CN109626768A - Oil-gas field drilling mud chip curing agent and application thereof - Google Patents
Oil-gas field drilling mud chip curing agent and application thereof Download PDFInfo
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- CN109626768A CN109626768A CN201811585808.5A CN201811585808A CN109626768A CN 109626768 A CN109626768 A CN 109626768A CN 201811585808 A CN201811585808 A CN 201811585808A CN 109626768 A CN109626768 A CN 109626768A
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- medicament
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
Abstract
The invention discloses an oil-gas field drilling mud chip curing agent and application thereof. The oil-gas field drilling mud chip curing agent comprises a curing agent consisting of HAS, steel slag powder and quick lime; the agent is used for curing and stabilizing drilling mud, toxic and harmful components in the mud can be encapsulated in a curing body, and the mobility of the toxic and harmful substances is reduced, so that the toxic and harmful substances meet the pollution control standard of hazardous waste landfill (GB 18598-2001), and are safely buried.
Description
Technical field
The present invention relates to a kind of oilfield drilling spare solidification medicament and its application, has and be related to one kind by HAS, steel-making slag powder
Solidify method of the medicament for efficient curing process oilfield drilling spare with the compositions such as quick lime, belongs to oil exploitation pollution
Object processing technology field.
Background technique
Shale gas is used as a kind of more cleaning, low-carbon, efficient fuel by a large amount of exploitation, but shale gas is being exploited
A series of environmental problem can be caused in the process, such as the drilling well generated in the water pollution of hydraulic fracturing bring and drilling process
Waste liquid, is mainly characterized by that COD is difficult to degrade, heavy metal concentration is high, turbidity is high, coloration is big, seriously polluted surface water and underground
Aquifer；The a large amount of landwaste sludge generated simultaneously, the heavy metal containing high concentration and various surfactants, to periphery ecology ring
It exerts heavy pressures in border.
With going deep into for exploitation of oil-gas field, the yield of waste liquid of drilling and spare is high year by year.According to incompletely statistics, it bores flatly
The waste liquid of drilling about 300m that the oil/gas well of deep 3000~4000m generates3, China has the oil gas field of such drilling depth very
It is more, and with the maturation of drilling technology, drilling depth is gradually deepened.This will bring a large amount of waste liquid of drilling.It is annual to generate
Waste liquid of drilling and spare it is increasing with a huge radix, the reason is that annual China has many oil gas fields to be produced,
If the estimated sum of 2015 older celebrating oil gas fields is up to 3000 mouthfuls of drilling wells, triumph oil gas field has put into 68 oil gas fields of exploitation.These are bored
If well waste liquid and spare are allowed to discharge, tremendous influence will be caused to ecological environment, while can also restrict enterprise development.
The processing technique method of waste liquid of drilling and spare is more, on the basis of with reference to domestic and foreign literature data, summarizes
Common several waste liquid of drilling methods of disposal: method, recycling and reusing method, chemical strengthening solid-liquid is recycled in decentralized processing
Partition method, cost is relatively low for first three, easy to operate, but there is a problem of identical: not being pollutant final disposal method and right
Equipment requirement is higher.Although separately having the influence of re-injection method, biological treatment, seal in a pit to environment smaller, expense is high；
There are also the methods that incineration method, seal in a pit and salt cave French are commonly used for processing spare, but processing cost is expensive.Therefore, anxious
A kind of pair of processing method that oilfield drilling liquid waste processing effect is good and cost performance is high need to be found.
Summary of the invention
For oilfield drilling spare processing method in the prior art, the first purpose of this invention
Be be to provide it is a kind of be simple and efficient, flexibly can be realized the low cost to oilfield drilling spare, innoxious governance is consolidated
Chemical drug agent.
Second object of the present invention is to be to provide a kind of oilfield drilling spare solidification medicament at efficient, inexpensive place
Manage the application in oilfield drilling spare.
In order to achieve the above technical purposes, the present invention provides a kind of oilfield drilling spares to solidify medicament comprising by
The curing agent of HAS, steel-making slag powder and quick lime composition.
Preferred scheme, the curing agent are made of following content of component: 65~80 parts of HAS；Steel-making slag powder 15~21
Part；5~7 parts of quick lime.
Preferred scheme, the oilfield drilling spare solidification medicament further includes molysite and normal sand.
Preferred scheme, the normal sand quality are the 12.5~50% of curing agent quality.
