CN102952536B - Multifunctional self diverting acid - Google Patents
Multifunctional self diverting acid Download PDFInfo
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- CN102952536B CN102952536B CN201110247626.9A CN201110247626A CN102952536B CN 102952536 B CN102952536 B CN 102952536B CN 201110247626 A CN201110247626 A CN 201110247626A CN 102952536 B CN102952536 B CN 102952536B
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- acid
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- limestone
- sequestrant
- acid solution
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- 239000002253 acid Substances 0.000 title claims abstract description 53
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 abstract description 21
- 239000006028 limestone Substances 0.000 abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001556 precipitation Methods 0.000 abstract description 10
- 230000006378 damage Effects 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- -1 iron ions Chemical class 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000003352 sequestering agent Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 208000027418 Wounds and injury Diseases 0.000 description 7
- 208000014674 injury Diseases 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a multifunctional self diverting acid which is prepared by two kinds of carboxylic acid chelating agents according to a certain proportion. The self diverting acid can not only react with a limestone and plays a role of a main acid system, but also effectively divert the acid solution, and simultaneously stabilize iron ions and prevent stratum damages caused by precipitation of polyvalent metal cation hydroxides or salts.
Description
Technical field
The invention belongs to limestone formation acidifying steering technique field, more specifically relate to a kind of for the multi-functional self-diverting acid in limestone formation acidifying transformation process.
Background technology
In limestone formation acidifying transformation process, acid solution can enter the high interval of rate of permeation usually, and the low section of rate of permeation just seldom or by acid do not enter; Acid solution itself and limestone can form acid hole after reacting in addition, more aggravate acid solution and enter the passage of these high flow conductivities and can not enter other stratum, so steering technique plays a part very important in limestone acidization.
Mainly contain four kinds of main acid liquid system at present to can be used to carry out limestone acidifying, i.e. hydrochloric acid, organic acid as formic acid or acetic acid, non-acid as sequestrant, ester class etc. with solid acid as PLA and PGA.In order to make speed of reaction slack-off, sometimes above-mentioned acid solution is carried out disperseing (surfactant acid) or emulsification (as emulsified acid).Usually along with the raising of Oil/gas Well formation temperature, above various main body acid solution is selected in order.
Except mechanical steering method, following four kinds of chemistry diversion method (1) oil-soluble resin balls or other polymer beads (2) supersaturated brine is had to form grain of salt crystals (3) foam (4) visco-elasticity self-diverting acid (real-time cross-linked polymer or tensio-active agent) at present.Chemistry diversion method is that current limestone acidifying transformation uses the most general steering technique, and various chemistry diversion technology respectively has relative merits.
Summary of the invention
The object of the present invention is to provide a kind of multi-functional self-diverting acid, this self-diverting acid not only can react with limestone the effect playing main acid liquid system, and can effectively acid solution be turned to, can also iron ion be stablized simultaneously, prevent multivalent metal cation oxyhydroxide or salt from the injury that precipitation causes formation occurring.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of multi-functional self-diverting acid, it is characterized in that, described multi-functional self-diverting acid is formulated by a certain percentage by two kinds of carboxylic-acid sequestrants.
Wherein, described carboxylic-acid sequestrant is selected from the sodium salt of EDTA, HEDTA, DTPA or GLA.
Wherein, described two kinds of carboxylic-acid sequestrant ratios are 40: 1.
Following test is carried out to the present invention:
(1) solubleness test
1. be at room temperature, in the beaker of 15%HCl, add 8 grams of Na filling 20ml mass concentration
3hEDTA pressed powder, stirs with glass stick and dissolves rapidly, measure solution ph and record.
2. in above-mentioned solution, add 0.2 gram of Na again
2eDTA obtains initial soln by glass stick stirring and dissolving equally.
3. carry out titration and observe solution changing to above-mentioned solution with 20%NaOH solution.
4., if there is solid crystal to separate out, add 15% hydrochloric acid more in the mixture, or dilute with water, observe the change of solution.
5. above-mentioned experiment is repeated in 80 DEG C of (in water-bath) environment.
Experimental result sees the following form: Na
3hEDTA and Na
2eDTA by a certain percentage (40: 1) joins in hydrochloric acid soln, and along with the change of solution ph, (when being titrated to pH value 2-3 by NaOH solution), has solid particulate to separate out from solution.Afterwards by after hydrochloric acid soln or water dilution, solid crystal or precipitate are dissolved in solution again.This experimental result can repeat when 80 DEG C.
