JP2022191294A - 石油およびガス産業における従来の酸の代替物としての新規改質酸組成物 - Google Patents
石油およびガス産業における従来の酸の代替物としての新規改質酸組成物 Download PDFInfo
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Abstract
Description
・強酸とアルカノールアミンとが、15:1以下のモル比で、好ましくは10:1以下のモル比で、さらに好ましくは8:1以下のモル比で、さらに一層好ましくは5:1以下のモル比で、さらになお一層好ましくは4.1:1以下のモル比で、さらになお一層好ましくは3:1以上のモル比で含まれる合成または改質酸組成物が提供される。
モノエタノールアミン(MEA)および塩酸を出発試薬として使用する。4.1:1のモル比のMEAとHClとを得るには、まず165gのMEAと835gの水とを混合しなければならない。これにより、モノエタノールアミン溶液が形成される。その後、先に調製したモノエタノールアミン溶液370mlを取り、36%のHCl水溶液(22 Baume)350mlと混合する。添加剤を使用する場合、MEA溶液とHClとを完全に混合してから添加剤を加える。例えば、この時点で、ヨウ化カリウム、および本発明による組成物の性能を最適化するために望ましい他の任意の成分を加えることができる。あらゆる生成物が可溶化されるまで循環を維持する。必要に応じて、この時点で追加の生成物を加えることができる。
本発明の好ましい実施形態による組成物を腐食試験に曝露した。ほとんどの場合、様々な酸性流体に腐食パッケージを加えた。腐食パッケージ成分の%は、最終配合組成(酸+腐食防止剤)内のその%を示す。腐食試験の結果を表3~25に報告する。使用した対照は、HClの組成物であった。様々な温度で様々な時間にわたり、様々な列挙された組成物に様々な鋼鉄グレードの試験片を曝露した。好ましい結果は、lb/ft2の腐食数が0.05以下のものである。さらに好ましくは、その数は0.02以下である。
本発明の好ましい実施形態による改質酸の効果を評価するために、溶解試験を実施して、炭酸カルシウム(表24)およびドロマイト(表25)への曝露時の様々な組成物の溶解力を試験した。試験は23℃の温度で実施し、15%HClおよび28%HClの溶液の効果と比較した。結果を以下の表24および25に報告する。
本発明の好ましい実施形態による組成物の反応性を評価するために試験を実施した。
所定量の合成酸を水浴中で60℃に加熱した。次いで、溶液を天秤上に置き、事前に秤量した炭酸カルシウムタイルを加熱溶液に浸した。重量は、1分間ごとに30分間記録した。記録された重量から重量損失率を計算し、時間の関数としてプロットした。
様々な温度での例1の組成物の安定性を評価するために、テフロンライナー付き加圧エージングセルを使用して試験を実施した。400psiの圧力で試験を実施した。試験の結果を以下の表26に報告する。
この試験の目的は、モル比1:4.1のMEA-HCl組成物を皮膚に単回塗布した後の例1の組成物の皮膚刺激性および腐食性を評価することであった。
被検物質の皮膚腐食の可能性を決定するために、例1の組成物を使用して、アルビノウサギに対して皮膚腐食/皮膚刺激試験を実施した。
石油およびガス産業で使用される一般的な封止要素が酸組成物と接触すると、劣化するか、少なくとも損傷の兆候を示す傾向がある。本発明の好ましい実施形態による組成物に、この産業での作業に共通する多くの封止要素を曝露して、それらの完全性に対する本発明の好ましい実施形態による組成物の影響を評価した。さらに具体的には、ブレークダウンでは欠陥のある封止要素の交換が必要とされるため、封止要素の硬化および乾燥ならびに機械的完全性の損失は、特定のプロセスの効率に大きな影響を及ぼし得る。様々なエラストマーに対する例1の組成物の曝露の影響を評価するために試験を実施した。70℃および28,000kPaでの例1の濃縮生成物の長期(72時間曝露)エラストマー試験では、Nitrile(登録商標)70、Viton(登録商標)75、Aflas(登録商標)80型の封止要素などの様々なエラストマーの劣化がほとんどまたは全くないことが示された。結果を表28に報告する。これは、例1の組成物が、石油およびガス産業で典型的に見られる様々なエラストマーと適合性があることを示している。
カーボナート酸処理におけるワームホーリングプロセスに関する多くの試験により、流動する酸によって生成される溶解パターンは、以下の3つのタイプ、すなわち、(1)酸の大部分が岩の表面の近くで消費されるコンパクト溶解、(2)少数の高導電性マイクロチャネル、すなわちワームホールの先端で周囲の壁よりも溶解が急速に進むワームホーリングおよび(3)均一な溶解のうち1つとして特徴付けることができることが示されている。
例1の組成物対15%HClの性能を評価するために、2組のマトリックス酸処理実験を実施した。実験では、0.3体積%の一般的な市販の腐食防止剤を含む濃度90%の例1の組成物を使用し、他の実験セットでは0.3体積%の腐食防止剤を含む15%のHCl溶液を使用した。実験はインディアナ石灰石のコアを利用して実施した。
マトリックス酸処理装置は、ポンプシステム、蓄積システム、コア封じ込めセル、圧力維持システム、加熱システムおよびデータ取得システムからなる。Teledyne Isco(登録商標)シリンジポンプを使用して、一定の速度で水および酸を注入した。背圧調整器を使用して、所望の最小システム圧力を2000psiに維持した。
