CN113509960A - 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 88
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 82
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- 230000004048 modification Effects 0.000 title claims abstract description 40
- 238000012986 modification Methods 0.000 title claims abstract description 40
- 238000002715 modification method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000000536 complexating effect Effects 0.000 claims abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 37
- 238000006722 reduction reaction Methods 0.000 claims description 20
- 150000003983 crown ethers Chemical class 0.000 claims description 19
- 150000003624 transition metals Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims description 6
- NBXKUSNBCPPKRA-UHFFFAOYSA-N 1,4,7,10,13-pentaoxa-16-azacyclooctadecane Chemical compound C1COCCOCCOCCOCCOCCN1 NBXKUSNBCPPKRA-UHFFFAOYSA-N 0.000 claims description 6
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 6
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 6
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 claims description 4
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 4
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003993 24-crown-8 derivatives Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 12
- 239000003921 oil Substances 0.000 description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000295 fuel oil Substances 0.000 description 11
- 230000008569 process Effects 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
- 238000005516 engineering process Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000534944 Thia Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 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
- 239000000203 mixture Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 241000152447 Hades Species 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 238000010796 Steam-assisted gravity drainage Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000010276 construction 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
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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- 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- B01J2531/02—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
-
- 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
- B01J2531/845—Cobalt
-
- 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
Abstract
The invention provides an application of crown ether transition metal complex in underground in-situ modification of thickened oil and an underground in-situ modification method of thickened oil. The crown ether transition metal complex is used as a viscosity reduction catalyst in underground in-situ modification of thickened oil, and is formed by complexing crown ether compounds and transition metal ions. Injecting viscosity-reducing catalyst crown ether transition metal complex into a target stratum, and raising the temperature of the stratum to a certain temperature after injecting the viscosity-reducing catalyst to carry out the viscosity-reducing reaction for modifying the thickened oil underground in situ; wherein the crown ether transition metal complex is formed by complexing crown ether compounds and transition metal ions.
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 complexes in underground in-situ modification of thickened oil and a method for underground in-situ modification of thickened oil.
Background
The heavy oil reserves are abundant, account for nearly 70% of the remaining recoverable reserves, have great development potential, and have been widely concerned all the time. However, the viscous oil has low efficiency in conventional water drive development due to high viscosity and poor flow property, and an efficient development mode capable of reducing the viscosity of the viscous oil and improving the performance of the viscous oil is urgently needed. At present, the main development mode of the heavy oil is a thermal recovery technology taking steam flooding and SAGD as the dominance. However, as thermal recovery development enters the middle and later stages, the problems of high energy consumption, high pollution, low output ratio and the like are increasingly highlighted, and the effective development of energy conservation, consumption reduction, economy and environmental protection of thickened oil becomes a hotspot of research in recent years.
The in-situ thickened oil modifying technology is one technology of injecting modifying catalyst into oil reservoir to realize irreversible viscosity reducing of thickened oil in the oil reservoir, and is one new generation of thickened oil developing technology. At present, viscosity-reducing catalysts used in the thickened oil in-situ modification technology mainly comprise three types, namely water-soluble catalysts, oil-soluble catalysts and nano-catalysts. The nano catalyst has many problems in the process of liquid preparation construction and injection on the ground, is easy to damage a reservoir and has high 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 common oil-soluble catalyst can be well dispersed in oil, so that the contact and catalysis efficiency is improved, but the oil-soluble catalyst cannot be dissolved in water, a large amount of organic solvent is needed to carry and enter a stratum, the environmental pollution is serious, and the cost is high. The viscous oil in-situ modification viscosity-reducing catalyst is in conflict between injectability and contact catalysis efficiency, and a new generation of viscous oil modification viscosity-reducing agent which is more efficient and has water-soluble injectability and lipophilic contact catalysis is needed.
Disclosure of Invention
The invention aims to find a viscosity-reducing catalyst suitable for underground in-situ modification of thickened oil, and the viscosity-reducing catalyst applied to underground in-situ modification of thickened oil can effectively solve the contradiction between the injectivity and the contact catalytic efficiency of the viscosity-reducing catalyst in the prior art and realize the synergy of water-soluble injectivity and high-efficiency contact catalysis.
