CN113444511A - 一种纳米铜基稠油改质剂 - Google Patents
一种纳米铜基稠油改质剂 Download PDFInfo
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- CN113444511A CN113444511A CN202110883789.XA CN202110883789A CN113444511A CN 113444511 A CN113444511 A CN 113444511A CN 202110883789 A CN202110883789 A CN 202110883789A CN 113444511 A CN113444511 A CN 113444511A
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- 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
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
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Abstract
本发明涉及一种纳米铜基稠油改质剂,其目的是采用科技创新技术,利用纳米铜宽温高效催化活性,配位催化作用,以及稠油热采加氢多因素协同作用下,发生稠油断键重组反应,把稠油原位改质并提高采收率,其能够在注蒸汽热采环境下把供氢剂和部分水分子催化分解产生高活性氢,在较宽温度范围内可以快速将稠油里沥青质和胶质中的碳硫、碳氧、碳氮键和有机碳环长分子链催化裂解成为小分子有机物,改质剂的表面活性成份可以不可逆地降低稠油粘度,实现稠油地下原位改质与地炼降粘,改质的稠油在油藏中波及面积增大,采出率得到很大的提高,是具有广阔前景的稠油开采新技术。
Description
技术领域:
本发明涉及石油开采技术领域,具体涉及一种纳米铜基稠油改质剂。
背景技术:
石油作为重要的石化能源和国家战略资源,随着原油的不断开采,低粘度轻质原油所占比例越来越少,而胶质与沥青质含量较高的稠油(占比60~70%)将成为全球原油开采的重点方向。由于地下稠油的粘度非常大(通常在18000~150000mpa.s,特稠油的粘度高达300000mpa.s)按常规方法开采非常困难,科技研发人员先后开发出了多种稠油开采的技术和方法,主要有表面活性剂驱、聚合物驱、蒸汽吞吐、蒸汽驱、火驱、SAGD,以及借助超声波、微生物强化、电化学、磁处理方法采油等,并添加多种化学降粘剂(包括乳化剂)等多种方式来提高稠油开采量,但由于稠油粘度高,化学驱效果十分有限,而热力采油的能源消耗过高,声波、电动学或电化学以及磁处理技术对设备要求高,束缚了这些技术的应用与推广,稠油开采收率比例仍不到60%。
现有稠油降粘技术中,主要以表面活性剂、乳化剂、催化降粘或溶剂等方式来辅助热采起到降粘的作用,例如:CN102260490A涉及一种稠油助采剂及其制备方法,该稠油助采剂的主要成分为:脲、高温防乳破乳剂、石油磺酸盐、乙二胺四乙酸二钠、高温起泡剂。CN101074367A涉及了一种稠油稀化剂,用于稠油热采中化学辅助蒸汽驱改善蒸汽吞吐效果的提高采收率,其主要成分为:乙二胺四乙酸二钠、低级脂肪酸、螯合分散剂、磺酸盐助排剂等。
纳米技术在石油领域主要应用于催化、磁力降粘或导热能力等方面。例如:CN102977254A涉及了一种稠油纳米降粘剂及其制备方法,该纳米降粘剂主要包括纳米聚(二乙烯基苯-丙烯酸短链酯-丙烯酸高碳质)。CN105542743A涉及一种纳米流体稠油热采助剂及其制备方法,用于提高原油的导热能力,进而提高蒸汽热量的利用率,其原料组成可以包括:纳米材料0.01-0.5%、乳化剂0-15%、辅助试剂0.1-5%、矿物离子0-6%、稠化剂0.1-1%、分散溶剂0-30%以及水余量。
