KR20200048560A - Enzyme Enhanced Oil Recovery - Google Patents
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- KR20200048560A KR20200048560A KR1020180130738A KR20180130738A KR20200048560A KR 20200048560 A KR20200048560 A KR 20200048560A KR 1020180130738 A KR1020180130738 A KR 1020180130738A KR 20180130738 A KR20180130738 A KR 20180130738A KR 20200048560 A KR20200048560 A KR 20200048560A
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/10—Transferases (2.)
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- C12Y204/00—Glycosyltransferases (2.4)
- C12Y204/01—Hexosyltransferases (2.4.1)
- C12Y204/01005—Dextransucrase (2.4.1.5)
Abstract
Description
본 발명은 미생물에서 추출한 효소를 이용한 오일 회수 공법으로, 구체적으로는 효소 반응으로 생성된 바이오폴리머를 이용하여 오일을 회수하는 3차 회수 공법에 관한 것이다.The present invention relates to an oil recovery method using an enzyme extracted from a microorganism, and specifically, to a third recovery method of recovering oil using a biopolymer produced by an enzymatic reaction.
지하 심부의 저류층(貯留層)에는 상당히 많은 양의 원유가 존재하며, 1차 회수 공정을 진행하여도 회수 초기에 생산한 원유의 양은 30% 내외이고 나머지는 유층(油層)과 암석에 그대로 남아있다. 이렇게 남아있는 원유를 더 회수하기 위해, 석유회수증산기술(EOR: Enhanced Oil Recovery)을 사용하여 2차 회수를 진행한다.There is a significant amount of crude oil in the reservoirs in the deep part of the underground, and even after the first recovery process, the amount of crude oil produced at the beginning of recovery is around 30% and the rest remains in the oil layer and rock. To recover more of the remaining crude oil, secondary recovery is performed using Enhanced Oil Recovery (EOR).
2차 회수는 일반적으로 주입정에 물을 주입하는 수공법(water flooding)이나 가스를 주입하는 가스주입법(gas injection)과 같은 방법으로 저류층의 압력을 높여 추가적으로 회수한다. 이러한 2차 회수 공법을 이용하여 약 60% 정도의 원유를 회수할 수 있다.Secondary recovery is generally recovered by increasing the pressure of the reservoir by the same method as water flooding or gas injection, which injects water into the injection well. About 60% of crude oil can be recovered using this secondary recovery method.
이에 더하여, 추가적으로 원유를 더 회수하기 위한 3차 회수 공법이 세계 각국에서 개발되고 있으며, 그 중 미생물을 이용한 오일 회수 공법인(MEOR: Microbial Enhanced Oil Recovery)이 친환경, 저비용 공법으로 주목 받고 있다. 미생물을 이용한 석유 회수 공법으로는 크게 미생물이 생산하는 생계면활성제를 이용한 원유의 점성을 낮추는 공법과, 미생물이 생산한 바이오폴리머(Biopolymer)와 바이오필름을 이용하여 고투수층을 막는 선택적 막힘 공법(Selective clogging)이 있다. 미생물을 이용한 선택적 막힘 공법은 1, 2차 회수 동안 고투수층의 원유가 빠져나간 공간을 바이오폴리머 및 바이오필름으로 막음으로써, 상대적으로 투수계수가 낮은 지역의 투수계수를 높여, 회수하지 못한 투수계수가 낮은 지역의 원유를 회수할 수 있도록 하는 공법이다. In addition, a third recovery method for recovering additional crude oil has been developed in countries around the world, and among them, microbial enhanced oil recovery (MEOR) using microorganisms has attracted attention as an eco-friendly and low-cost method. As a method of recovering oil using microorganisms, a method of significantly lowering the viscosity of crude oil using a bioactive agent produced by microorganisms, and a selective blocking method of blocking a high permeable layer using biopolymers and biofilms produced by microorganisms (Selective clogging). The selective clogging method using microorganisms prevents the space in which the crude oil of the high-permeable layer has escaped during the first and second recovery with biopolymer and biofilm, thereby increasing the permeability coefficient in areas with relatively low permeability coefficients, resulting in a low permeability coefficient This is a method that allows local crude oil to be recovered.