In order to achieve the purpose, the invention provides application of a crown ether transition metal complex (also called crown ether transition metal complex) as a viscosity reduction catalyst in underground in-situ modification of thickened oil, wherein the crown ether transition metal complex is formed by complexing a crown ether compound (with a crown ether macrocyclic structure) and transition metal ions.
The main structure of the crown ether transition metal complex is a crown ether macrocyclic structure, the crown ether transition metal complex is formed by complexing crown ether compounds and transition metals, and transition metal ions with catalytic activity are coated in crown ether molecules. The crown ether transition metal complex is a transition metal complex which can be dissolved in water, the hydrophilic performance of the crown ether group of the crown ether transition metal complex is influenced by the temperature, and when the temperature is higher than the cloud point of the crown ether group of the crown ether transition metal complex, the hydrophilic performance is greatly reduced, and the lipophilic performance is improved. The crown ether transition metal complex has the functions of catalyzing cracking and viscosity reduction of thick oil, has good water-soluble performance at normal temperature, can be injected into a stratum along with water, has the characteristic of high-temperature oil solubility because the hydrophilic performance can be reduced along with the increase of temperature, and can spontaneously enter an oil phase catalytic modification reaction after the oil layer is heated.
The crown ether transition metal complex is used as the 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 spontaneously diffuses to an oil phase to catalyze the thickened oil to perform a modification viscosity-reducing reaction, and the synergy of water solubility injectability and efficient contact catalysis is achieved. The invention uses crown ether transition metal complex compound in the technical field of underground in-situ modification of thickened oil for the first time.
In the above application, preferably, the crown ether compound includes one of a perhydroxy crown ether compound, an aza crown ether compound, a thia crown ether compound and a derivative thereof; more preferably, the lipophilic alkyl group of the derivative includes one or a combination of two or more of straight-chain alkane, branched-chain alkane, benzene ring and the like.
In the above application, preferably, the main structure of the crown ether compound comprises 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 a specific embodiment, the crown ether compound includes one of 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, and dibenzo-aza-18-crown-6.
In the above application, preferably, the crown ether transition metal complex has a structure of:
wherein n is 1, 2, 3 or 5; 1,1 … … n; x1、X2、X3、X3+iIndependently selected from one of O, N-H, S; r1、R2、R3、R4、R5、R6、R5+2i、R6+2iIndependently selected from one of hydrogen, straight-chain alkane, branched-chain alkane, benzene ring and the like; m is selected from one of transition metals (preferably Co,One of 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, the cloud point temperature of the crown ether-based transition metal complex is preferably 80 ℃ or lower.
The invention also provides a method for underground in-situ modification of thickened oil, 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 temperature of the stratum to a certain temperature after injecting the viscosity-reducing catalyst to carry out a thickened oil modification viscosity-reducing reaction; wherein the crown ether transition metal complex is formed by complexing crown ether compounds (with a crown ether macrocyclic structure) and transition metal ions.
The crown ether transition metal complex used in the thickened oil underground in-situ modification method is the same as the crown ether transition metal complex (also called crown ether transition metal complex) used in the application of the crown ether transition metal complex as a viscosity reduction catalyst in thickened oil underground in-situ modification.
The method for underground in-situ modification of the heavy oil refers to a technology for realizing irreversible modification and viscosity reduction of the heavy oil in a stratum aiming at a heavy oil reservoir (the viscosity is usually more than 50mPa & s), and the technology belongs to a branch of a heavy oil thermal recovery technology in tertiary oil recovery.
In the underground in-situ modification process of the thickened oil, the crown ether transition metal complex is used as the viscosity-reducing catalyst, so that the viscosity-reducing catalyst can be injected into a stratum along with water (namely, the water-based high-efficiency injection of the thickened oil modified catalyst can be realized), and the viscosity-reducing catalyst spontaneously diffuses into an oil phase to catalyze the thickened oil to generate a modification viscosity-reducing reaction, thereby achieving the synergy of water-soluble injectability and high-efficiency contact catalysis. 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 underground in-situ modification of oil provided by the invention uses crown ether transition metal complex as a viscosity reduction catalyst for the first time.
In the method for underground in-situ modification of the thickened oil, preferably, the crown ether compound comprises one of a total-oxygen crown ether compound, an aza crown ether compound, a thia crown ether compound and a derivative thereof; more preferably, the lipophilic alkyl group of the derivative includes one or a combination of two or more of straight-chain alkane, branched-chain alkane, benzene ring and the like.
