CN109804039A - 用于压裂开采法的涂覆的支撑装置 - Google Patents
用于压裂开采法的涂覆的支撑装置 Download PDFInfo
- Publication number
- CN109804039A CN109804039A CN201680089739.1A CN201680089739A CN109804039A CN 109804039 A CN109804039 A CN 109804039A CN 201680089739 A CN201680089739 A CN 201680089739A CN 109804039 A CN109804039 A CN 109804039A
- Authority
- CN
- China
- Prior art keywords
- coating
- proppant
- polymer
- vinyl
- ethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 238000000605 extraction Methods 0.000 title abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 30
- -1 alkyl carboxylic acid Chemical class 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
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- 150000001993 dienes Chemical class 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 4
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- 239000012876 carrier material Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
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- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- UXUDJAVFUJMRFG-UHFFFAOYSA-N COC(C=C)=O.[C] Chemical compound COC(C=C)=O.[C] UXUDJAVFUJMRFG-UHFFFAOYSA-N 0.000 claims 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于压裂开采法的涂覆的支撑装置，其含有无机基质材料和涂层，该涂层含有来自于含有具有1至15个碳原子的无支链或支链烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、乙烯基芳族化合物、烯烃、二烯和乙烯基卤化物的组中的一种或多种烯键式不饱和单体的聚合物，其特征在于聚合物通过在水性介质中自由基引发的聚合来获得，其中相对于单体的总重量，共聚了0.5至20wt.％的含有硅烷基团的烯键式不饱和单体。
Description
技术领域
本发明涉及包含无机载体材料和用于涂覆该无机载体材料的烯键式不饱和单体(ethylenically unsaturated monomer，烯属不饱和单体)的聚合物的涂覆的支撑剂(coated proppant)，涉及用于生产涂覆的支撑剂的方法，以及涉及涂覆的支撑剂在用于矿物油和天然气的压裂(fracking，水力压裂)生产方法中的用途。
背景技术
压裂方法用于矿物油和天然气生产，并且是一种在地下深层沉积岩中产生、扩大和稳定裂缝的技术，旨在增加沉积岩的渗透性。因此，其中存在的气体或液体能够更容易且更稳定地流到井中并被回收。
产生的裂缝必须用支撑剂保持打开。目前可用的涂覆的或未涂覆的支撑剂是脆性的，并且对于在深度很大的情况下生产，不具有必要的抗压强度。在高压下支撑剂的破裂会释放出阻挡裂缝并降低油气生产速率的细颗粒。
与未涂覆的支撑剂相比，根据现有技术可获得的涂覆的支撑剂具有改善的稳定性。然而，具有有机树脂的涂层的效果例如受到以下事实的限制：可用的涂层本身非常脆，并且同时具有破裂或剥落的倾向。