試験に使用したコアは、直径1.5インチ、長さ8インチであった。線形特性を確保するために、露頭の1つのサンプルからインディアナ石灰石サンプルを取得した。
例1の組成物(濃度90%)と15%HCl組成物とのワームホーリング性能を比較するために、2つの間隙速度値でいくつかのモデリング作業を行った。
単純化されたHawkinsの式によってスキンを計算した。
以下の式4を使用して、全体的な産出指数を計算した。
次いで、各酸の産出を0および10の全体的なスキンでのJD値と比較した。
スキンの項は0または10の値を有する。次いで、使用した酸の量とともに、この比率をグラフ化した。計算のために、2bpmの注入速度、14%の気孔率、1,000フィートの坑井厚、0.4フィートの初期坑井半径、2,980フィートの油層半径、3,000psiの坑井圧、5,000psiの油層圧、30mDの浸透率、1cpの流体粘度および1.117の地層体積係数を想定した。
モノエタノールアミンの環境への影響を評価するために、一連の試験を実施した。純度98~99%のモノエタノールアミンの原液を試験に供した。必要に応じて溶液を希釈した。
この試験は、海洋カイアシ類アカルチア・トンサ(Acartia tonsa)に対するモノエタノールアミンの水相毒性を決定するために委託された。A.トンサ毒性LC50試験は、以下の逸脱および干渉を除いて試験計画に従って実施され、他の関連する妥当性基準をいずれも満たしていた。最終試験では、希釈水の温度は許容限度を最大0.7℃下回っており、pHは許容限度を最大0.01単位下回っていた。これらの逸脱は、対照群に死亡例が認められなかったことから、試験に影響を及ぼすとは予測されなかった。
この試験は、潮間帯の端脚類コロフィウム・ボルタトル(Corophium volutator)に対するモノエタノールアミンの組成物の堆積物相毒性を決定するために委託された。C.ボルタトル毒性LC50試験は、試験計画に従って実施され、関連する妥当性基準をいずれも満たしていた。10,000mg/kg(公称重量)での複製物のpHは、通常必要とされる7.5~8.5の範囲と比較してはるかに高いpHを示したが、これは被検物質自体の直接的な影響である。モノエタノールアミンの組成物は、堆積相の海洋端脚類C.ボルタトルに対して、6,660mg/kgの10日LC50値(乾燥堆積物による)を示した。結果は名目上濃度に基づいており、統計解析のCETISパッケージソフト内の線形補間によって計算された。
この試験は、海洋単細胞藻類スケルトネマ種に対するモノエタノールアミンの組成物の水相毒性を決定するために委託された。スケルトネマ種毒性EC(r)50試験は、試験計画に従って実施され、関連する妥当性基準をいずれも満たしていた。この試験から得られた結果を報告する。観察により、1000mg/lストックのpHは物理的変化をもたらしたことが示され、このストックは混濁から透明に変化したことから、100mg/lストックとは別に未調整ストックを用量反応区域検出試験および最終試験に使用したところ、物理的変化は観察されなかった。
この試験は、海水中のモノエタノールアミンの組成物の好気的分解性を決定するために委託された。試験は試験計画に従って実施され、関連する妥当性基準をいずれも満たしていた。この試験では逸脱はなかった。ThODNO3値は、試験した化合物の化学式から決定された。窒素含有成分が存在していたため、完全な硝化が想定された。
この試験は、海産魚キプリノドン・ヴァリエガータスに対するモノエタノールアミンの組成物の水生(96時間限界試験)毒性を決定するために委託された。
表33は、約1~90%希釈の範囲の希釈時の本発明による組成物の多くの潜在的な使用(または用途)を列挙するものであり、それらには、限定するものではないが、注入/廃棄処理;マトリックス酸の圧搾、浸漬またはブルヘッド(bullhead);酸フラクチャリング、酸洗浄;破砕スピアヘッド(ブレークダウン);パイプラインスケール処理、セメントブレークダウンまたは穿孔洗浄;pH制御;ならびにスケール除去用途、高温(最高190℃)循環スチームスケール処理およびスチーム補助重力排油法(SAGD)スケール処理(最高190℃)が挙げられる。
Claims (33)
- 15:1以下のモル比で鉱酸およびアルカノールアミン
を含む水性改質酸組成物。 - 15:1以下のモル比で塩酸およびアルカノールアミン
を含む水性改質酸組成物。 - 前記塩酸およびアルカノールアミンが10:1以下のモル比で存在する、請求項2に記載の水性改質酸組成物。
- 前記塩酸およびアルカノールアミンが7.0:1以下のモル比で存在する、請求項2に記載の水性改質酸組成物。
- 前記塩酸およびアルカノールアミンが4.1:1以下のモル比で存在する、請求項2に記載の水性改質酸組成物。
- 前記塩酸およびアルカノールアミンが3:1以上のモル比で存在する、請求項2に記載の水性改質酸組成物。
- 前記アルカノールアミンが、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンおよびそれらの組合せからなる群から選択される、請求項1~6のいずれか一項に記載の水性改質酸組成物。
- 前記アルカノールアミンがモノエタノールアミンである、請求項1~7のいずれか一項に記載の水性改質酸組成物。