More preferably scheme, dioxide-containing silica > 96wt% of the normal sand, clay content are less than 0.2wt%, loss on ignition
Less than 0.04wt%, particle size range is 0.08~2mm.
More preferably scheme, the quality of the molysite are the 10~30% of curing agent quality.
More preferably scheme, the molysite are iron chloride.
The present invention also provides the applications that a kind of oilfield drilling spare solidifies medicament, and it is solid to be used for oilfield drilling spare
Change processing.
Preferred scheme by drilling well spare and solidifies medicament and water after mixing evenly, stands, maintenance.
More preferably scheme, drilling well spare are 55~80:20~45 with the mass ratio for solidifying medicament.
More preferably scheme, the additional amount of water are 0.25~0.45mg:1mL metering with mixed system solid-to-liquid ratio.
Curing agent of the invention has solidification effect to drilling well spare: 1) with the increase of curing agent volume, mud stirring is equal
It is even and be not susceptible to precipitate.Main reason is that the HAS in curing agent can be modified drilling well spare.2) with curing agent
The bleeding quantity of the increase of volume, solidified body substantially reduces.Reason is mainly steel-making slag powder in exciting agent (clinker obtained in HAS and life
Lime can excite the activity of steel-making slag powder) excitation under meet water hydration reaction, HAS, steel-making slag powder and quick lime aquation occur rapidly
Reaction can consume a large amount of water.It is gradually decreased so that with the water percolating capacity of the increase solidified body of curing agent volume.3) with curing agent
The drying shrinkage phenomenon of the increase solidified body of volume is improved.Main cause is the water-retaining property that HAS curing agent improves slurry, by water
Code insurance reduces water evaporation quantity there are in solidified body structure.4) as the increase cured body strength of curing agent volume increases.It is main
It wants reason to be that spare can be solidified in curing agent, intensity can be increased when there are also plentiful.Although using single curing agent
There is certain solidification effect to drilling well spare, but effect is not too much good, block a couple of days such as occur can not embark on journey shape, it can not demould,
Slight amount surface does not have hardness, and bleeding and drying shrinkage phenomenon occurs.Main cause is complicated component in drilling well spare, organic
Matter content is high (83.2%), and organic matter can seriously affect solidification effect.Organic matter contains humic acid and fulvic acid, when both have
Machine acid will affect hydration reaction when reaching certain concentration, wherein fulvic acid can disintegrate hydrated product.In addition drilling well spare is at mud
Shape, particle is small, and particle size range about 0.1~1mm, the particle major part particle size range of curing materials causes to solidify in 3~10mm
Internal portion is loosely organized shapeless, so that cured body strength is lower than 0.25MPa.
The present invention has further been incorporated molysite and normal sand on the basis of solidifying medicament and using curing agent, after being applied in combination
The solidification effect of drilling well spare is had obvious synergistic function.The present invention is bright to forming for slurry by the addition of molysite
Aobvious help, while bleeding quantity is significantly reduced.Main cause is that molysite also there is demulsification to make other than with coagulation effect
With.Drilling well spare does not carry out demulsification processing, and the addition of molysite, certain demulsification is played to spare, in addition molysite exists
Ferric hydroxide colloid is generated under alkaline environment, with the hydrated products such as calcium hydroxide, stratlingite, C-S-H, hydrated calcium ferrite
Mutually blending, collaboration solidification drilling well spare.And the addition of normal sand, solidification effect are obviously improved, main cause may be standard
The addition of sand reduces the content of organic matter in entire curing system.The different contents of organic matter is to the compression strength of solidified body
Difference is influenced, there are a concentration to limit (4.3%).I.e. when the content of organic matter is lower than 4.3%, the content of organic matter increases to strong
Degree has positive influence；When the content of organic matter is higher than 4.3%, content of organic matter increase has negative influence to intensity.Normal sand
The sand coarse aggregate ratio for the system that improves is added, improves the water-retaining property of slurry.And normal sand serves as fine aggregate in curing system, fills up mud
Gap between bits and curing agent, makes entire solidified body structure more closely knit.Good grain composition can improve the water-retaining property of slurry,
Conducive to the growth of intensity.Therefore, three is applied in combination in appropriate proportion, is obviously improved to the solidification effect of drilling well spare, can
To reduce bleeding quantity, cured body strength increases.
