CN106433605A - Oil shale in-situ porosity-increasing activating treating agent and preparation method thereof - Google Patents
Oil shale in-situ porosity-increasing activating treating agent and preparation method thereof Download PDFInfo
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- CN106433605A CN106433605A CN201510472598.9A CN201510472598A CN106433605A CN 106433605 A CN106433605 A CN 106433605A CN 201510472598 A CN201510472598 A CN 201510472598A CN 106433605 A CN106433605 A CN 106433605A
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- acid
- oil shale
- inorganic agent
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- nickel
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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
- C09K2208/32—Anticorrosion additives
Abstract
The invention belongs to the field of oil shale in-situ mining, and provides an oil shale in-situ porosity-increasing activating treating agent and a preparation method thereof, wherein the raw materials of the treating agent comprise, by mass, 5-28% of an acid, 0.1-1% of a cobalt salt and/or nickel salt, 1-3% of a corrosion inhibitor, 0.1-20% of a mutual solvent, and 6.2-52% of water. The invention further provides the preparation method of the treating agent, wherein the preparation method comprises: adding the acid, the cobalt salt and/or nickel salt, the corrosion inhibitor and the mutual solvent into the water, and stirring to obtain the treating agent. According to the present invention, the treating agent integrates the oil shale in-situ porosity increasing, the permeability increasing and the in-situ thermal conversion catalysis synergism, such that the porosity of the oil shale can be increased, and the oil yield of the oil shale can be increased at the same temperature under the same time; and the preparation method is simple, the treating agent can be prepared in the liquid preparing station or can be directly prepared in site, and the use is easy.
Description
Technical field
The invention belongs to oil shale in-situ exploitation field is and in particular to a kind of oil shale in-situ increases hole activating treatment agent,
And the preparation method of this inorganic agent.
Background technology
Oil shale takes over one of energy as the important of conventional gas and oil, and its exploitation are increasingly subject to the world each
The attention of state.According to statistics, current world oil shale oil stock number is about 411,000,000,000 tons, and China's shale oil money
Source is about 476.44 hundred million tons, and the ranking whole world second is only second to the U.S..China's oil shale resources bury relatively deep, oil
Shale average thickness is about 20-30m, and accompanies sandstone, mud stone etc. more, and quite a few is oil content
Lean ore (accounting for 45.4%) less than 5%, and oil content is more than 10% rich ore less (17.6%), between 5%-10%
The resource of oil content accounts for 37%.
The mining type of oil shale can be divided into ground dry distilling and two kinds of in-situ retorting, although ground dry distilling has technique
Ripe, heating cycle is short, investment instant effect the advantages of, but environmental pollution is extremely serious, considerable damage soil,
Residue treatment wastes substantial amounts of water resource again, water quality and air is also resulted in very big pollution simultaneously, after exploitation terminates
Also need to carry out backfilling working.With the increase of environmental protection pressure, oil shale in-situ exploitation has become following oil shale business
The inexorable trend of industry large-scale development.
Each abroad major oil companies with shell as representative have carried out substantial amounts of grinding in terms of oil shale in-situ exploitation
Study carefully.Shell adopts electrical heating ICP (In-situ Conversion Process) technology in the area success of the U.S. green river
Produce shale oil, but electric-heating technology firing rate is slow, heating cycle is long, generally requires 2-4, need to disappear
Consume substantial amounts of electric energy.Because not having the supplement of outside energy, tar productivity is relatively low to lead to deficiency in economic performance.
Fluid heating technique is because firing rate is fast, heating cycle is short, the advantages of can make full use of carbonization gas and wide
General concern.But oil shale porosity is low, and permeability is extremely low, hot fluid cannot inject rock stratum it is necessary to carry out early stage
Reservoir reconstruction is so as to have certain permeability.Common concern at present is fracturing and explosion fracturing technology,
But the crack that fracturing is formed may lead to inject the direct channelling of fluid to producing well so that the thermal efficiency is low, greatly
Part rock stratum cannot be heated to kerogen cracking temperature (more than 350 DEG C).Although explosion fracturing can be in nearly well week
Enclose formation multiple cracking, but process range is little, and the surface area phase contacting with oil shale that crack provides to hot fluid
To less, oil shale heating surface area is little, and firing rate is relatively low, and oil shale in-situ conversion rate is slow, efficiency
Low.
In order to increase oil shale heating surface area in oil shale in-situ heating recovery process, improve the oil shale efficiency of heating surface,
Oil shale formation can be carried out increasing the process such as hole, activation.But oil shale is entered in domestic prior art at present
The process of row is substantially all and is confined in oil shale retort process, oil shale particle to be carried out to be catalyzed etc.