- 前記アルカノールアミンがジエタノールアミンである、請求項1~7のいずれか一項に記載の水性改質酸組成物。
- 金属ヨウ化物またはヨーダートをさらに含む、請求項1~9のいずれか一項に記載の水性改質酸組成物。
- 前記鉱酸が、HCl、硝酸、硫酸、スルホン酸、リン酸およびそれらの組合せからなる群から選択される、請求項1に記載の組成物。
- 金属ヨウ化物またはヨーダートをさらに含む、請求項1~11のいずれか一項に記載の水性改質酸組成物。
- アルコールまたはその誘導体をさらに含む、請求項1~12のいずれか一項に記載の改質酸組成物。
- 前記金属ヨウ化物またはヨーダートが、ヨウ化第一銅、ヨウ化カリウム、ヨウ化ナトリウム、ヨウ化リチウムおよびそれらの組合せからなる群から選択される、請求項12に記載の改質酸組成物。
- 前記金属ヨウ化物またはヨーダートがヨウ化カリウムである、請求項12に記載の改質酸組成物。
- 前記アルコールまたはその誘導体がアルキニルアルコールまたはその誘導体である、請求項13~15のいずれか一項に記載の改質酸組成物。
- 前記アルキニルアルコールまたはその誘導体がプロパルギルアルコールまたはその誘導体である、請求項16に記載の改質酸組成物。
- 前記アルキニルアルコールまたはその誘導体が、0.01から5%w/wの範囲の濃度で存在する、請求項16に記載の改質酸組成物。
- 前記アルキニルアルコールまたはその誘導体が、0.2%w/wの濃度で存在する、請求項16に記載の改質酸組成物。
- 前記金属ヨウ化物が、前記組成物の総重量の0.1~2重量%の範囲の濃度で存在する、請求項12~19のいずれか一項に記載の改質酸組成物。
- α位にメチル基を有しないα,β-不飽和アルデヒドを含む腐食防止剤をさらに含む、請求項1~20のいずれか一項に記載の改質酸。
- α位にメチル基を有しない前記α,β-不飽和アルデヒドが、シトラールおよびシンナムアルデヒドからなる群から選択される、請求項21に記載の改質酸。
- 石油産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、地層の刺激;ダウンホールポンプ作業中のブレークダウン圧の低減の支援;掘削作業後の坑井フィルターケークの処理;詰まったパイプの解放の支援;パイプラインおよび/または生産井のスケール除去;注入油井の注入性の向上;流体のpHの低下;設備、油井ならびに関連する設備および施設からなる群から選択される表面上の望ましくないスケールの除去;油井の破砕;マトリックス刺激;環状およびブルヘッドの圧搾および浸漬の実施;管、パイプおよび/またはコイル状管の酸洗;地層の効果的な浸透率の向上;坑井損傷の軽減または排除;穿孔の洗浄;ならびに石灰石、ドロマイト、方解石およびそれらの組合せの可溶化からなる群から選択される作業を含む使用。
- 鉱業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、スケールの処理、および流体系におけるpHレベルの調整からなる群から選択される使用。
- 水処理産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、pHの調整およびアルカリ性廃液の中和からなる群から選択される使用。
- 土壌のpHレベルを調整するための、肥料/造園業における請求項1~22のいずれか一項に記載の改質酸組成物の使用。
- イオン交換ベッドを再生するための、請求項1~22のいずれか一項に記載の改質酸組成物の使用。
- 建設産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、コンクリートのエッチング、ならびに設備および建物からのコンクリートの洗浄からなる群から選択される使用。
- 発電産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、パイプラインおよび関連設備のスケール除去、ならびに施設のスケール除去からなる群から選択される使用。
- 食品および酪農産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用であって、前記使用が、タンパク質の製造、デンプンの製造、ホエーの脱塩、カゼインの製造およびイオン交換樹脂の再生からなる群から選択される使用。
- 流体のpHを低下させるための、プール産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用。
- 鋼鉄の酸洗および金属の洗浄からなる群から選択される作業を実施するための、製造産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用。
- 低pH洗浄添加剤としての、小売産業における請求項1~22のいずれか一項に記載の改質酸組成物の使用。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2969174A CA2969174A1 (en) | 2017-06-02 | 2017-06-02 | Novel modified acid compositions as alternatives to conventional acids in the oil and gas industry |
CA2,969,174 | 2017-06-02 | ||