上述现有技术主要是在降粘或调节热导率等方面进行研究,未能够从本质上解决稠油降粘及开采难度大等根本性的问题,纳米金属作为纳米金属粉体材料中非常重要的一员,因具有突出的表面晶格缺陷,在催化裂解方面表现为独有的宽温催化活性,且温度越高其表面活性与催化活性就越好,在常温环境下可用于短链有机物的催化合成,在中温环境下可替代“活性氢”用于长链有机物的催化裂解,在650℃以上高温与光热环境下可催化分解水分子为高活性氧与高活性氢,因此可用于稠油的催化裂化与地炼降粘。
专利CN111434384A介绍了一种稠油水热裂解催化剂及其制备方法于应用,该稠油水热裂解催化剂为在油、水体系中具有良好分散性的负载型纳米镍催化剂,其对地下稠油具有高催化裂解活性,其制备方法包括:(1)向含镍前驱体水溶液中加入氨水调节其PH值;(2)向步骤(1)中所得含镍前驱体水溶液中加入固体酸粒子,搅拌后得到悬浮液;再对该悬浮液进行离心、洗涤、干燥后得到固体粉末;(3)将固体粉末在氢气气氛下进行煅烧,得到表面负载有纳米镍的固体酸粒子;(4)向有机溶剂中加入油酸及表面负载有纳米镍的固体酸粒子,以进行接枝反应,反应结束后再经离心洗涤和干燥,得到表面经两亲性改性的催化剂粒子,即稠油水热裂解催化剂。其催化剂采用的的是纳米镍改性后进行调制,纳米镍价格较为昂贵,成本较高,其介绍的制备方法也较为繁琐,应用也有限定条件,其稠油水热催化裂解反应的温度为180-250℃,压力为2.5-5.0MPa,受温度和压力的限制适用范围窄。
稠油催化改质用催化剂主要分为多相催化剂和均相催化剂两大类,例如CAPRI技术所用的催化剂是成熟的炼油催化剂,属于多相催化剂,均相催化剂又分为水溶性催化剂和油溶性催化剂,水溶性催化剂,例如无机金属盐类,廉价易得,但与原油接触有限,催化效果相对较差;油溶性催化剂,例如有机金属盐类,催化效果好,但价格较贵。
近年来,纳米金属催化剂受到了广泛关注,相较于纳米贵金属催化剂来说,其有着处理效果良好,催化效率较高等优势,但其应用条件苛刻,以及高昂的价格,使得其作为稠油开采助剂或改质剂等的应用具有了限制性,采用性价比较高,价格较低,催化效果较好的纳米金属做为采油助剂中的催化剂,在现有油田采油工况复杂的应用条件下,能够达到较低的投入成本,提高采收率、产量和采油速度,获得较高的收益,具有十分重要的意义。
发明内容:
为解决上述技术问题,本发明的目的在于提供一种纳米铜基稠油改质剂,将纳米铜代替其他纳米金属用于催化剂中,催化剂被注入地层之中,在地层岩石的多孔介质中与稠油接触,在地层高温高压的条件下,利用纳米铜宽温高效催化活性,配位催化作用,以及稠油热采加氢多因素协同作用下,打开稠油C-C键,发生稠油断键重组反应,不可逆地改质稠油并降低粘度。改质剂产生的活性气体膨胀能够快速恢复油藏压力和拓展蒸汽腔,产生弹性驱动能量,扩大蒸汽的波及体积,提高蒸汽带和热水带的驱油效率,强化回采,提高峰值产量和采油速度,并降低稠油采、集、输、炼制加工成本,从而实现稠油的原位地炼降粘与改质,提高稠油采收率。
本发明提供一种纳米铜基稠油改质剂,其由纳米铜(0.5~5%)、使纳米铜悬浮的分散剂(35~70%)以及供氢剂(25~60%)等助剂调和而成,为均相油溶性改质剂,外观为悬浮性良好的棕红色纳米铜浆,其PH值为:7.5~9.5,密度为:1~1.2g/cm3(克/立方厘米),改质剂注入油藏后,能够与原油良好的互溶,有效地提高催化效率,合理高效彻底的实现稠油的原位地炼降粘与改质,提高稠油采收率,其所谋求的目的将通过以下方法进行实现:
