature of 80 ℃ or less.
7. The method according to claim 4, wherein the method comprises: after injecting crown ether transition metal complex aqueous solution into the target stratum, raising the stratum temperature to above 200 ℃ to perform heavy oil modification viscosity reduction reaction.
8. The method of claim 7, wherein the formation temperature is raised to 250-350 ℃.
9. The method of claim 7, wherein the soaking is performed after raising the formation temperature to the target temperature.
10. The method of claim 7, wherein the method comprises: firstly injecting crown ether transition metal complex aqueous solution into a target stratum, then injecting high-temperature superheated steam and/or heating the stratum to 250-350 ℃ by using an electric heating mode, closing the well for 5-25 days, and opening the well to produce.
11. The method according to any one of claims 7 to 10, wherein the concentration of the crown ether transition metal complex in the crown ether transition metal complex aqueous solution is 10 based on the total volume of the crown ether transition metal complex aqueous solution -3 mmol/L-1mmol/L。
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| CN106693962A (en) * | 2017-01-21 | 2017-05-24 | 杨林 | Method for preparing dual-precious-metal nanometer catalyst |
| CN110669489A (en) * | 2019-10-14 | 2020-01-10 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
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| CN106693962A (en) * | 2017-01-21 | 2017-05-24 | 杨林 | Method for preparing dual-precious-metal nanometer catalyst |
| CN110669489A (en) * | 2019-10-14 | 2020-01-10 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
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