Preferred scheme, the solidification medicament are added in appropriate proportion in drilling well spare, carry out curing process to it.
Drilling well spare COD leaching concentration after solidification is lower than GB8978-1996 primary standard limit value；The Leaching of total cadmium is lower than
GB18598-2001 limit value.COD and leaching rate when total cadmium 28d age are as the increase of curing materials volume gradually decreases.
Using 55~80 parts of drilling well spares as reference, when HAS (4000 type) curing agent volume is 40 parts, molysite volume is 5 parts, and normal sand is mixed
Solidification effect is optimal when amount is 5 parts.
HAS of the invention is to have disclosed the HAS curing agent of report in the prior art (China Patent Publication No. is
CN1067663C, the application number CN98113594.3 applying date: 1998-06-12, soil-solidified-agent), preparation method are as follows: HAS master
If industrial residue, gypsum, clinker and masterbatch pass through slag cementitious material made of mechanical activation.According to certain proportion
Weigh the liquid slag (accounting for 80% of gross mass or more) of blast furnace slag, slag, phosphorus slag, flyash, addition gypsum, clinker and mother
Material carries out mechanical activation after mixing evenly in a reservoir.
The present invention is using solidify the specific method that medicament solidifies drilling well spare: weigh raw material importing mix pot, charging it is suitable
Sequence is successively drilling well spare, solidifies medicament, and water etc. first stirs at a slow speed 2min, stops shelves, scrape off the mortar on wall, then quickly stir
3min is mixed, so that slurry is uniformly fine and smooth to be advisable.Slurry is poured into mold (7.07cm*7.07cm*7.07cm) in three times with spoon,
1/3 be added in slot every time under smashing 10 along inner wall with the pole of 1~2cm of diameter, repeats above-mentioned step after standing 30min
Suddenly.During grouting, since the time that grouting front and back is stagnated is longer, slurry needs hand operated mixing equal after layering and precipitating occurs
It is in the milk again after even, is numbered after the completion of grouting and move mold to the shady and cool place being protected from light and placed.Finger presses lightly on block after for 24 hours
Surface, without obviously deforming and there is certain degree of hardness can then demould.Solidified body after demoulding is placed in standard curing box and is conserved
7d,14d,28d.The measurement for carrying out compression strength is removed to corresponding age.
The present invention carries out solidity test by evaluation index of the Leaching of compression strength, COD leaching concentration and total cadmium, really
Determine the selection and proportion of curing materials.
The compression strength (unconfined compressive strength) of solidified body refer to solidified body under conditions of no lateral pressure, institute's energy
The ultimate strength of the maximum axial pressure of receiving.It is normally used for evaluating the solidification effect of solidified body.In general, no lateral confinement is anti-
Compressive Strength is bigger, then solidification effect is better.The good solidified body of compression strength is easy to carry out waste resource recovery utilization.Solidified body resists
Compressive Strength can be increased with the extension of age, therefore compression strength need to be just significant under certain age.Generally have 3d,
The age of 7d, 14d, 28d, 90d.What is chosen herein is the age of 7d, 14d, 28d.It is handled referring to house refuse sanitary landfills
Technical specification (GB50869-2013), the compression strength of solidified body are greater than 0.25MPa (including 0.25MPa), the survey of compression strength
Measuring equipment is NYL-300 type pressure testing machine.
Toxicity leaching refers to solidified body in toxic and harmful components therein after water or other solution leach from solidified body
It moves in environment, pollutes the process of environment.The leaching of solidified body toxicity is one of important evaluation index of solidification effect.China master
It is carried out with reference to nitric acid-sulfuric acid method (HJ/T299-2007).Using nitric acid-sulfuric acid mixed liquor as digestion agent, simulation is not advised when waste
The landfill stabilization of model is stored up or after harmless treatment when waste land use, and poisonous and hazardous ingredient therein is in acidity
Under the action of precipitation, surrounding enviroment are moved to from waste.Landfill leachate toxic leaching is simulated in the environment of laboratory
It has troubles.Overturning oscillation or horizontal oscillations can be taken according to the condition in laboratory.Test herein is using overturning oscillation.To cadmium and
COD does leaching test, obtains the concentration of leachate.
Steel slag be steel-making discharge waste residue pass through quenching formed a kind of industrial residue, main chemical CaO,
SiO2、Al2O3、Fe2O3、MgO、MnO、TiO2Deng.Steel slag generally requires carry out mechanical activation.Steel-making slag powder activity after general grinding
It can be higher.