Reason, thus improving quality and the yield of oil shale oil product, not referring to and injecting any material to oil shale in situ
Reservoir carries out increasing hole, activation or catalysis etc..Abroad in a small amount of patent (as patent AU2011348120,
US8727000 etc.) mention and the reactant liquor containing oxidant, organic solvent etc. can be injected in oil shale formation,
So that it is contacted with subterranean oil shale, and react, so that kerogen is separated from oil shale, but at present not
See that injection increases the relevant report of the inorganic agent of hole and activation for oil shale in-situ.
Content of the invention
The present invention provides a kind of oil shale in-situ to increase hole, activating treatment agent.By will be compounding for each group division reason, right
Oil shale carries out increasing hole in situ, improves its permeability, changes the reaction path of kerogen pyrolytic process simultaneously, plus
Fast conversion rate, reduces the purpose of thermal energy consumption, improve production efficiency and oil productivity.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows：
A kind of oil shale in-situ increases hole activating treatment agent, the inclusion based on weight/mass percentage composition of its raw material：Sour 5%-28%,
Cobalt salt and/or nickel salt 0.1%-1%, corrosion inhibiter 1%-3%, mutual solvent 0.1%-20%, water 6.2%-52%.
In a particular embodiment of the present invention, its raw material is calculated as by weight/mass percentage composition：Sour 5%-28%, cobalt salt
And/or nickel salt 0.1%-1%, corrosion inhibiter 1%-3%, mutual solvent 0.1%-20%, remaining is water.
In a particular embodiment of the present invention, described acid selected from hydrochloric acid, Fluohydric acid., phosphoric acid, sulphuric acid, nitric acid,
At least one in fluoboric acid, hexafluosilicic acid, formic acid and acetic acid, act as oil shale layer being corroded and reaming.
Two or more acid is applied in combination effect more preferably, preferably combination includes the combining of hydrochloric acid and Fluohydric acid., hydrochloric acid and
The combining of the combination of fluoboric acid, the combining of hydrochloric acid and hexafluosilicic acid, hydrochloric acid and Fluohydric acid. and acetic acid." matter is pressed in acid
Amount percentage composition is calculated as 5%-28% " it is meant that weight/mass percentage composition in inorganic agent for the pure solute, example hydrochloric acid
For 5%-28%, content refers to that weight/mass percentage composition in inorganic agent for the hydrogen chloride is 5%-28%.Each acid is equal above
For the industrial chemically pure reagent that can buy, and there is known concentration.
In a particular embodiment of the present invention, described cobalt salt is selected from cobaltous sulfate, cobaltous chloride, cobalt carbonate, cobaltous formate
With at least one in cobalt acetate, described nickel salt is in Nickel dichloride., nickel sulfide, nickel sulfate and nickel sulfamic acid
At least one.The acting as of described cobalt salt and/or nickel salt, as catalyst in increasing hole and activation process, promotes
Organic matter decomposition in oil shale layer.
In a particular embodiment of the present invention, described corrosion inhibiter is selected from formaldehyde, o-xylene thiourea, alkyl sulfonic acid
At least one in sodium and zephiran chloride pyridine, act as making the increasing hole of oil shale and activation process steadily occur,
Mitigate the corrosion to metal pipe material for the acid.
In a particular embodiment of the present invention, the formula of described mutual solvent is：R-O-(-CH2CH2O-)n-H.Formula
In, R is C1-C8Alkyl, preferably C1-C8Alkyl, more preferably C1-C4Alkyl；N is 0-4
Integer.Described mutual solvent is preferably selected from methanol, and (R is C1, n be 0), ethanol (R be C2, n is 0),
(R is C to propanol3, n be 0), butyl glycol ether (R be C4, n is 1), (R is diethylene glycol ether
C2, n be 2), butyl (R be C4, n be 2) and triethylene glycol butyl ether (R be C4, n is 3)
In at least one, act as making the oil-wetted surface in aqueous phase base fluid and oil shale layer and organic matter therein to fill
Tap is touched.
Present invention also offers the preparation method of above-mentioned inorganic agent, including by described acid, cobalt salt and/or nickel salt, slow
Erosion agent and mutual solvent are added to the water stirring and obtain.
In a particular embodiment of the present invention, methods described includes adding in partly or entirely desired amount of water
Acid, cobalt salt and/or nickel salt, corrosion inhibiter and mutual solvent, stirring while adding, if necessary, then plus remaining water extremely
Design quantity, obtains described inorganic agent after stirring.Preferably first above-mentioned raw materials are dissolved in and account for total Water 2/3～4/5
Water in, add remaining water after being sufficiently stirred for, make dissolving more abundant.
