CN106497540A - A kind of chemical formulation of the souring soln for improving coal seam permeability - Google Patents
A kind of chemical formulation of the souring soln for improving coal seam permeability Download PDFInfo
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- CN106497540A CN106497540A CN201610930776.2A CN201610930776A CN106497540A CN 106497540 A CN106497540 A CN 106497540A CN 201610930776 A CN201610930776 A CN 201610930776A CN 106497540 A CN106497540 A CN 106497540A
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- coal seam
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a kind of chemical formulation of the souring soln for improving coal seam permeability, is made up of by weight percentage following component：Hydrochloric acid 12%～15%, hydrofluoric acid 2%～2.5%, acidifying retardant 2.5%～3%, acidification corrosion inhibitor 1.5%～1.8%, ferrous stability 0.3%～0.5, expansion-resisting agent 2%～2.2%, balance of water.Present invention achieves chemical method improves coal seam permeability, mainly for mineralogical compositions such as the calcite contained by coal seam, dolomite, silicate, after these mineralogical compositions are acidified solution dissolving, flow out from coal seam with souring soln, increased the connectedness in the crack and crack in coal seam, the permeability in coal seam is increased, so as to improve the extracting result of coal bed gas (mine gas).
Description
Technical field
The present invention relates to coal bed gas (mine gas) field and Chemical activator field, in particular it relates to a kind of improve coal seam
The chemical formulation of the souring soln of permeability.
Background technology
Coal seam permeability directly decides the extracting result of coal bed gas (mine gas), due to the universal permeability in China coal seam
Difference, as the increase of China's coal-mine mining depth, mining conditions more they tend to complexity, occurs in that high-ground stress, high methane, Gao Feijun
Matter, hypotonicity, low intensive coal body feature, the initial fissure and porosity of coal body are tapered into, the permeability in coal seam with
Reduction.The effective coverage of single extraction borehole is little, and pre-draining borehole quantities is big, and extraction efficiency is low, conventional coal bed gas (ore deposit
Well gas) pumping method is difficult to play a role, and gas explosion and the threat of Gas Outburst are also increasingly severe, the low shadow of extraction concentration
The utilization of coal bed gas (mine gas) is rung.Permeability is low have become the key of restriction coal bed gas (mine gas) extraction because
Element, improves coal seam permeability, is the fundamental way of China's Achievements of Gas Control and the utilization of resources.
For the rare problem of low permeability coal seam down-hole coal bed gas (mine gas) extraction, China's coal-mine researcher is adopted
Hydraulic fracturing, hydraulic flushing in hole, counter-boring techniques, hydraulic slotted liner technique, N2Foam fracturing, CO2The physical methods such as foam fracturing are carried out to coal seam
Transformation, changes the flow conductivity in coal seam, consumes substantial amounts of human and material resources, financial resources, achieve some effects in the area having,
But it is not satisfactory in some regional correctional effects.
Content of the invention
For deficiencies of the prior art, the invention provides a kind of souring soln for improving coal seam permeability
Chemical formulation, mainly for the mineralogical compositions such as the calcite contained by coal, dolomite, silicate, these mineralogical composition quilts
After souring soln dissolving, flow out from coal seam with souring soln, increased the connectedness in the crack and crack in coal seam, increased
The permeability in coal seam, so that improve the extracting result of coal bed gas (mine gas).
In order to solve above-mentioned technical problem, following technical scheme is present invention employs：
A kind of chemical formulation of the souring soln for improving coal seam permeability, is made up of by weight percentage following component：
Used as a preferred embodiment of the present invention, the acidifying retardant is that BZ-51 is acidified retardant.
Used as another kind of preferred version of the present invention, the acidification corrosion inhibitor is ALS-2 acidification corrosion inhibitors.
Used as a modification of the present invention scheme, the ferrous stability is IRON-2066A ferrous stabilities.
Used as another kind of improvement project of the present invention, the expansion-resisting agent is ammonium chloride.
Compared with prior art, the present invention has the following technical effect that：
1st, the present invention dissolves carbonate mineral composition using hydrochloric acid as main acid, effectively, and keeps in coal seam
Relatively low pH value, can suppress ferric hydroxide precipitate to generate；Hydrofluoric acid is as a kind of auxiliary acid, contained in coal seam for dissolving
Silicates mineralogical composition；Acidifying retardant is simultaneously introduced, has been adsorbed in coal surface by retardant, is slowed down acid solution and coal
The reaction of layer surface, and retardant can also suppress H+Mass transfer velocity, extend acid and reaction time in coal seam, so as to increase acid
With the EFFECTIVE RANGE of coal seam reaction, deep acidizing purpose is reached.
2nd, a kind of chemical method is provided for improving coal seam permeability, in the physical method such as hydraulic fracturing coal seam, antireflective effect is not
In the case of significantly, using chemical method realize on a large scale, remote depth is anti-reflection.