专利US 4,969,522描述了聚合物涂覆的支撑剂，其通过在硅胶或硅砂存在下聚合多烯键式不饱和单体来制备。专利US 5,218,038涉及涂覆有可交联的酚醛树脂的支撑剂。US 2005/0244641 A1公开了涂覆有疏水材料如硅酮或硅氧烷的支撑剂。在US 2006/0035790 A1中也描述了用于压裂的支撑剂，其中细碎的砂子载体颗粒涂覆有弹性体，例如聚烯烃或聚氨酯。专利US 7,624,802描述了由酚醛树脂涂覆的载体材料组成的支撑剂，所述载体材料来自无机或有机材料或者无机和有机材料的复合物。WO 2008/088449A2描述了具有由树脂、交联剂、粘合促进剂和固化剂组成的涂层的支撑剂。US 2014/0124200 A1公开了具有由硅酮改性的甲醛树脂组成的涂层的支撑剂。WO 2016/070044 A1描述了一种用一系列功能性涂层处理支撑剂的方法。WO 2016/089599 A1描述了具有包含处理剂的涂层的支撑剂。
发明内容
本发明的目的是提供可适用于矿物油和天然气的压裂生产方法的支撑剂。这些支撑剂应具有必要的硬度，同时显示出弹性性质，以最小化涂层的破裂或剥落。在破裂或剥落的情况下，碎片应该形成附聚物。
本发明的主题是用于压裂生产方法的涂覆的支撑剂，其包含无机载体材料和涂层，该涂层包含来自含有具有1至15个碳原子的无支链或支链烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、乙烯基芳族化合物(vinylaromatics)、烯烃、二烯和乙烯基卤化物的组中的一种或多种烯键式不饱和单体的聚合物，其特征在于聚合物通过在水性介质(aqueous medium，含水介质)中的自由基引发的聚合反应获得，其中基于单体的总重量，共聚0.5至20wt％的包含硅烷基团的烯键式不饱和单体。
合适的无机载体材料早已从现有技术而为本领域技术人员所知，并且可用于本发明的支撑剂。载体材料通常是砂或岩石(例如石灰石、大理石、白云石、花岗岩)以及玻璃珠、陶瓷颗粒、陶瓷球等，此列表是说明性和非限制性的。载体颗粒优选呈现基本上球形的形式，因为这种形式允许足够的间隙以便原油或气体可以流过。砂、玻璃珠和中空玻璃球(称为微球)是优选的载体材料。使用的特别优选的载体材料是砂。载体材料颗粒的平均直径优选为50至5000μm，更优选平均直径为100至1500μm。
载体材料的涂层包含来自含有具有1至15个碳原子的无支链或支链烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、乙烯基芳族化合物、烯烃、二烯和乙烯基卤化物的组中的一种或多种烯键式不饱和单体的聚合物。优选的乙烯基酯是乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯和具有9至13个碳原子的α-支链一元羧酸的乙烯基酯，例如或(Momentive的商品名)。乙酸乙烯酯是特别优选的。
优选的甲基丙烯酸酯或丙烯酸酯是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸降冰片酯(norbornyl acrylate)。特别优选的是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯和丙烯酸2-乙基己酯。烯烃和二烯的实例是乙烯、丙烯和1,3-丁二烯。合适的乙烯基芳族化合物是苯乙烯和乙烯基甲苯。优选的乙烯基卤化物是氯乙烯。
包含硅烷基团的烯键式不饱和单体是具有通式RSi(CH3)0-2(OR1)3-1的单体，其中R的定义为CH2＝CR2-(CH2)0-1或CH2＝CR2CO2-(CH2)1-3，R1是具有1至12个碳原子的无支链或支链的任选被取代的烷基基团并且可以任选地被醚基中断，并且R2是H或CH3。
优选的是式CH2＝CR2-(CH2)0-1Si(CH3)0-1(OR1)3-2和CH2＝CR2CO2-(CH2)3Si(CH3)0-1(OR1)3-2的硅烷，其中R1是具有1至8个碳原子的支链或无支链的烷基基团且R2是H或CH3。
特别优选的烯键式不饱和硅烷是乙烯基甲基二甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三乙氧基硅烷、γ-丙烯酰氧基丙基三甲氧基硅烷、γ-丙烯酰氧基丙基三乙氧基硅烷。
所述烯键式不饱和硅烷化合物也可以任选地以其(部分)水解产物的形式存在。
优选地，基于单体的总重量，另外地共聚0.05至20wt％、更优选0.1至10wt％的一种或多种官能共聚单体。官能共聚单体的实例是烯键式不饱和单羧酸和二羧酸，优选丙烯酸、甲基丙烯酸、富马酸和马来酸以及马来酸酐；烯键式不饱和羧酰胺和腈，优选丙烯酰胺和丙烯腈；烯键式不饱和磺酸及其盐，优选乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸。官能共聚单体的其它实例是环氧官能共聚单体，诸如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。官能共聚单体的实例还包括具有羟基的单体，例子是甲基丙烯酸羟烷基酯和丙烯酸羟烷基酯，诸如丙烯酸或甲基丙烯酸的羟乙酯或羟丙酯或羟丁酯。优选烯键式不饱和单羧酸和二羧酸。