(2) resistance to flow test
1. prepare each 300 milliliters of two liquid described in solubleness test, one is initial soln (15%HCl 20ml+8g Na
3hEDTA+0.2g Na
2eDTA), another is that initial soln is titrated to the solution of pH2-3 through 20%NaOH.
2. with polytetrafluoroethylraw raw material band, the syringe needle of needle tubing is sealed in order to avoid liquid flows out in needle tubing.
3. slowly pour 50 milliliters of initial solns into in needle tubing.Without injection plunger, needle tubing mouth is kept to open wide.
4. the needle tubing filling liquid is fixed on iron stand, and keeps vertical.
5. open syringe needle sealing, and timing at once, record the time after 50 milliliters of liquid flowings.
6. separately get each 200 milliliters of two liquid (is initial soln, and another is that initial soln is titrated to the solution of pH2-3 through 20%NaOH) prepared, join respectively in the sample cup of Fann35A.
7. measure the reading of two sample F ann35A 600rpm and record.
Resistance to flow test result sees the following form:
After adopting technique scheme, its beneficial effect is: two kinds of sequestrants join in main body hydrochloric acid can dissolve completely with specific proportions, when main body acid solution and limestone formation are reacted and are made residual acid solution pH value raise, the chelant mix added with specific proportions will crystalline deposit be out from solution, the sequestrant solid particulate of separating out just can block the rock gap of high permeability interval or the hole of acid etching, thus acid solution is turned to.The sequestrant of separating out by acid solution afterwards or can return discharging liquid dilution dissolving, thus reaches the effect of fanout free region.Sequestrant can iron ion in Simultaneous Stabilization acidization and other likely produce other metallic cation of precipitation.
(1) solubleness test and resistance to flow test result show, with EDTA, HEDTA, DTPA, the solution that the carboxylic-acid sequestrants such as GLA are made into alone or by a certain percentage, alone or can as the chemical diverter of limestone acidifying after joining limestone acidifying main body acid solution.
(2) above-mentioned sequestrant or chelant mix dissolve in main body acid solution, but along with solution ph change (along with acid solution and limestone generation chemical reaction) meeting crystallization or precipitation from solution, the solid particulate of separating out will block limestone hole or wormhole, increase resistance to flow and acid solution is turned to.
(3) crystallization of separating out or solid particulate also can be dissolved in acid solution or water (dilution) again, thus avoid the injury turning to formation or wormhole.
(4) above-mentioned sequestrant or the mixture with turning function also can increase the dissolving power of main body acid solution to limestone, thus improve acidifying efficiency (unit acid fluid system can produce more wormholes and flow area), increase recovery ratio.
(5) there is the above-mentioned sequestrant of turning function or mixture or effectively Fe stabilizer, to avoid in acidization produce precipitation of iron ions and cause stratum or wormhole injury.
(6) there is the above-mentioned sequestrant of turning function or mixture also has effectively scale removal and anti-scaling function, to avoid in acidization produce polyvalent cation (as Ca
2+, Mg
2+, Ba
2+, Sr
2+, Al
3+, Fe
3+, Fe
2+, Ni
2+) run into related anion (as CO
3 2-, SO
4 2-, S
2-) precipitation fouling occurs and causes formation or wormhole injury.
Embodiment
The present invention is further detailed explanation to lift several specific embodiment below.
Embodiment one
By Na
3hEDTA and Na
2it is obtain the multi-functional self-diverting acid of the present invention in 15% hydrochloric acid soln that EDTA joins mass concentration in 40: 1 ratios.
Embodiment two
The solution obtained according to embodiment one proportioning is carried out following solubleness test:
1. be at room temperature, in the beaker of 15%HCl, add 8 grams of Na filling 20ml mass concentration
3hEDTA pressed powder, stirs with glass stick and dissolves rapidly, measure solution ph and record.
2. in above-mentioned solution, add 0.2 gram of Na again
2eDTA obtains initial soln by glass stick stirring and dissolving equally.
3. carry out titration and observe solution changing to above-mentioned solution with 20%NaOH solution.
4., if there is solid crystal to separate out, add 15% hydrochloric acid more in the mixture, or dilute with water, observe the change of solution.
5. above-mentioned experiment is repeated in 80 DEG C of (in water-bath) environment.
Experimental result is for seeing the following form: Na
3hEDTA and Na
2eDTA by a certain percentage (40: 1) joins in hydrochloric acid soln, along with the change (when being titrated to pH value 2-3 by NaOH solution) of solution ph, has solid particulate to separate out from solution.Afterwards by after hydrochloric acid soln or water dilution, solid crystal or precipitate are dissolved in solution again.This experimental result can repeat when 80 DEG C.