최근 중국(Fuyu Oilfield, China)에서 적용하고자 하는 저류층에 존재하는 미생물(CJF-002)을 채취하여, 바이오폴리머인 셀룰로오스를 생산하도록 함으로써 추가적으로 원유를 생산한 사례가 있으며, 미국 등록특허 제8,746,334호 또한 미생물을 주입하여 원유를 회수하는 방법을 개시하고 있다.Recently, there is a case in which crude oil was additionally produced by collecting microorganisms (CJF-002) present in the reservoir to be applied in China (Fuyu Oilfield, China) to produce cellulose, a biopolymer, and US Patent No. 8,746,334 Disclosed is a method for recovering crude oil by injecting microorganisms.
그러나, 이렇게 미생물을 직접 주입하는 방법은, 주입정 막힘 현상, 외부 미생물 주입으로 인한 환경 오염, 바이오폴리머 생성 여부 및 생성 위치에 관한 불확실성 등의 문제점이 있다.However, the method for directly injecting microorganisms has problems such as clogging of the injection well, environmental pollution due to injection of external microorganisms, and uncertainty regarding whether or not to produce biopolymers and where they are produced.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 미생물을 직접 주입하는 것이 아니라, 미생물에서 추출한 효소를 이용하여 미생물 없이 바이오폴리머를 생산할 수 있도록 하는 방법을 이용한 것이다. 즉, 본 발명은 미생물을 이용한 문제점을 해결하면서, 보다 친환경적이고 회수량을 증대시킬 수 있는, 3차 오일 회수 공법을 제공하고자 하는 것이다.The present invention is intended to solve the above problems, rather than directly injecting microorganisms, and using a method to produce biopolymers without microorganisms using enzymes extracted from microorganisms. That is, the present invention is to provide a tertiary oil recovery method, which solves the problem using microorganisms and is more environmentally friendly and can increase the recovery amount.
상기 기술적 과제를 해결하기 위하여, 본 발명의 오일 회수 방법은, 덱스트란수크라제(Dextransucrase) 효소를 가진 미생물에서 덱스트란수크라제를 추출하는 단계; 상기 단계에서 추출한 효소와 수크로스(Sucrose) 수용액을 혼합하는 단계; 및 상기 단계에서 혼합한 용액을 토양에 주입하여 바이오폴리머를 생산하는 단계; 를 포함하는, 오일 회수 방법을 제공한다. 본 발명의 미생물은, 덱스트란수크라제 효소를 갖는 것을 특징으로 하며, 일 예로서 류코노스톡 메센테로이데스(Leuconostoc mesenteroides)를 이용하는 것을 특징으로 한다.In order to solve the above technical problem, the oil recovery method of the present invention includes the steps of extracting dextran sucrase from microorganisms having a dextransucrase enzyme; Mixing the enzyme extracted in the step and an aqueous sucrose solution; And injecting the solution mixed in the step into the soil to produce a biopolymer; It provides an oil recovery method comprising a. The microorganism of the present invention is characterized by having a dextran sucrase enzyme, and as an example, it is characterized by using Leuconostoc mesenteroides.
본 발명은 또한, 덱스트란수크라제 및 수크로스 수용액의 혼합액을 포함하며, 상기 혼합액을 토양에 주입하는 것을 특징으로 하는, 오일 회수용 바이오 폴리머 생성 물질을 제공한다. The present invention also includes a mixture solution of an aqueous solution of dextran sucrase and sucrose, and provides a biopolymer production material for oil recovery, characterized in that the mixture is injected into the soil.
본 발명의 원유 회수 공법은, 미생물을 직접 주입하는 것이 아니라 미생물이 생산하는 효소를 이용하여, 미생물을 직접 이용하는 3차 회수 공법 이용 시 발생하는 문제점을 해결하고, 원유 회수량을 증대시킬 수 있는 3차 오일 회수 공법을 제공한다.The crude oil recovery method of the present invention, rather than directly injecting microorganisms, uses enzymes produced by microorganisms to solve problems that occur when using the third recovery method using microorganisms directly, and can increase the amount of crude oil recovery. Provide a primary oil recovery method.
도 1은 본 발명의 (일 구현 예로서), 미생물에서 효소를 추출하여 물을 혼합한, 덱스트란수크라아제 수용액의 사진이다.
도 2는 본 발명의 효소를 이용하여 바이오폴리머 물질이 생산된 것을 나타낸 사진이다.1 is a photograph of an aqueous solution of dextran sucrase, in which water is extracted by extracting an enzyme from a microorganism (as an embodiment) of the present invention.