优选的是乙烯基酯(尤其是乙酸乙烯酯)与0.5至20wt％的包含硅烷基团的烯键式不饱和单体(诸如乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷或乙烯基甲基二乙氧基硅烷)和任选的0.1至10wt％烯键式不饱和羧酸(诸如丙烯酸或甲基丙烯酸)的聚合物，
其中聚合物可以任选地在每种情况下另外地包括5至45wt％来自包括具有3至15个碳原子的无支链或支链烷基羧酸的乙烯基酯(不同于共聚的乙烯基酯)、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、苯乙烯、乙烯、丁二烯和氯乙烯的组中的一种或多种单体单元，并且其中以wt％计的数字在每种情况下加起来为100wt％。
还优选的是具有1至15个碳原子的醇的(甲基)丙烯酸酯(诸如(甲基)丙烯酸甲酯和/或(甲基)丙烯酸正丁酯)与0.5至20wt％包含硅烷基团的烯键式不饱和单体(诸如乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷或乙烯基甲基二乙氧基硅烷)和任选的0.1至10wt％烯键式不饱和羧酸(诸如丙烯酸或甲基丙烯酸)和任选的0.1至50wt％、优选5至30wt％的苯乙烯的聚合物；
其中以wt％计的数字在每种情况下加起来为100wt％。
进行单体选择和/或共聚单体重量分数的选择，使得通常得到的玻璃化转变温度Tg为+10℃至+100℃。可以通过DSC(差示扫描量热法,DIN EN ISO 11357-1/2)，使用例如来自Mettler-Toledo的DSC1动态扫描量热仪在开放式坩埚中以10K/min的加热速率来确定聚合物的玻璃化转变温度Tg。所采用的玻璃化转变温度是热流图中第二加热曲线的步阶的中点处的温度(中点＝热流步阶的半步高度)。也可以使用Fox方程大致预先计算Tg。根据FoxT.G.,Bull.Am.Physics Soc.1,3,第123页(1956)：1/Tg＝x1/Tg1+x2/Tg2+...+xn/Tgn，其中xn是单体n的质量分数(wt％/100)，并且Tgn是单体n的均聚物的玻璃化转变温度(单位：开尔文)。Polymer Handbook第2版,J.Wiley&Sons,New York(1975)中列示了各均聚物的Tg值。
聚合物可通过乳液聚合方法制备，如例如Encyclopedia of Polymer Scienceand Engineering,第8卷，第659至677页,John Wiley and Sons,Inc.,1987或DE102006050336 A1中所描述的。在这种情况下，烯键式不饱和单体在乳化剂和/或保护胶体存在下在水性介质中通过自由基引发的聚合来聚合。获得聚合物的水性分散体，优选固含量为40至70％。
用于涂层的聚合物也可以以由有机聚合物和至少一种无机固体组成的复合颗粒的形式使用，在此种情况下，基于复合颗粒中有机聚合物和无机固体的总重量，无机固体的重量分数为15至40wt％。
复合颗粒是现有技术并且可商购获得，并且可以采用水性颗粒分散体或水分散性聚合物粉末的形式。复合颗粒包含有机聚合物相，其中分散有细碎的无机固体颗粒，这些颗粒优选通过物理键(例如，通过聚合物中的羧基官能单体单元)或通过化学键(例如，通过聚合物中的硅官能单体单元)而连接到有机聚合物相的聚合物链。
优选的细碎的无机固体颗粒是金属氧化物或半金属氧化物。对于分散在水中的固体颗粒，这些优选具有4至150nm、更优选5至100nm的粒径。粒径是重均粒径dw，是例如使用来自Coulter的Nanosizer通过统计光散射测量来确定的。
合适的金属氧化物的实例是钛、锆、铝、钡、镁或铁的氧化物。这些种类的金属氧化物可商购获得，例子是二氧化钛、锆(IV)氧化物、锡(II)氧化物、锡(IV)氧化物、氧化铝、羟基氧化铝、氧化钡、氧化镁、铁(II)氧化物、铁(III)氧化物、铁(II/III)氧化物。优选的半金属氧化物可以是二氧化硅。二氧化硅可以以无定形形式和/或以各种晶体结构存在。二氧化硅可以采用例如水玻璃或二氧化硅溶胶的形式。合适的二氧化硅也以商品名称和已知。特别优选的是二氧化硅溶胶、和铝酸盐或环氧硅烷改性的二氧化硅溶胶。为了制备改性二氧化硅溶胶，在搅拌和任选地加热的同时向常规二氧化硅溶胶中加入铝酸盐水溶液(例如NaAl(OH)4)或环氧硅烷(例如3-缩水甘油氧基丙基三甲氧基硅烷)。