根据所述的一种纳米铜基稠油改质剂,其纳米铜采用球状纳米铜、片状纳米铜或球状和片状纳米铜的混合体,球状纳米铜的尺寸为:0.05~5μm(微米),片状纳米铜的尺寸为:1~10μm(微米),厚度为0.05~0.2μm(微米);
根据所述的一种纳米铜基稠油改质剂,其分散剂组分包括:聚α-烯烃油类合成润滑油基础油(20~90%)、三乙醇胺(20~80%)、乙二醇(10~40%)、丙酮(5~20%)、甘油(5~40%)、月桂酸(5~20%)、油酸(5~20%)、硼酸(2~20%)等,两种至多种调和而成;
根据所述的一种纳米铜基稠油改质剂,其供氢剂采用四氢萘、甲基环乙烷、环乙烷、甲酸酯基类物质等制剂,一种或两种至多种调和使用,可以很大程度上改善稠油的黏度,使原油裂解反应向着加氢脱硫的方向进行,达到稠油裂解的作用,该剂用量少、成本低。
附图说明:
图1为本发明实施例1所提供的原油裂解前后黏度对比图
图2为本发明实施例1所提供的原油裂解前后全烃色谱对比表图
图3为本发明实施例1所提供的原油裂解前全烃色谱图
图4为本发明实施例1所提供的原油裂解后全烃色谱图
图5为本发明实施例1所提供的原油裂解前后原油族组成分析表图
具体实施方式:
高活性纳米铜基稠油改质剂借助地温高压水环境产生活性氢与纳米铜共同参与催化裂解稠油,并取代稠油中的碳、硫、氮,破坏有机链与有机环,实现稠油的催化裂解与降粘,提高稠油开采率与原油品质。
1、金属铜属于过渡金属元素,具有特殊的电子结构,在元素周期表中位于IB族,外围电子构型为3d104s1,其3d轨道刚充满能级不稳,3d电子可以失去或参与成键,具有极强的极化力,可形成氧化值+1(CU2O)、+2(CUO)、+3(KCUO2)、+4(CS2CUF6)的物质。
1980年Kummert发现CuO在CO反应中具有类似贵金属催化剂的活性,因此负载型铜基催化剂被认为是可取代贵金属催化剂的最佳替代品。国内外学者分别研究了基于不同载体,如γ-Al2O3、TiO2、ZrO2、SiO2、ZSM-5等的铜基催化剂对NOx和CO催化活性的影响,证明这一系列催化剂在较宽的温度范围内均有优异的催化氧化活性。
纳米铜粉存在突出的晶格缺陷,经研究发现,纳米级超微细铜粉活性高,在高温、高压环境下可催化分解水蒸汽中水分子成为活性氧与活性氢,其能够在稠油开采过程中,借助地下高温水环境,通过电子传递与氧传递,破坏并打破稠油的有机链。
潘秋红、张锡凤在《油溶性纳米铜的制备及其在SF15W/40汽油中的摩擦学性能》中介绍通过液相化学还原法结合界面上次仪醋酸铜为母体维生素C(Vc)为还原剂,聚乙二醇2000为修饰剂,正丁醇为生长剂,制得粒度分布为18.2-80.2nm、平均粒度为44.7nm的油溶性球形纳米Cu。CN102925253A介绍了一种通过将锡纳米颗粒分散到具有润湿剂的分散介质中经过搅拌和超声波处理得到油溶性纳米锡颗粒的制作方法。CN103769605A介绍了一种油溶性金纳米颗粒的合成方法,其提供了一种温和条件下在油相体系中合成高浓度、高稳定性,尺寸在30-100nm的油溶性金纳米颗粒的合成方法。油溶性纳米材料利用微乳液的制备方法可以参考:蔡逸飞硕士毕业论文《微乳液法制备油溶性纳米金属铜及其在摩擦学中的应用》控制微乳液粒径在1-100纳米之间,制备得到了10-50纳米的油溶性铜纳米颗粒。赵法军,刘永健,曹广胜等发明了一种用于稠油改质降粘用超分散催化剂的制备方法,得到所需的用于稠油改质降粘用超分散催化剂。本发明将上述文献的全文引用于此作为参考,可以采用上述方法制备得到本发明的油溶性表面修饰纳米材料以及改质剂,但不限于上述文献中的方法。