PCT/CA2018/000105 WO2018218333A1 (en) | 2017-06-02 | 2018-05-30 | Novel modified acid compositions as alternatives to conventional acids in the oil and gas industry |
JP2019566830A JP7204682B2 (ja) | 2017-06-02 | 2018-05-30 | 石油およびガス産業における従来の酸の代替物としての新規改質酸組成物 |
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US11414970B2 (en) * | 2017-06-06 | 2022-08-16 | Schlumberger Technology Corporation | Acid stimulation methods |
CA2989929A1 (en) | 2017-12-22 | 2019-06-22 | Fluid Energy Group Ltd. | Novel modified acid compositions as alternatives to conventional acids in the oil and gas industry |
US11187051B2 (en) * | 2018-08-10 | 2021-11-30 | The Board Of Trustees Of The Leland Stanford Junior University | Fracture fluid alteration to mitigate barite scale precipitation in unconventional oil/gas shale systems |
CA3028229A1 (en) * | 2018-12-20 | 2020-06-20 | Fluid Energy Group Ltd. | Novel corrosion inhibition package |
CA3028226A1 (en) * | 2018-12-20 | 2020-06-20 | Fluid Energy Group Ltd. | Novel alkylsulfonic acid compostions |
CA3039235A1 (en) * | 2019-04-05 | 2020-10-05 | Fluid Energy Group Ltd. | Novel mud acid composition and methods of using such |
US11740004B2 (en) | 2019-06-26 | 2023-08-29 | Carrier Corporation | Transportation refrigeration unit with adaptive defrost |
CA3054052A1 (en) * | 2019-09-04 | 2021-03-04 | Fluid Energy Group Ltd. | Composition to reduce friction reducer fouling in wellbores |
CN113185959B (zh) * | 2021-03-15 | 2022-11-25 | 中海石油(中国)有限公司天津分公司 | 一种变形耐高温油溶颗粒蒸汽剖面调整剂、制备方法及其应用 |
US11492539B1 (en) * | 2021-10-28 | 2022-11-08 | Halliburton Energy Services, Inc. | Acid generation for filtercake removal in subterranean applications |
GB2616071A (en) | 2022-02-28 | 2023-08-30 | Swellfix Uk Ltd | Materials and compositions for reservoir stimulation treatment |
KR102458084B1 (ko) * | 2022-03-10 | 2022-10-24 | 전남대학교산학협력단 | 탄산염암저류층 산처리용 유화산조성물 및 그 제조방법 |
US11884878B1 (en) | 2022-07-22 | 2024-01-30 | Halliburton Energy Services, Inc. | Substituted amine acid salt activation of furfuryl alcohol-based resins |
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JPS52136204A (en) * | 1976-05-11 | 1977-11-14 | Kao Corp | Detergent compositions |
US5006258A (en) * | 1989-10-26 | 1991-04-09 | Conoco Inc. | Regeneration of acidic cationic exchange resin used in the reactivation of spent alkanolamine |