细碎的无机固体的制备是本领域技术人员已知的，并且例如通过在气相中的沉淀反应或化学反应来实现(在这方面参照E.Matijevic,Chem.Mater.1993,5,第412至426页；Ullmann's Encyclopedia of Industrial Chemistry,第A 23卷，第583至660页,VerlagChemie,Weinheim,1992)。
可使用上文描述为现有技术的方法来制备包含有机聚合物和细碎的无机固颗粒的复合颗粒。此处的细碎的无机固体颗粒优选以稳定的水性固体分散体的形式使用。
包含细碎的无机固体的水性分散体优选在有机聚合物生产的聚合过程中加入，或者将其加入到完成的聚合物分散体中。还优选的方法是将细碎的无机固体的水性分散体与聚合物分散体混合，以便在无机颗粒和有机颗粒之间可以发生化学或物理结合。
同样优选的方法是将包含细碎的无机固体的水性分散体与水性聚合物分散体并与环氧硅烷化合物(例如3-缩水甘油氧基丙基三甲氧基硅烷或3-缩水甘油氧基丙基甲基二乙氧基硅烷)混合。
所述混合操作优选在20℃至70℃的温度下进行优选1至12小时的时间段。
复合颗粒至少部分地具有核-壳结构。在这一结构中，无机颗粒形成核且聚合物链形成壳。基于复合颗粒中有机聚合物和无机固体的总重量，无机固体在复合颗粒中的重量分数为15至45wt％。
可由此获得的复合颗粒通常以水性分散体的形式存在，优选固含量为40至70％，更优选45至65％且最优选50至60％。
本发明的另一主题是用于生产根据本发明涂覆的支撑剂的方法。
本领域技术人员知道现有技术中用于涂覆支撑剂的各种可能性。这些方法也可用于使用本发明的聚合物涂覆支撑剂。在一个优选的实施方式中，例如通过浸渍或喷涂或混合，将聚合物以水性聚合物分散体或水性复合材料分散体(aqueous compositedispersion，水性复合颗粒分散体，水性复合分散体)的形式施加到无机载体材料上，然后干燥。在施加涂层的过程中，也可以加入添加剂，例如粘合促进剂、抗静电剂。施加和干燥优选在20℃至50℃的温度下进行。
在涂覆的支撑剂中，支撑剂的表面可具有完全或部分涂层。当在扫描电子显微镜下检查时，优选无机载体材料可见表面的至少50％涂有聚合物，更优选至少95％。载体材料上的涂层厚度为0.1至100μm，优选0.1至30μm。涂覆的支撑剂优选涂有少于三层的涂层，更优选仅涂有一层涂层。
在每种情况下基于支撑剂的总重量，通常以0.1至10wt％、优选0.5至5wt％、且更优选0.5至2wt％的量向无机载体材料施加涂层。
本发明的进一步主题是涂覆的支撑剂在用于矿物油和天然气的压裂生产方法中的用途。
本发明的涂覆的支撑剂的优点可总结如下：
与现有技术的涂覆的支撑剂相比，水性聚合物分散体形式的聚合物可以在相当低的温度下施加和干燥，因为与交联体系相比，它们不是热固化的，而是通过聚结来形成膜。与交联酚醛清漆涂料相比，还可以在不释放VOC如甲醛的情况下进行固化或干燥。
聚合物或聚合物复合材料的水性分散体具有相对低的粘度，因此当施加涂层时表现出明显更好的扩散。因此，表面涂覆更均匀，并且可以获得更光滑的表面。
涂覆的支撑剂对于相同的硬度表现出增强的弹性和可变形性。因此，支撑剂在载荷(如冲击、变形或压力)面前更加坚固并且具有较低的断裂倾向。传统的现有技术支撑剂非常脆并且具有很大的破裂倾向。支撑剂的破碎释放出细小的碎片。细小碎片的释放不利于原油或气体流动的传输速率，因为支撑剂颗粒之间的间隙被堵塞。相反，使用根据本发明涂覆的支撑剂，细小碎片在破裂时发生附聚，并且防止或者至少显著减少细小碎片的释放。
依靠根据本发明涂覆的支撑剂的这些有利特性，油或气体的流动可以保持更长时间。这在经济和保护环境方面产生了决定性的优势。
具体实施方式
以下实施例用于说明本发明，而没有任何限制作用。
实施例1(聚合物分散体1)：
在氮气氛下，向体积为3升的反应器中装入1.0g去离子水、4.6g月桂基硫酸钠和1.4g过硫酸钾，并且在搅拌下将该初始装料加热至40℃。在该温度下，将具有以下组成的混合物引入反应器中：
随后将温度升至80℃，并在达到该温度时，在3小时的过程中计量加入引发剂溶液(1.4g过硫酸钾在86.8g水中)；同时但分开地，在2.5小时的过程中，将具有下列组成的溶液引入反应器中：
在计量加入结束后，在80℃下搅拌2小时并在85℃下搅拌1小时。
随后用水稀释聚合物分散体，并使用氨水溶液(12.5％强度)将pH调节至9。这得到固含量(DIN EN ISO 3251)为43.0wt％的聚合物溶液。最低成膜温度(DIN ISO 2115)为5℃。
实施例2(复合材料分散体2)：