2、根据所述的一种纳米铜基稠油改质剂,其供氢剂为四氢萘、甲基环乙烷、环乙烷、甲酸酯基类物质等药剂,一种或两种至多种调和使用,其在温度达到150℃分解,可以很大程度上改善稠油的黏度,降低硫和沥青的含量,微观上可以起到溶剂的作用稀释烃类大分子自由基,减少自由基的碰撞机会,提供活性氢原子,抑制稠油聚合生焦,有利于C-S等键的断裂,使原油裂解反应向着加氢脱硫的方向进行,因而稠油中的饱和烃、芳香烃含量增加,胶质和沥青质含量降低,达到稠油裂解的作用,该剂用量少、成本低。
3、本发明一种纳米铜基稠油改质剂,其纳米铜粉采购于上海茂果纳米科技有限公司或上海攀田粉体材料有限公司以及其他纳米材料制备公司,球状纳米铜选用的尺寸为:直径0.05~5μm(微米),片状纳米铜选用的尺寸为:1~10μm(微米),厚度为0.05~0.2μm(微米)。
4、稠油催化改质用催化剂主要分为多相催化剂和均相催化剂两大类,例如:井筒催化(CAPRI)技术所用的催化剂是成熟的炼油催化剂,属于多相催化剂,均相催化剂又分为水溶性催化剂和油溶性催化剂,水溶性催化剂,例如无机金属盐类,廉价易得,但与原油接触有限,催化效果相对较差,油溶性催化剂,例如有机金属盐类,催化效果好,但价格较贵,本发明一种纳米铜基稠油改质剂采用的是油溶性改性方法制备,其油溶性改性方法参考文献蔡逸飞硕士毕业论文《微乳液法制备油溶性纳米金属铜及其在摩擦学中的应用》。
5、本发明一种纳米铜基稠油改质剂,其制备方法为:将油溶性改性后的纳米铜(0.5~5%)、分散剂(35~70%)以及供氢剂(25~60%),按重量百分比计进行配比,将原料在20~95℃温度下进行混合,控制在100~10000r/min搅拌5~360min后,控制超声频率在5~50kHz范围内,经超声振荡5~25min,得到所需的用于稠油位地炼降粘与改质的纳米铜基稠油改质剂,外观为悬浮性良好的棕红色纳米铜浆,其PH值为:7.5~9.5,密度为:1~1.2g/cm3(克/立方厘米),改质剂注入油藏后,能够与原油良好的互溶,有效地提高催化效率,提高稠油采收率。
6、本发明一种纳米铜基稠油改质剂,其具有较宽温催化活性,该改质剂在低温(100℃以下)加氢反应为打开稠油C-O键,在高温、高压(100~300℃)加氢反应为打开稠油C-C键,可催化裂解降低稠油粘度,缩短了稠油在地下油层反应时间至72小时以内,在不同温度下展现不同的催化效果,不会失活,微小的尺寸赋予纳米铜稠油改质剂更大的表面积/体积比,可提高催化剂迁移性以及催化剂与油滴之间的接触性能,催化剂在多孔介质内的传输和原位反应产生的小分子物质,使得稠油的溶解性更好,且可大幅度降低粘度,其催化转化时间长,且不需要更新催化剂,原位改质降粘可降低操作费用,并且对环境影响小,可减少温室气体、含硫气体和氮氧化合物和固体废弃物的污染,减少水资源的消耗,其拥有更低的制作成本。
7、实施例1
本实施例提供了一种纳米铜基稠油改质剂的实验方法及结果,其中所述的实验方法和结果包括以下内容:
(1)实验方法:将200±1g稠油(选自辽河油田杜813区块试验井采出原油)置于高温高压反应釜中,加入纳米铜基稠油改质剂,按油水比例7∶3加入蒸馏水,纳米铜基稠油改质剂用量2%,密封装置,通氮气,加压至8±0.5MPa,确保密封,排除釜内空气后,将温度升至200±0.1℃,恒温24小时停止反应,待冷却至室温后,取出稠油样品,测定原油黏度、粘温曲线、全烃、族组成、产出气等,并分析稠油改质实验前后各项目的变化情况。
计算稠油的降粘率公式:
η=(μ0-μ)/μ0×100%
式中η为稠油降粘率,μ0为稠油初始粘度,μ为稠油改质降粘后粘度。
(2)试验结果1:原油黏度变化