Figure 2 is a photograph showing that the biopolymer material was produced using the enzyme of the present invention.
본 발명은 오일 회수 방법으로, 상세하게는 3차 회수공법에 관한 것으로서, 미생물에서 추출한 효소를 이용해 바이오폴리머를 생성하여 오일을 회수하는 방법(EEOR; Enzyme Enhanced Oil Recovery)이다.The present invention relates to an oil recovery method, and specifically, to a third recovery method, which is a method of recovering oil by generating a biopolymer using enzymes extracted from microorganisms (EEOR; Enzyme Enhanced Oil Recovery).
미생물을 이용하여 저류층의 오일을 회수하는 기술(MEOR; Microbial Enhanced Oil Recovery)은 미생물을 직접 주입하는 등의 과정을 이용하여, 다른 공법에 비해 친환경적이지만, 외부 미생물을 주입함으로써 발생하는 환경 오염 및 주입정 막힘 현상, 바이오폴리머 생성 여부 및 생성 위치에 대한 불확실성이 있다는 문제점이 있었다. 그러나, 본 발명은 미생물을 직접 이용하는 것이 아닌, 효소를 이용함으로써 상기의 문제점을 해결하고, 오일 회수량을 높일 뿐 아니라, 미생물에 비해 보관 및 적용이 용이하여 상용성을 높일 수 있다.Microbial Enhanced Oil Recovery (MEOR), which uses microorganisms to recover oil in the reservoir layer, is more environmentally friendly than other methods, but it is environmentally friendly and injected by introducing external microorganisms. There was a problem that there was uncertainty about the static clogging phenomenon, whether to produce biopolymer, and where to produce it. However, the present invention solves the above problems by using enzymes rather than directly using microorganisms, and not only increases oil recovery, but also facilitates storage and application compared to microorganisms, thereby increasing compatibility.
본 발명은 기존의 선택적 막힘 공법(Selective clogging)을 개선한 것으로서, 선택적 막힘 공법이란 미생물을 이용해 바이오폴리머 물질을 생산하여, 1, 2차 회수 동안 원유가 빠져나간 저류층의 고투수층을 막음으로써, 상대적으로 투수계수가 낮은 지역의 투수계수를 높여 투수계수가 낮은 지역의 회수하지 못한 원유를 회수할 수 있도록 하는 방법이다. 하지만 기존의 방법은 외부 미생물의 사용으로 발생하는 생태계 파괴, 미생물의 크기(1 ~ 10 μm)로 인한 초고투수층에의 적용이 어려운 문제점, 저류층의 조건에 따라 미생물의 생장 및 바이오폴리머의 생성이 어려운 문제점 등이 존재한다. 이의 개선을 위하여, 본 발명은 미생물을 직접 사용하는 것이 아니라 미생물에서 효소를 추출하여 바이오폴리머 물질을 생산하는 방법을 이용한 것으로, 미생물로 인한 환경 문제가 없을 뿐 아니라, 미생물보다 크기가 훨씬 큰 효소(1 ~ 10 ηm)의 사용으로 인해 초고투수층에 적용 가능하며, 보다 외부 환경에 대한 영향이 미비(특히, 효소는 보다 높은 온도에서도 덱스트란 생성 가능)하여 원유 회수율을 높일 수 있는 공법이다.The present invention is to improve the existing selective clogging method (Selective clogging), by producing a biopolymer material using a microorganism called the selective clogging method, by blocking the high permeability layer of the storage layer through which the crude oil escaped during the first and second recovery, relatively This is a method to increase the permeability coefficient in areas with low permeability coefficient so that unrecovered crude oil in areas with low permeability coefficient can be recovered. However, the existing method is difficult to apply to the ultra-high permeable layer due to the destruction of the ecosystem caused by the use of external microorganisms, the size of the microorganism (1 ~ 10 μm), and it is difficult to grow microorganisms and produce biopolymers depending on the conditions of the reservoir. There are problems, etc. In order to improve the present invention, the present invention uses a method of producing a biopolymer material by extracting enzymes from microorganisms rather than directly using microorganisms, and there is no environmental problem caused by microorganisms, and enzymes that are much larger in size than microorganisms ( Due to the use of 1 ~ 10 ηm), it is applicable to ultra-high permeable layers, and has a small influence on the external environment (especially, enzymes can produce dextran even at higher temperatures), which is a method that can increase the recovery of crude oil.