在50℃下在搅拌的同时向夹套反应器中装入1000g 43％的水性聚合物分散体1，并且加入460g二氧化硅水溶胶(固含量40％,来自Akzo Nobel的Bindzil 2040)。
所得的分散体的固含量为42.7％并且基于总固体含量的二氧化硅含量为30wt％。
生产涂覆的支撑剂：
在混合器中，使用喷嘴将基于砂为2wt％的实施例1和2的分散体分别喷雾到12/18目和20/40目的压裂砂上，并在80℃下干燥分散体。
用电子显微镜(SEM)研究压裂砂的涂层质量：
在每种情况下实现了>95％的表面覆盖率。
涂覆的支撑剂压力稳定性的研究：
在每种情况下，根据DIN EN ISO 13503-2在7500psi和10000psi压力下研究涂覆的支撑剂的压力稳定性。
结果显示在表1和2中。
表1：
表2：
使用本发明的支撑剂，在每种情况下的结果是在压力加载后的细小碎片少得多。
Claims (10)
1.一种用于压裂生产方法的涂覆的支撑剂，包含无机载体材料和涂层，所述涂层包含一种或多种烯键式不饱和单体的聚合物，所述烯键式不饱和单体来自包含以下各项的组：具有1至15个碳原子的无支链或支链烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、乙烯基芳族化合物、烯烃、二烯和乙烯基卤化物，其特征在于，所述聚合物通过在水性介质中进行自由基引发的聚合来获得，其中，基于单体的总重量，共聚0.5至20wt％的包含硅烷基团的烯键式不饱和单体。
2.根据权利要求1所述的涂覆的支撑剂，其特征在于，所述包含硅烷基团的烯键式不饱和单体是具有通式RSi(CH3)0-2(OR1)3-1的单体，其中，R具有定义CH2＝CR2-(CH2)0-1或CH2＝CR2CO2-(CH2)1-3，R1是无支链或支链的、任选取代的具有1至12个碳原子的烷基基团并且可以任选地被醚基团中断，并且R2是H或CH3。
3.根据权利要求1或2所述的涂覆的支撑剂，其特征在于，所述涂层包含乙烯基酯与0.5至20wt％的包含硅烷基团的烯键式不饱和单体和任选的0.1至10wt％的烯键式不饱和羧酸的聚合物，其中，所述聚合物在每种情况下可以任选地还包含5至45wt％的来自包含以下各项的组的一种或多种单体单元：具有3至15个碳原子的无支链或支链烷基羧酸的不同于共聚的乙烯基酯的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、苯乙烯、乙烯、丁二烯和氯乙烯，并且其中，在每种情况下以wt％计的数字加起来为100wt％。
4.根据权利要求1或2所述的涂覆的支撑剂，其特征在于，所述涂层包含具有1至15个碳原子的醇的(甲基)丙烯酸酯与0.5至20wt％的包含硅烷基团的烯键式不饱和单体和任选的0.1至10wt％的烯键式不饱和羧酸以及任选的0.1至50wt％、优选5至30wt％的苯乙烯的聚合物；其中，在每种情况下以wt％计的数字加起来为100wt％。
5.根据权利要求1或2所述的涂覆的支撑剂，其特征在于，所述涂层包含复合颗粒形式的聚合物，所述复合颗粒由有机聚合物和至少一种无机固体组成，其中，基于所述复合颗粒中的有机聚合物和无机固体的总重量，无机固体的重量分数为15至40wt％。
6.根据权利要求5所述的涂覆的支撑剂，其特征在于，包括的无机固体颗粒是金属氧化物或半金属氧化物。
7.根据权利要求1至6所述的涂覆的支撑剂，其特征在于，所使用的无机载体材料是砂、岩石、玻璃珠、陶瓷颗粒或陶瓷球。
8.根据权利要求1至7所述的涂覆的支撑剂，其特征在于，载体材料颗粒具有50至5000μm的平均直径。
9.一种用于生产权利要求1至8所述的涂覆的支撑剂的方法，其特征在于，将所述聚合物以水性聚合物分散体或水性复合材料分散体的形式施加到所述无机载体材料并且随后干燥。
10.权利要求1至8所述的涂覆的支撑剂在用于矿物油和天然气的压裂生产方法中的用途。
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018059714A1 (de) | 2018-04-05 |
| EP3519530B1 (de) | 2020-12-02 |
| EP3519530A1 (de) | 2019-08-07 |
| RU2719833C1 (ru) | 2020-04-23 |
| CN109804039B (zh) | 2021-06-11 |
| US10995264B2 (en) | 2021-05-04 |
| US20200157414A1 (en) | 2020-05-21 |
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