从图1上看:40℃时稠油黏度太稠无法测出数据,50℃时裂解前原油黏度为155000mpa.s,改质后原油黏度为7435mpa.s,降粘率为95.5%。降粘效果非常明显,在常温下原油可以流动。
(3)试验结果2:原油全烃参数变化
从图2、图3、图4参数来看,原油的轻质组分明显增加,原油的轻重比由改质前的5.46变为13.81,全烃色谱图中可以看出,谱图向左偏移明显,改质后的轻质组成增加,裂解效果非常明显。
(4)试验结果3:原油改质前后族组成变化
从图5来看,改质后原油的饱和烃、芳烃含量增加非常明显,非烃和沥青质含量大幅度减少,通过以上原油黏度、全烃、族组成三个方面的相互认证,可以肯定改质剂的改质降粘,提高了原油的流动性。
本发明一种纳米铜基稠油改质剂,其优点在于:
1、添加量少,分散性好,注入的改质剂可以通过多孔介质携带分布,在注入井周围构建一个催化床,波及范围大,时效长;
2、宽温催化活性好,温度适应性好,温度越高其表面活性与催化活性就越好,在地下温场可使稠油重组分裂解率达到60%以上;
3、饱和烃加氢发生自由基裂化,避免了烯烃和芳烃分子的形成,减少了焦炭形成的可能性;
4、具有不受地质条件限制、地下转化的轻质原油、提高采收率、降低开成本、无污染等优点;
5、快速恢复油藏压力和拓展蒸汽腔,产生弹性驱动能量,回采率高,自然沉降分离出的水和固相物杂质补加改质剂后直接注入地下循环利用,对于环境保护效果非常显著;
6、该改质剂在油藏中就地将稠油部分裂解处理,使其中硫等杂原子在地下部分脱除,不可逆地降低重质组分含量或改变其分子结构,不仅可以提高稠油品质、降低稠油粘度、增加其在油层内的流动性,在一定程度上使稠油轻质化,还会减轻下游炼制加工过程中的催化剂中毒和环境污染等问题。
本发明一种纳米铜基稠油改质剂是用于稠油原位改质与地炼降粘,并提高采收率的新技术,即利用纳米铜宽温高效催化活性,配位催化作用,在稠油热采加氢多因素协同作用下,发生稠油断键重组反应,能够在注蒸汽热采环境下把供氢剂和部分水分子催化分解产生高活性氢,在较宽温度范围内快速地将稠油里的沥青质和胶质中的碳硫、碳氧、碳氮键和有机碳环长分子链,催化裂解成为小分子有机物,不可逆地降低稠油粘度,实现稠油地下原位改质与地炼降粘,改质的稠油在油藏中波及面积大,采出程度提高,是具有广阔前景的稠油开采新技术。
Claims (4)
1.本发明一种纳米铜基稠油改质剂,其由纳米铜(0.5~5%)、使纳米铜悬浮的分散剂(35~70%)以及供氢剂(25~60%)调和而成,为均相油溶性改质剂,外观为悬浮性良好的棕红色纳米铜浆,其PH值为:7.5~9.5,密度为:1~1.2g/cm3(克/立方厘米),注入油藏后,能够与原油良好的互溶,有效地提高催化效率,合理高效彻底的实现稠油的原位地炼降粘与改质,提高稠油采收率。
2.根据权利要求1所述的一种纳米铜基稠油改质剂,其纳米铜采用球状纳米铜、片状纳米铜或球状和片状纳米铜的混合体,球状纳米铜的尺寸为:0.05~5μm(微米),片状纳米铜的尺寸为:1~10μm(微米),厚度为0.05~0.2μm(微米)。
3.根据权利要求1所述的一种纳米铜基稠油改质剂,其分散剂组分包括:聚α-烯烃油类合成润滑油基础油(20~90%)、三乙醇胺(20~80%)、乙二醇(10~40%)、丙酮(5~20%)、甘油(5~40%)、月桂酸(5~20%)、油酸(5~20%)、硼酸(2~20%),两种至多种调和而成。
4.根据权利要求1所述的一种纳米铜基稠油改质剂,其供氢剂采用四氢萘、甲基环乙烷、环乙烷、甲酸酯基类物质,一种或两种至多种调和使用。
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