Specific embodiment
A kind of chemical formulation of the souring soln for improving coal seam permeability, is made up of by weight percentage following component：
Wherein, acidifying retardant is that BZ-51 is acidified retardant；Acidification corrosion inhibitor is ALS-2 acidification corrosion inhibitors；Iron ion is steady
Agent is determined for IRON-2066A ferrous stabilities；Expansion-resisting agent is ammonium chloride.The present invention, is mainly dissolved as main acid using hydrochloric acid
In coal seam, contained calcite, dolomite etc. contain carbonate mineral matter.Hydrofluoric acid mainly dissolves coal as main auxiliary acid
The silicates mineral matter such as contained quartz in layer.Acidifying retardant reduces acidification reaction speed, improves acidification distance；
Acidification corrosion inhibitor reduces acid solution to storage and the corrosion of shipping container.Solution pH value rising is carried out with reacted, iron ion is steady
Determine agent free iron is prevented with Fe (OH)3Form is precipitated, and causes secondary pollution.Expansion-resisting agent is prevented with the carrying out of reaction
Mineralogical composition expands.
1. coal dust corrosion rate determination experiment
From Qian Jiaying coal samples, the coal dust that coal sample is ground to form 80 mesh weighs each 3g of 4 parts of coal dusts, precision with assay balance
For 0.001g.
Coal dust and acid solution are poured in glass cylinder by a certain percentage, is heated in the water bath with thermostatic control platform for placing into 60 DEG C
Reaction.
After reaction reaches scheduled time 3h, graduated cylinder is taken out from water bath with thermostatic control platform, filtered remaining coal dust and filter
Paper is put in drying box, until constant weight.
According to the mass change of coal dust before and after acidifying, corrosion rate of each acid solution to coal dust is calculated, it is suitable to determine
Acid solution mass fraction.
The computing formula of corrosion rate K：
In formula：m1Quality of pc before acidifying, g；
m2Quality of pc after acidifying, g.
Embodiment 1
It is configured to using hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water
Solution.In solution, each component percentage by weight is：Hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability,
Expansion-resisting agent is respectively 9%, 2%, 2.5%, 1.5%, 0.3%, 2%；Balance of water.Acid solution is slowly mixed together at room temperature, is shaken
Even standing.
Embodiment 2
It is configured to using hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water
Solution.In solution, each component percentage by weight is：Hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability,
Expansion-resisting agent is respectively 12%, 2%, 2.5%, 1.5%, 0.3%, 2%；Balance of water.Acid solution is slowly mixed together at room temperature, is shaken
Even standing.
Embodiment 3
It is configured to using hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water
Solution.In solution, each component percentage by weight is：Hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability,
Expansion-resisting agent is respectively 15%, 2%, 2.5%, 1.5%, 0.3%, 2%；Balance of water.Acid solution is slowly mixed together at room temperature, is shaken
Even standing.
Embodiment 4
It is configured to using hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water
Solution.In solution, each component percentage by weight is：Hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability,
Expansion-resisting agent is respectively 18%, 2%, 2.5%, 1.5%, 0.3%, 2%；Balance of water.Acid solution is slowly mixed together at room temperature, is shaken
Even standing.
The corrosion experimental result of the acidifying of table 1
Experiment proves that the solution system has preferable corrosion rate to coal dust, and acidizing effect is good, can meet raising coal seam and ooze
The requirement of rate thoroughly.
2. permeability contrast experiment before and after acidification reaction
Select coal seam of the thickness uniformly without obvious crack to be sampled in down-hole, by coal sample sealing preserve, be transported to experiment
Indoor.
Coal sample is made the coal cinder that thickness is 10cm using rock cutter.
The coal sample that coal sample is made the high 10cm of standard, diameter 5cm using frequency-changing vertical corning machine.
The original permeability that 1# coal samples are determined using permeability determination device.
It is configured to using hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water
Solution.In solution, each component percentage by weight is：Hydrochloric acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability,
Expansion-resisting agent is respectively 15%, 2%, 2.5%, 1.5%, 0.3%, 2%；Balance of water.
By 2#, 3#, 4#, 5# coal sample be respectively placed in percentage by weight for 9%, 12%, 15% and 18% hydrochloric acid be main acid,
In the mixed solution that hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water are configured to, will burn
Cup sealing, is put in 25 DEG C of insulating box, is acidified 3 hours.
By 6#, 7#, 8#, 9# coal sample be respectively placed in percentage by weight for 9%, 12%, 15% and 18% hydrochloric acid be main acid,
In the mixed solution that hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water are configured to, will burn
Cup sealing, is put in 25 DEG C of insulating box, is acidified 6 hours.
10#, 11#, 12#, 13# coal sample is respectively placed in percentage by weight for based on 9%, 12%, 15% and 18% hydrochloric acid
The mixed solution that body acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water are configured to
In, beaker is sealed, is put in 25 DEG C of insulating box, be acidified 9 hours.