The oil shale in-situ that the present invention provides increases hole activating treatment agent, and oil shale in-situ is increased hole, improves permeability
With in-situ heat conversion catalyst potentiation integration, oil shale porosity can be increased, in identical temperature and time condition
Under make oil shale oil-collecting ratio increase.And described inorganic agent preparation method is simple, can prepare in make-up station, also can be
Scene is directly prepared, easy to use.
Specific embodiment
Further describe the present invention below by embodiment.
Embodiment 1
A kind of oil shale in-situ increases hole activating treatment agent, and its raw material is by mass percentage：Hydrochloric acid 12%, hydrogen
Fluoric acid 1.5%, cobaltous chloride 0.1%, formaldehyde 1%, butyl glycol ether 12.4%, water 73%.Its preparation method is：
Calculate needed raw material consumption according to formula concentration, first measure clear water 30.00 weight portion, be slowly added to in clear water
Industrial hydrofluoric acid 3.75 weight that technical hydrochloric acid 33.33 weight portion that mass concentration is 36%, mass concentration are 40%
Amount part, butyl glycol ether 12.40 weight portion, mass concentration are 37% industrial formol 2.70 weight portion, six water
Cobaltous chloride 0.18 weight portion, stirring while adding, add clear water 17.64 weight portion after solid all dissolves,
Described inorganic agent is obtained after stirring.
Embodiment 2
A kind of oil shale in-situ increases hole activating treatment agent, and its raw material is by mass percentage：Fluohydric acid. 5%,
Acetic acid 15%, cobalt acetate 1%, formaldehyde 2%, butyl glycol ether 6%, water 71%.Its preparation method is：Press
Calculate needed raw material consumption according to formula concentration, first measure clear water 40 weight portion, in clear water, be slowly added to quality
Glacial acetic acid 15.31 weight portion that industrial hydrofluoric acid 12.50 weight portion that concentration is 40%, mass concentration are 98%,
Ethylene glycol monobutyl ether 6.00 weight portion, mass concentration are 37% industrial formol 5.41 weight portion, four hydration second
Sour cobalt 1.41 weight portion, stirring while adding, add clear water 19.37 weight portion after solid all dissolves, stir
Described inorganic agent is obtained after mixing uniformly.
Embodiment 3
A kind of oil shale in-situ increases hole, activating treatment agent, and its raw material is by mass percentage：Hydrochloric acid 12%,
Fluohydric acid. 3%, acetic acid 10%, nickel sulfamic acid 0.5%, formaldehyde 3%, ethanol 18%, water 53.5%.Its
Preparation method is：Calculate needed raw material consumption according to formula concentration, measure clear water 22.22 weight portion, to clear water
In be slowly added to the industrial hydrogen that technical hydrochloric acid 33.33 weight portion, mass concentration that mass concentration is 36% is 40%
Fluoric acid 7.5 weight portion, mass concentration be 98% glacial acetic acid 10.20 weight portion, ethanol 18.00 weight portion, matter
Amount concentration is 37% industrial formol 8.11 weight portion, four hydration nickel sulfamic acid 0.64 weight portions, side edged
Stirring, treats that solid all dissolves, obtains described inorganic agent after stirring.
Inorganic agent performance test process is as follows：Take the oil shale particle sample 30g that particle size range is 3.35-4.75mm,
Add the inorganic agent 100g of embodiment 1-3 preparation, react 2 hours under 40 DEG C of environment；Place is poured out after having reacted
Reason agent, with clear water wash oil shale samples, sample is placed in 105 DEG C of baking ovens and is dried 4 hours；Test oil page
Porosity under normal temperature and pressure conditionses for the rock sample product, and under the conditions of 350 DEG C heating 15 hours after oil-collecting ratio.
Result is as shown in table 1.
Comparative example 1
The oil shale particle sample 30g taking particle size range to be 3.35-4.75mm, sample is placed in 105 DEG C of baking ovens
It is dried 4 hours, porosity under normal temperature and pressure conditionses for the test oil shale samples, and under the conditions of 350 DEG C
Oil-collecting ratio after heating 15 hours.Result is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Porosity (%) | 28 | 29 | 29 | 15 |
| Oil-collecting ratio (%) | 37 | 39 | 40 | 29 |
As shown in Table 1, under the conditions of acid extraction identical, embodiment 1-3 is compared with comparative example, oil
Shale porosity increases, and oil-collecting ratio significantly improves.Show that the inorganic agent of the present invention can carry out increasing hole and change to oil shale
Make, improve permeability, accelerate oil shale thermal transition speed simultaneously, realize catalysis potentiation.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention, the present invention is carried out
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, and on the contrary, the present invention can be extended to other and all has identical function
Methods and applications.