In the method for underground in-situ upgrading of thickened oil, preferably, the main crown ether structure of the crown ether compound comprises one of 12 crown 4 ether, 15 crown 5 ether, 18 crown 6 ether, 24 crown 8 ether and derivatives thereof.
In a specific embodiment, the crown ether compound includes one of 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, and dibenzo-aza-18-crown-6.
In the above 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 method for underground in-situ upgrading of the thickened oil, the cloud point temperature of the crown ether transition metal complex is preferably below 80 ℃.
In the above method for underground in-situ upgrading of heavy oil, preferably, the crown ether transition metal complex has the structure:
wherein n is 1, 2, 3 or 5; 1,1 … … n; x1、X2、X3、X3+iIndependently selected from one of O, N-H, S; r1、R2、R3、R4、R5、R6、R5+2i、R6+2iIndependently selected from one of hydrogen, straight-chain alkane, branched-chain alkane, benzene ring and the like; 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 method for underground in situ upgrading of heavy oil, preferably, the method comprises: after crown ether transition metal complex aqueous solution is injected into a target stratum, the stratum temperature is raised to more than 200 ℃ for thickened oil modification viscosity reduction reaction; more preferably, the formation temperature is raised to 250-350 ℃; more preferably, the formation temperature is raised to a target temperature and then smoldering is carried out; more preferably, the formation temperature elevation is performed by injecting high temperature superheated steam and/or using electrical heating;
the formation temperature is increased to more than 200 ℃, which is more beneficial to the thickened oil modification and viscosity reduction reaction, and the temperature of 200 ℃ far exceeds the cloud point temperature of the crown ether transition metal complex, so that the oleophylic property is greatly improved and can be efficiently diffused into the crude oil; therefore, the underground in-situ modification of the heavy oil can be better realized by raising the formation temperature to more than 200 ℃.
In one embodiment, after the crown ether transition metal complex aqueous solution is injected into the target stratum, high-temperature superheated steam is injected and/or the stratum is heated to more than 200 ℃ by using an electric heating mode to carry out thickened oil modification viscosity reduction reaction.
In one embodiment, the crown ether transition metal complex aqueous solution is injected into the target stratum, then high-temperature superheated steam is injected and/or the stratum is heated to 350 ℃ by using an electric heating mode, the well is closed for 5-25 days, and the well is opened for production.
In the method for underground in-situ modification of heavy 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-3mmol/L-1mmol/L。
The technical scheme provided by the invention applies crown ether transition metal complex as viscosity-reducing catalyst in the method for underground in-situ modification of thickened oil, the crown ether transition metal complex has temperature-sensitive characteristic, the cloud point temperature is usually below 80 ℃, the crown ether transition metal complex has strong water solubility at low temperature, can be directly dispersed in water phase, and the lipophilicity is greatly improved along with the temperature rise; therefore, the following excellent effects are provided: the crown ether transition metal complex is used as the viscosity-reducing catalyst in the underground in-situ modification method of the thickened oil, so that the viscosity-reducing catalyst can be injected into the deep part of an oil reservoir along with water in the underground in-situ modification process of the thickened oil, and then heating the bottom layer to a certain temperature (meeting the requirement of the viscosity reduction catalyst on the reaction temperature for catalyzing the thickened oil to carry out the upgrading viscosity reduction reaction) to carry out the upgrading viscosity reduction reaction of the thickened oil, wherein the formation temperature is higher than the cloud point temperature of the crown ether transition metal complex, the lipophilicity of the crown ether transition metal complex is greatly improved, and the crown ether transition metal complex is diffused into the crude oil to catalyze the crude oil to carry out the upgrading viscosity reduction reaction, so that the dual-function cooperation of the water-based injection of the thickened oil underground upgrading catalyst and the high-efficiency catalysis of the oil phase is realized, the complex injection process of the common oil-soluble catalyst is greatly simplified (no surfactant, organic solvent, cosolvent and the like need to be added), and the catalytic contact efficiency and the catalytic viscosity reduction effect of the common water-soluble catalyst are enhanced.
Drawings
FIG. 1A is a schematic diagram showing the distribution of an aqueous solution of a crown ether-based transition metal complex and a kerosene mixture at room temperature in example 1 of the present invention.