Embodiment three
The solution obtained according to embodiment two proportioning is carried out following resistance to flow test:
1. two liquid each 300 milliliter of preparation described in embodiment two, one is initial soln (15%HCl 20ml+8g Na
3hEDTA+0.2g Na
2eDTA), another is that initial soln is titrated to the solution of pH2-3 through 20%NaOH.
2. with polytetrafluoroethylraw raw material band, the syringe needle of needle tubing is sealed in order to avoid liquid flows out in needle tubing.
3. slowly pour 50 milliliters of initial solns into in needle tubing.Without injection plunger, needle tubing mouth is kept to open wide.
4. the needle tubing filling liquid is fixed on iron stand, and keeps vertical.
5. open syringe needle sealing, and timing at once, record the time after 50 milliliters of liquid flowings.
6. separately get each 200 milliliters of two liquid (is initial soln, and another is that initial soln is titrated to the solution of pH2-3 through 20%NaOH) prepared, join respectively in the sample cup of Fann35A.
7. measure the reading of two sample F ann35A 600rpm and record.
Resistance to flow test result sees the following form:
After adopting technique scheme, its beneficial effect is: two kinds of sequestrants join in main body hydrochloric acid can dissolve completely with specific proportions, when main body acid solution and limestone formation are reacted and are made residual acid solution pH value raise, the chelant mix added with specific proportions will crystalline deposit be out from solution, the sequestrant solid particulate of separating out just can block the rock gap of high permeability interval or the cavity of acid etching, thus acid solution is turned to.The sequestrant of separating out by acid solution afterwards or can return discharging liquid dilution dissolving, thus reaches the effect of fanout free region.Sequestrant can iron ion in Simultaneous Stabilization acidization and other likely produce the metallic cation of precipitation.
(1), solubleness is tested and resistance to flow test result shows, can as the chemical diverter of limestone acidifying after joining limestone acidifying main body acid solution with the solution that the carboxylic-acid sequestrants such as EDTA, HEDTA, DTPA, GLA are made into alone or by a certain percentage.
(2), above-mentioned sequestrant or chelant mix dissolve in main body acid solution, but along with solution ph change (along with acid solution and limestone generation chemical reaction) meeting crystallization or precipitation from solution, the solid particulate of separating out will block limestone hole or wormhole, increase resistance to flow and acid solution is turned to.
(3), the crystallization of separating out or solid particulate also can be dissolved in acid solution or water (dilution) again, thus avoids the injury turning to formation or wormhole.
(4), there is the above-mentioned sequestrant of turning function or mixture also can increase the dissolving power of main body acid solution to limestone, thus improve acidifying efficiency (unit acid fluid system can produce more wormholes and flow area), increase recovery ratio.
(5), there is the above-mentioned sequestrant of turning function or mixture or effectively Fe stabilizer, to avoid in acidization produce precipitation of iron ions and cause stratum or wormhole injury.
(6), there is the above-mentioned sequestrant of turning function or mixture also has effectively scale removal and anti-scaling function, to avoid in acidization produce polyvalent cation (as Ca
2+, Mg
2+, Ba
2+, Sr
2+, Al
3+, Fe
3+, Fe
2+, Ni
2+) run into related anion (as CO
3 2-, SO
4 2-, S
2-) precipitation fouling occurs and causes formation or wormhole injury.
Meanwhile, polyamine group carboxylic acid cpd EDTA or HEDTA in the present invention is replaced with DTPA or GLA, above-mentioned beneficial effect can be reached equally.
Above-described is only the preferred implementation of a kind of multi-functional self-diverting acid of the present invention; it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention; can also make some changes and improvements, these all belong to protection scope of the present invention.