14#, 15#, 16#, 17# coal sample is respectively placed in percentage by weight for based on 9%, 12%, 15% and 18% hydrochloric acid
The mixed solution that body acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water are configured to
In, beaker is sealed, is put in 25 DEG C of insulating box, be acidified 12 hours.
18#, 19#, 20#, 21# coal sample is respectively placed in percentage by weight for based on 9%, 12%, 15% and 18% hydrochloric acid
The mixed solution that body acid, hydrofluoric acid, acidifying retardant, acidification corrosion inhibitor, ferrous stability, expansion-resisting agent and water are configured to
In, beaker is sealed, is put in 25 DEG C of insulating box, be acidified 18 hours.
The permeability that 2#～21# coal samples are determined respectively using permeability determination device, contrasts the hydrochloric acid of variable concentrations
(HCL), under different acidificatoin time effects, coal sample permeability variation.
Coal sample must be chosen in same place, and keeps the integrality of coal sample.
Experiment must be completed under steady temperature indoors.
Hydrochloric acid (HCL), hydrofluoric acid (HF) are respectively provided with corrosivity, notably protected working in experimentation, prevent from splashing wound.
Acidifying permeability improvement device in simulation coal seam includes：Rock cutter, frequency-changing vertical corning machine, hydrochloric acid (HCL), hydrofluoric acid
(HF), ammonium chloride (NH4CL), distilled water, beaker, hermetic bag, insulating box, drying baker, permeability determination device.
Permeability determination experimental result unit before and after the acidifying of table 2：mD
The results show, acidifying are conducive to improving coal seam permeability, and acidizing recipe can realize carrying for coal seam permeability
High.
Finally illustrate, above example is only unrestricted in order to technical scheme to be described, although with reference to compared with
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, and without deviating from the objective and scope of technical solution of the present invention, which all should be covered at this
In the middle of the right of invention.
Claims (5)
1. a kind of improve coal seam permeability souring soln chemical formulation, it is characterised in that by following component percentage by weight
Than composition：
2. a kind of chemical formulation of the souring soln of the raising coal seam permeability according to claim 1, it is characterised in that institute
It is that BZ-51 is acidified retardant to state acidifying retardant.
3. a kind of chemical formulation of the souring soln of the raising coal seam permeability according to claim 1, it is characterised in that institute
Acidification corrosion inhibitor is stated for ALS-2 acidification corrosion inhibitors.
4. a kind of chemical formulation of the souring soln of the raising coal seam permeability according to claim 1, it is characterised in that institute
Ferrous stability is stated for IRON-2066A ferrous stabilities.
5. a kind of chemical formulation of the souring soln of the raising coal seam permeability according to claim 1, it is characterised in that institute
Expansion-resisting agent is stated for ammonium chloride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610930776.2A CN106497540A (en) | 2016-10-31 | 2016-10-31 | A kind of chemical formulation of the souring soln for improving coal seam permeability |
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| CN201610930776.2A CN106497540A (en) | 2016-10-31 | 2016-10-31 | A kind of chemical formulation of the souring soln for improving coal seam permeability |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810687A (en) * | 2019-03-01 | 2019-05-28 | 中国地质大学（武汉） | A kind of environment-friendly type acidification working solution suitable for the volume increase of hypotonic coalbed methane reservoir |
| CN113863915A (en) * | 2021-10-15 | 2021-12-31 | 中国华能集团有限公司 | System and method for improving physical properties of low-permeability structural coal reservoir by utilizing acidification technology |
Citations (2)
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| CN103436247A (en) * | 2013-08-23 | 2013-12-11 | 中国石油大学(华东) | Retarded-acid acidizing fluid |
| CN105295886A (en) * | 2014-08-01 | 2016-02-03 | 中国石油天然气股份有限公司 | Composite retarded acid |
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2016
- 2016-10-31 CN CN201610930776.2A patent/CN106497540A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103436247A (en) * | 2013-08-23 | 2013-12-11 | 中国石油大学(华东) | Retarded-acid acidizing fluid |
| CN105295886A (en) * | 2014-08-01 | 2016-02-03 | 中国石油天然气股份有限公司 | Composite retarded acid |
Non-Patent Citations (1)
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| 李瑞等: "提高煤岩渗透性的酸化处理室内研究", 《煤炭学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810687A (en) * | 2019-03-01 | 2019-05-28 | 中国地质大学（武汉） | A kind of environment-friendly type acidification working solution suitable for the volume increase of hypotonic coalbed methane reservoir |
| CN109810687B (en) * | 2019-03-01 | 2020-11-27 | 中国地质大学（武汉） | Environment-friendly acidizing working fluid suitable for increasing yield of low-permeability coal bed gas reservoir |
| CN113863915A (en) * | 2021-10-15 | 2021-12-31 | 中国华能集团有限公司 | System and method for improving physical properties of low-permeability structural coal reservoir by utilizing acidification technology |
| CN113863915B (en) * | 2021-10-15 | 2024-01-19 | 中国华能集团有限公司 | System and method for improving physical properties of low-permeability structural coal reservoir by using acidification technology |
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