구체적으로 본 발명은, 글루칸수크라제(Glucansucrase) 효소를 가진 미생물에서 글루칸수크라제를 추출하는 단계; 상기 단계에서 추출한 효소와 수크로스(Sucrose) 수용액을 혼합하는 단계; 및 혼합한 용액을 토양에 주입하여 바이오폴리머를 생산하는 단계;를 포함하는, 오일 회수 방법을 제공한다.Specifically, the present invention, glucan sucrase (Glucansucrase) step of extracting glucan sucrase from a microorganism having an enzyme; Mixing the enzyme extracted in the step and an aqueous sucrose solution; And injecting the mixed solution into the soil to produce a biopolymer.
상기 글루칸수크라제는 뮤탄수크라제(Mutansucrase), 덱스트란수크라제(Dextransucrase), 알터난수크라제(Alternansucrase), 또는 류테란수크라제(Reuteransucrase) 중 어느 하나 일 수 있으나, 그 중 덱스트란수크라제인 것이 가장 바람직하다.The glucan sucrase may be any of Mutansucrase, Dextransucrase, Alternansucrase, or Reuteransucrase, but dex of them Most preferred is transsucrase.
본 발명에서 덱스트란수크라제는, 락트산(Lactic acid)균에 존재하는 효소의 일종으로, 수쿠로스 수용액과 혼합하여 바이오폴리머 물질을 생산한다. 구체적으로, 덱스트란수크라제 효소를 가진 미생물에서 덱스트란수크라제를 추출하여, 이를 수크로스(C12H12O11) 수용액과 혼합하면, 하기 화학식 1에서 볼 수 있는 것과 같이 포도당 외 부산물(하기 화학식 1에서 C6H10O5에 해당)인 바이오폴리머 물질을 생성한다. 도 2는 상기 단계를 통해 생성된 바이오폴리머 물질을 나타내고 있다.In the present invention, dextran sucrase is a type of enzyme present in the lactic acid bacteria, and is mixed with an aqueous sucrose solution to produce a biopolymer material. Specifically, when dextran sucrase is extracted from microorganisms having dextran sucrase enzyme and mixed with sucrose (C 12 H 12 O 11 ) aqueous solution, by-products other than glucose as shown in the following Chemical Formula 1 A biopolymer material (corresponding to C 6 H 10 O 5 in Chemical Formula 1) is produced. 2 shows the biopolymer material produced through the above steps.
본 발명의 미생물은, 글루칸수크라제 효소, 그 중에서도 덱스트란수크라제 효소를 갖는 것을 특징으로 하며, 류코노스톡 메센테로이데스(Leuconostoc mesenteroides), 스트렙토쿠스 뮤탄스(Streptococcus mutans), 락토바실러스(Lactobacillus), 웨이셀라(Weisella)로 이루어진 군으로부터 선택되는 1종 이상이나, 이에 한정되지 않는다.The microorganism of the present invention is characterized by having a glucan sucrease enzyme, and in particular a dextran sucrase enzyme, Leuconostoc mesenteroides, Streptococcus mutans, Lactobacillus ( Lactobacillus), one or more selected from the group consisting of Weisella (Weisella), but is not limited thereto.
구체적으로, 상기 덱스트란수크라제 효소는 수크로스를 포함한 미생물 배지에 미생물을 주입하여 미생물을 배양한 후, 그 배양액을 원심분리기를 이용하여 상층액을 분리하거나 초음파기기를 이용하는 방법 등에 의해 추출할 수 있으며, 일 방법을 예시하였으나 이에 제한되지 않는다.Specifically, the dextran sucrase enzyme is incubated with microorganisms by injecting microorganisms into a microbial medium containing sucrose, and then the culture medium is extracted using a centrifuge to separate the supernatant or use an ultrasonic device. It may be, but it is not limited thereto.