FIG. 1B is a schematic diagram showing the distribution of an aqueous solution of a crown ether-based transition metal complex in example 1 of the present invention in a kerosene mixture at 60 ℃.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a potential verification that the crown ether transition metal complex has application as a viscosity-reducing catalyst in underground in-situ modification of thickened oil.
Preparing crown ether transition metal complex used as viscosity-reducing catalyst in underground in-situ modification of thickened oil, wherein the crown ether transition metal complex is N3O2The specific synthetic method and structure verification of the aza crown ether cobalt complex are shown in the literature: wanyan, luyi, Liugang, etc. N3O2Synthesis of aza crown ether and solid phase synthesis of cobalt complex thereof [ C]The proceedings of inorganic chemistry, chemical engineering academy conference in the western region of the chinese chemical society 2008, 2008: 173-174.
Dissolving the prepared crown ether transition metal complex in water at the concentration of 0.4mmol/L, mixing and fully dissolving to prepare crown ether transition metal complex aqueous solution;
adding kerosene into the crown ether transition metal complex aqueous solution, gradually raising the temperature to 60 ℃, and observing that the prepared crown ether transition metal complex spontaneously expands into an upper oil phase (see fig. 1A-1B), thereby verifying that the crown ether transition metal complex has excellent water solubility at normal temperature and has the temperature-sensitive characteristic of increasing oil solubility along with the temperature rise;
adding crown ether transition metal complex aqueous solution and an ultra-thick oil sample (crude oil viscosity is 23586mPa & s at 50 ℃) of a certain oil field in northwest 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 finishing the reaction; the rotating 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 2777mPa & s at 50 ℃, and the viscosity reduction rate reaches 88.2%.
From this, it is known that the crown ether transition metal complex has a potential to be applied as a viscosity-reducing catalyst in underground in-situ upgrading of thick oil, and can be applied as a viscosity-reducing catalyst in underground in-situ upgrading of thick oil.
Example 2
The embodiment provides a method for underground in-situ upgrading of thickened oil.
Selecting a certain thickened oil field in northwest China as a single-well small test block, and preferably selecting a 1# well with better sealing property as a test well; the depth of the test well is about 500m, and the formation pressure is 4.96 MPa.
The thickened oil underground in-situ modification provided by the invention uses a crown ether transition metal complex as a viscosity reduction catalyst, specifically uses a nickel 18-crown-6 aza-crown ether complex as the viscosity reduction catalyst, and the specific synthesis process and ligand structure verification are shown in the literature Wangzhilin, Hades and Haaishih, Liaozheng and the like, Co (II), Ni (II) and the research of a tetraoxadinitrogen macrocyclic ligand complex I2Ni(ClO4)2Synthesis and Properties of Isotetraoxydiazadole macrocyclic ligand complexes [ J]Journal of chemistry, 1986(02) 196-.
The specific synthesis method comprises the following steps: equimolar of Ni (ClO)4)2·5H2Respectively dissolving O and the dinitrogen tetroxide macrocyclic ligand in absolute ethyl alcohol, slowly dripping the ethanol solution of the ligand into the refluxing ethanol solution of nickel salt, continuously stirring and refluxing for 4 hours, separating out a green solid product, cooling, filtering, washing with absolute ethyl alcohol for three times, and drying in vacuum at room temperature to obtain the required nickel 18-crown-6 aza crown ether complex.
The method for underground in-situ upgrading of the thickened oil provided by the embodiment comprises the following steps:
dissolving the nickel 18-crown-6 aza-crown ether complex into 6 tons of injected water to prepare an aqueous viscosity-reducing catalyst solution with the concentration of 0.8mmol/L (based on the total volume of the aqueous viscosity-reducing catalyst solution);
injecting the viscosity-reducing catalyst aqueous solution into a test well;
then injecting 1200m into the test well3The superheated steam is used for the steam generation,soaking the well for 10 days when the temperature of the near-well stratum reaches about 280 ℃; and (5) well opening and oil recovery.
Single well test results: the average dehydration viscosity of crude oil produced by the round of well opening is 759mPa & s at 50 ℃, and the viscosity reduction rate reaches 98.0%. The mining effect is good.