Claims (10)
1. a kind of oil shale in-situ increases hole activating treatment agent, the inclusion based on weight/mass percentage composition of its raw material：Acid
5%-28%, cobalt salt and/or nickel salt 0.1%-1%, corrosion inhibiter 1%-3%, mutual solvent 0.1%-20%, water 6.2%-52%.
2. inorganic agent according to claim 1 it is characterised in that described acid selected from hydrochloric acid, Fluohydric acid.,
At least one in phosphoric acid, sulphuric acid, nitric acid, fluoboric acid, hexafluosilicic acid, formic acid and acetic acid.
3. inorganic agent according to claim 1 and 2 it is characterised in that described cobalt salt be selected from cobaltous sulfate,
At least one in cobaltous chloride, cobalt carbonate, cobaltous formate and cobalt acetate.
4. inorganic agent according to any one of claim 1 to 3 is it is characterised in that described nickel salt is selected from
At least one in Nickel dichloride., nickel sulfide, nickel sulfate and nickel sulfamic acid.
5. inorganic agent according to any one of claim 1 to 4 is it is characterised in that described corrosion inhibiter selects
At least one from formaldehyde, o-xylene thiourea, sodium alkyl sulfonate and zephiran chloride pyridine.
6. inorganic agent according to any one of claim 1 to 5 is it is characterised in that described mutual solvent
Formula is R-O- (- CH2CH2O-)n- H, wherein R are C1-C8Alkyl, preferably C1-C8Alkyl, more
It is preferably C1-C4Alkyl；N is the integer of 0-4.
7. inorganic agent according to claim 6 it is characterised in that described mutual solvent be selected from methanol, ethanol,
At least one in propanol, butyl glycol ether, diethylene glycol ether, butyl and triethylene glycol butyl ether.
8. a kind of method preparing inorganic agent according to any one of claim 1 to 7, including by described acid,
Cobalt salt and/or nickel salt, corrosion inhibiter and mutual solvent are added to the water stirring and obtain.
9. method according to claim 8 it is characterised in that by described acid, cobalt salt and/or nickel salt,
Corrosion inhibiter and mutual solvent are first dissolved in the water account for total Water 2/3～4/5, add remaining water after stirring.
10. the inorganic agent any one of claim 1 to 7 increases the application in the activation of hole in oil shale in-situ.
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| CN201510472598.9A CN106433605B (en) | 2015-08-04 | 2015-08-04 | A kind of oil shale in-situ increases hole activating treatment agent and preparation method thereof |
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| CN201510472598.9A CN106433605B (en) | 2015-08-04 | 2015-08-04 | A kind of oil shale in-situ increases hole activating treatment agent and preparation method thereof |
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| CN106433605B CN106433605B (en) | 2019-04-02 |
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Citations (4)
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|---|---|---|---|---|
| US20120160486A1 (en) * | 2010-12-22 | 2012-06-28 | Chevron U.S.A. Inc. | In-situ kerogen conversion and recovery |
| CN102643636A (en) * | 2012-04-10 | 2012-08-22 | 中国海洋石油总公司 | Auxiliary enhancement chemical agent for oil extraction with heat |
| CN103421483A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Nano catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof |
| CN103464179A (en) * | 2013-09-24 | 2013-12-25 | 吉林大学 | Catalyst used for extracting shale oil from oil shale and application method of catalyst |
-
2015
- 2015-08-04 CN CN201510472598.9A patent/CN106433605B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120160486A1 (en) * | 2010-12-22 | 2012-06-28 | Chevron U.S.A. Inc. | In-situ kerogen conversion and recovery |
| CN102643636A (en) * | 2012-04-10 | 2012-08-22 | 中国海洋石油总公司 | Auxiliary enhancement chemical agent for oil extraction with heat |
| CN103421483A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Nano catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof |
| CN103464179A (en) * | 2013-09-24 | 2013-12-25 | 吉林大学 | Catalyst used for extracting shale oil from oil shale and application method of catalyst |
Non-Patent Citations (4)
| Title |
|---|
| A AL-HARAHSHEH: "Effect of demineralization of El-lajjun Jordanian oil shale on oil yield", 《FUEL PROCESSING TECHNOLOGY》 * |
| ABOULKAS: "Effects of acid treatments on Moroccan Tarfaya oil shale and pyrolysis of oil shale and their kerogen", 《燃料化学学报》 * |
| 张永强: "提高油页岩中页岩油提取率方法研究", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
| 盖蓉华: "矿物质对油页岩热解行为的影响", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
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