CA2157916C (en) * | 1993-03-23 | 2000-01-25 | Allen C. Hieatt | Method of cleaning and maintaining potable water distribution pipe systems |
US7476371B2 (en) * | 2002-02-14 | 2009-01-13 | Phibro-Tech, Inc. | Dissolution of copper metal in aqueous alkanolamine to form copper containing aqueous solution |
US8163826B2 (en) * | 2006-11-21 | 2012-04-24 | Schlumberger Technology Corporation | Polymeric acid precursor compositions and methods |
US9796490B2 (en) | 2013-10-24 | 2017-10-24 | Schlumberger Technology Corporation | Aqueous solution and method for use thereof |
WO2015034478A1 (en) * | 2013-09-04 | 2015-03-12 | Halliburton Energy Services, Inc. | Scale-inhibiting cocrystals for treatment of a subterranean formation |
CA2931998C (en) * | 2014-01-03 | 2017-11-28 | Halliburton Energy Services, Inc. | Wellbore servicing methods and compositions comprising degradable polymers |
US10064805B2 (en) * | 2014-05-02 | 2018-09-04 | Hercules Llc | Personal care composition for a keratin substrate comprising conditioning and/or styling polymer |
US10253249B2 (en) | 2014-08-01 | 2019-04-09 | Schlumberger Technology Corporation | Compositions and methods for treating subterranean formations |
CA2866512A1 (en) | 2014-10-02 | 2016-04-02 | Fluid Energy Group Ltd. | Synthetic acid compositions and uses thereof |
US20160177173A1 (en) * | 2015-12-04 | 2016-06-23 | Shell Oil Company | Method of treating a hydrocarbon containing formation |
CA2950370A1 (en) * | 2016-12-02 | 2018-06-02 | Fluid Energy Group Ltd. | Novel corrosion inhibition package |
CA2956939A1 (en) * | 2017-02-03 | 2018-08-03 | Fluid Energy Group Ltd. | Novel corrosion inhibition package |
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UA124288C2 (uk) | 2021-08-18 |
JP7204682B2 (ja) | 2023-01-16 |
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BR112019025199A2 (pt) | 2020-06-23 |
CA3006476C (en) | 2019-07-02 |
CN110945098B (zh) | 2023-02-17 |
CA2969174A1 (en) | 2018-12-02 |
AU2018276317A1 (en) | 2019-12-12 |
CN110945098A (zh) | 2020-03-31 |
US11879092B2 (en) | 2024-01-23 |
EA201992799A1 (ru) | 2020-07-15 |
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US10822535B2 (en) | 2020-11-03 |
ZA201908449B (en) | 2021-04-28 |
US11920081B2 (en) | 2024-03-05 |
US11912929B2 (en) | 2024-02-27 |
CA3041484A1 (en) | 2018-12-02 |
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