The dewatering viscosity of the thick oil extracted from the test well in the huffing and puff round before the underground in-situ modification of the thick oil is 37664mPa & s at 50 ℃, the number of open-up self-blowout days in the previous round is 8 days, and the well head temperature is only 80 ℃ after 8 days of open-up. After injecting the viscosity-reducing catalyst aqueous solution, the well head temperature of the test well is still higher than 100 ℃ after the test well is opened for 27 days and 32 days.
Claims (17)
1. The crown ether transition metal complex is used as a viscosity reduction catalyst in underground in-situ modification of thickened oil, and is formed by complexing crown ether compounds and transition metal ions.
2. Use according to claim 1, wherein the crown ether-based compound comprises one of a perhydroxycrown ether-based compound, an azacrown ether-based compound, a thiacrown ether-based compound and derivatives thereof.
3. The use according to claim 2, wherein the lipophilic alkyl group of the derivative comprises one or a combination of two or more of linear alkane, branched alkane, benzene ring and the like.
4. The use of any one of claims 1 to 3, wherein the main structure of the crown ether compound comprises one of 12 crown 4 ether, 15 crown 5 ether, 18 crown 6 ether, 24 crown 8 ether and derivatives thereof.
5. Use according to claim 4, wherein the crown ether compound comprises one of 18-crown-6, benzo-15-crown-5, dibenzo-18-crown-6), dibenzo-24-crown-8, 1-aza-18-crown-6, 1, 10-diaza-18-crown-6, dibenzo-aza-15-crown-5 and dibenzo-aza-18-crown-6.
6. Use according to any one of claims 1 to 5, wherein the transition metal comprises one of Co, Ni, Mn, Cu, Mo and Ag.
7. Use according to claim 1, wherein the crown ether-based transition metal complex has a cloud point temperature below 80 ℃.
8. A method for underground in-situ modification of thickened oil comprises the steps of injecting a viscosity-reducing catalyst crown ether transition metal complex into a target stratum, and raising the temperature of the stratum to a certain temperature after injecting the viscosity-reducing catalyst so as to carry out a thickened oil modification viscosity-reducing reaction; wherein the crown ether transition metal complex is formed by complexing crown ether compounds and transition metal ions.
9. The method of claim 8, wherein the crown ether-based compound comprises one of a perhydroxycrown ether-based compound, an azacrown ether-based compound, a thiacrown ether-based compound, and derivatives thereof.
10. The method according to claim 9, wherein the lipophilic alkyl group of the derivative comprises one or a combination of two or more of a linear alkane, a branched alkane, a benzene ring and the like.
11. The method of any one of claims 8-10, wherein the crown ether host structure of the crown ether based compound comprises one of 12 crown 4 ether, 15 crown 5 ether, 18 crown 6 ether, 24 crown 8 ether, and derivatives thereof.
12. The method of claim 11, wherein the crown ether compound comprises one of 18-crown-6, benzo-15-crown-5, dibenzo-18-crown-6, dibenzo-24-crown-8, 1-aza-18-crown-6, 1, 10-diaza-18-crown-6, dibenzo-aza-15-crown-5, and dibenzo-aza-18-crown-6.
13. The method of any of claims 8-12, wherein the transition metal comprises one of Co, Ni, Mn, Cu, Mo, and Ag.
14. The method according to claim 8, wherein the cloud point temperature of the crown ether-based transition metal complex is below 80 ℃.
15. The method according to any one of claims 8-13, wherein the method comprises: after crown ether transition metal complex aqueous solution is injected into a target stratum, the stratum temperature is raised to more than 200 ℃ for thickened oil modification viscosity reduction reaction;
preferably, the formation temperature is raised to 250-350 ℃;
preferably, the formation temperature is raised to a target temperature and then allowed to soak.
16. The method of claim 15, wherein the method comprises: injecting crown ether transition metal complex aqueous solution into a target stratum, then injecting high-temperature superheated steam and/or heating the stratum to 350 ℃ by using an electric heating mode, closing the well for 5-25 days, and opening the well for production.
17. The method according to claim 15 or 16, wherein the concentration of the crown ether-based transition metal complex in the crown ether-based transition metal complex aqueous solution is 10, based on the total volume of the crown ether-based transition metal complex aqueous solution- 3mmol/L-1mmol/L。
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