Claims (1)
1. a multi-functional self-diverting acid, is characterized in that, described multi-functional self-diverting acid is 40: 1 formulated in proportion by the sodium salt of HEDTA and EDTA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110247626.9A CN102952536B (en) | 2011-08-26 | 2011-08-26 | Multifunctional self diverting acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110247626.9A CN102952536B (en) | 2011-08-26 | 2011-08-26 | Multifunctional self diverting acid |
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| Publication Number | Publication Date |
|---|---|
| CN102952536A CN102952536A (en) | 2013-03-06 |
| CN102952536B true CN102952536B (en) | 2014-12-17 |
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| CN201110247626.9A Active CN102952536B (en) | 2011-08-26 | 2011-08-26 | Multifunctional self diverting acid |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820098B (en) * | 2014-02-24 | 2016-01-20 | 中国石油大学(华东) | A kind of fanout free region self-diverting acid and preparation method thereof and application |
| CN103953324B (en) * | 2014-04-29 | 2016-08-31 | 惠建龙 | Polynary turn to acid adjustable slit height acidifying fracturing process |
| CN106928955A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of complexing cleaning liquid and its preparation method and application |
| CN109294551A (en) * | 2018-10-18 | 2019-02-01 | 顺泰能源科技发展有限公司 | A kind of cleaning low damage agent of molecular cluster and its application |
| CN116474672B (en) * | 2023-04-17 | 2024-02-23 | 东营东方化学工业有限公司 | Scale remover for steering acid system and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| US5059333A (en) * | 1990-07-26 | 1991-10-22 | Mobil Oil Corporation | Dissolution of sulfate scales |
| US5190656A (en) * | 1989-04-03 | 1993-03-02 | Mobil Oil Corporation | Method for removing scale via a liquid membrane in combination with an amino carboxylic acid and a catalyst |
| WO2008073233A2 (en) * | 2006-12-12 | 2008-06-19 | Rhodia Inc. | Scale squeeze treatment systems and methods |
| WO2009086954A1 (en) * | 2008-01-09 | 2009-07-16 | Akzo Nobel N.V. | Acidic aqueous solution containing a chelating agent and the use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6903054B2 (en) * | 2002-08-30 | 2005-06-07 | Schlumberger Technology Corporation | Reservoir treatment fluids |
-
2011
- 2011-08-26 CN CN201110247626.9A patent/CN102952536B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| US5190656A (en) * | 1989-04-03 | 1993-03-02 | Mobil Oil Corporation | Method for removing scale via a liquid membrane in combination with an amino carboxylic acid and a catalyst |
| US5059333A (en) * | 1990-07-26 | 1991-10-22 | Mobil Oil Corporation | Dissolution of sulfate scales |
| WO2008073233A2 (en) * | 2006-12-12 | 2008-06-19 | Rhodia Inc. | Scale squeeze treatment systems and methods |
| WO2009086954A1 (en) * | 2008-01-09 | 2009-07-16 | Akzo Nobel N.V. | Acidic aqueous solution containing a chelating agent and the use thereof |
| CN101918510A (en) * | 2008-01-09 | 2010-12-15 | 阿克佐诺贝尔股份有限公司 | Contain acidic aqueous solution of sequestrant and uses thereof |
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Effective date of registration: 20160718 Address after: 100000, room 8, floor 41, No. 812 East Fourth Ring Road, Beijing, Chaoyang District Patentee after: OPT PETROLEUM TECHNOLOGIES CO.,LTD. Address before: 100080 No. 19, No. 1, gate 601, No. 18, Xueyuan Road, Haidian District, Beijing Patentee before: Xiao Zhijun |
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Address after: 100000, room 8, floor 41, No. 812 East Fourth Ring Road, Beijing, Chaoyang District Patentee after: Beijing Petroleum Technology Limited by Share Ltd. Address before: 100000, room 8, floor 41, No. 812 East Fourth Ring Road, Beijing, Chaoyang District Patentee before: OPT PETROLEUM TECHNOLOGIES CO.,LTD. |
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Effective date of registration: 20180111 Address after: 257000 south two road, No. 1240, Shengli Industrial Park, Dongying, Shandong Patentee after: SHANDONG OUBOTE PETROLEUM ENGINEERING TECHNOLOGY Co.,Ltd. Address before: 100000, room 8, floor 41, No. 812 East Fourth Ring Road, Beijing, Chaoyang District Patentee before: Beijing Petroleum Technology Limited by Share Ltd. |
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Denomination of invention: A multifunctional self-steering acid Effective date of registration: 20220920 Granted publication date: 20141217 Pledgee: Dongying rural commercial bank Limited by Share Ltd. Dongcheng sub branch Pledgor: SHANDONG OUBOTE PETROLEUM ENGINEERING TECHNOLOGY Co.,Ltd. Registration number: Y2022980015516 |
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Date of cancellation: 20230907 Granted publication date: 20141217 Pledgee: Dongying rural commercial bank Limited by Share Ltd. Dongcheng sub branch Pledgor: SHANDONG OUBOTE PETROLEUM ENGINEERING TECHNOLOGY Co.,Ltd. Registration number: Y2022980015516 |
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Denomination of invention: A multifunctional self rotating acid Effective date of registration: 20230919 Granted publication date: 20141217 Pledgee: Dongying rural commercial bank Limited by Share Ltd. Dongcheng sub branch Pledgor: SHANDONG OUBOTE PETROLEUM ENGINEERING TECHNOLOGY Co.,Ltd. Registration number: Y2023980057557 |