본 발명의 효소가 생산한 바이오폴리머 물질은, 고분자 물질로서, 섬유소, 덱스트란, 녹말, 글리코겐, 리그닌, 키틴, 알긴산과 같은 다당류, 및 고분자 단백질로 이루어진 군으로부터 선택되는 1종 이상을 포함한다. 상기 바이오폴리머 물질은 반고체형태, 즉 젤리 형태의 바이오폴리머 물질들이 지반의 공극에 축적됨으로써 형성된다. 이를 통해 토양을 안정화하고 및 투수계수를 감소시킨다.The biopolymer material produced by the enzyme of the present invention is a polymer material, and includes one or more selected from the group consisting of polysaccharides such as fibrin, dextran, starch, glycogen, lignin, chitin, alginic acid, and polymer proteins. The biopolymer material is formed by accumulating semi-solid, i.e., jelly-type biopolymer materials in pores of the ground. This stabilizes the soil and reduces the permeability coefficient.
본 발명은 효소 용액 및 영양분을 혼합한 수용액 형태로서, 보관이 편리하고 사용이 용이하다. 투수계수를 감소시키기 위해, 바이오폴리머 층을 형성하기 위한 수크로스 용액을 혼합한 효소 용액을 토양에 주입하는 것이 일반적이며, 원유를 회수하고자 하는 저류층 깊이에 효소를 주입하는 장치를 추가적으로 설치할 수 있다. 본 발명의 효소 용액은 바이오폴리머 층의 형성에 필요한 pH 완충제 등을 추가적으로 포함할 수 있다.The present invention is in the form of an aqueous solution in which an enzyme solution and nutrients are mixed, which is convenient for storage and easy to use. In order to reduce the permeability coefficient, it is common to inject the enzyme solution in which the sucrose solution for forming the biopolymer layer is mixed into the soil, and an apparatus for injecting the enzyme into the depth of the reservoir layer to recover crude oil may be additionally installed. The enzyme solution of the present invention may additionally include a pH buffering agent or the like required for the formation of the biopolymer layer.
Claims (6)
상기 단계에서 추출한 효소와 수크로스(Sucrose) 수용액을 혼합하는 단계; 및
상기 단계에서 혼합한 용액을 토양에 주입하여 바이오폴리머를 생산하는 단계;를 포함하는, 오일 회수 방법.
Extracting a glucan sucrase enzyme from a microorganism having a glucansucrase enzyme;
Mixing the enzyme extracted in the step and an aqueous sucrose solution; And
Including the step of injecting the solution mixed in the step into the soil to produce a biopolymer; containing, oil recovery method.
상기 글루칸수크라제 효소는 덱스트란수크라제(Dextransucrase) 효소인 것을 특징으로 하는, 오일 회수 방법.
The method according to claim 1,
The glucan sucrase enzyme is characterized in that the dextran sucrase (Dextransucrase) enzyme, oil recovery method.
상기 미생물은,
류코노스톡 메센테로이데스(Leuconostoc mesenteroides), 스트렙토쿠스 뮤탄스(Streptococcus mutans), 락토바실러스(Lactobacillus) 및 웨이셀라(Weisella)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는, 오일 회수 방법.
The method according to claim 2,
The microorganism,
A method for recovering oil, characterized in that at least one member selected from the group consisting of Leuconostoc mesenteroides, Streptococcus mutans, Lactobacillus and Weisella.
수크로스(Sucrose) 수용액;을 혼합하여, 토양에 주입하는 것을 특징으로 하는, 오일 회수용 바이오 폴리머 생성 물질.
A glucan sucrase enzyme extracted from a microorganism having a glucansucrase enzyme; And
Sucrose (Sucrose) aqueous solution; characterized in that by injecting into the soil, bio-polymer production material for oil recovery.
상기 글루칸수크라제 효소는 덱스트란수크라제(Dextransucrase) 효소인 것을 특징으로 하는, 오일 회수용 바이오 폴리머 생성 물질.
The method according to claim 4,
The glucan sucrase enzyme is characterized in that the dextran sucrase (Dextransucrase) enzyme, bio polymer production material for oil recovery.
상기 미생물은,
류코노스톡 메센테로이데스(Leuconostoc mesenteroides), 스트렙토쿠스 뮤탄스(Streptococcus mutans), 락토바실러스(Lactobacillus) 및 웨이셀라(Weisella)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는, 오일 회수용 바이오 폴리머 생성 물질.
The method according to claim 4,
The microorganism,
Biopolymer for oil recovery, characterized by at least one member selected from the group consisting of Leuconostoc mesenteroides, Streptococcus mutans, Lactobacillus, and Weisella Products.
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