Compared with the conventional method, technical solution of the present invention has the beneficial effect that
Technical solution of the present invention utilizes high-level oxidation technology processing and solidification and stabilization processing technique harmless treatment oil gas
Field waste liquid of drilling and spare, waste liquid of drilling use H2O2/ UV can substantially reduce COD concentration, and water quality is clarified without precipitating, and drilling well mud
Bits not only fix the moisture in spare as curing materials using HAS curing agent, normal sand and molysite composition, and can reduce
The leaching concentration of COD and cadmium in spare, greatly reduce the secondary pollution to environment.
Detailed description of the invention
Fig. 1 is sample made from embodiment 7~13, the relationship of COD leaching rate and age；
Fig. 2 is sample made from embodiment 7~13, the relationship of total cadmium leaching rate and age.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Water-based drilling muds involved in method of the invention are from the oil-gas mining of Chongqing shale gas company.It will be oily
Water-based drilling muds are separated by solid-liquid separation during gas-field exploitation, obtain waste liquid of drilling and drilling well spare；Drilling well spare cadmium exceeds
5.5 times of hazardous waste judging standard (GB5085.3-2007), COD is beyond integrated wastewater discharge standard (GB8978-1996)
4.2 times, curing process is carried out using solidification medicament.
Following embodiment and curing method are using the drilling well spare in the above method as experimental subjects.
Steel-making slag powder used in following embodiment is derived from Wuhan Iron and Steel Plant, be canescence it is unformed powdered, particle size range be 0~
10mm.Main component is as shown in table 1:
1 steel slag component list of table
Quick lime is linen amorphous powder, the content of free calcium oxide 81.68%.
HAS soil-solidified-agent: specific gravity 3.10, bulk density are about 1.04g/cm3, gray fine powdered, fineness
3170cm2The testing result of/mg, X-fluorescence are shown in Table 2:
Table 2 HAS (4000) type curing agent X-fluorescence testing result
| Composition | Al2O3 | SiO2 | SO3 | CaO | Fe2O3 |
| Content (%) | 11.03 | 30.51 | 7.256 | 39.13 | 2.692 |
The preparation of curing materials needs raw material in following embodiment are as follows: oil drilling spare, HAS curing agent, steel-making slag powder,
Quick lime, molysite.
HAS's the preparation method comprises the following steps: according to certain proportion weigh blast furnace slag, slag, phosphorus slag, flyash liquid slag (account for
80% or more of gross mass), it is (specific that addition gypsum, clinker and masterbatch carry out mechanical activation after mixing evenly in a reservoir
Referring to CN98113594.3).
Embodiment 1
According to volume be 80 parts of HAS, curing agent A1 is made in 15 parts of steel-making slag powders, 5 parts of quick limes；
It adds 20 parts of A1 curing agent again to be added in the drilling well spare that volume is 80 parts, water-solid ratio 0.3.
Embodiment 2
Curing agent A1 is prepared according to embodiment 1, the brill that volume is 80 parts is added in the A1 curing agent of 20 parts of addition and 5 parts of molysite
In well spare, water-solid ratio 0.3.
Embodiment 3
Curing agent A1 is prepared according to embodiment 1, the drilling well that volume is 70 parts is added in the A1 curing agent that addition volume is 30 parts
In spare, water-solid ratio 0.3.
Embodiment 4
Curing agent A1 is prepared according to embodiment 1, it is 70 parts of drilling wells that volume, which is added, in the A1 curing agent of 30 parts of addition and 5 parts of molysite
In spare, water-solid ratio 0.3.
Embodiment 5
Curing agent A1 is prepared according to embodiment 1, it is water in 65 parts of drilling well spares that volume, which is added, in the A1 curing agent of 35 parts of addition
Gu than being 0.3.
Embodiment 6
Curing agent A1 is prepared according to embodiment 1, it is 65 parts of drilling wells that volume, which is added, in the A1 curing agent of 35 parts of addition and 5 parts of molysite
In spare, water-solid ratio 0.3.
Examples 1 to 6 experimental result is as shown in table 3.
The solidification effect of 3 curing agent A1 of table
| Number | Slurry property | Hardened forming | Intensity | Drying shrinkage phenomenon | Bleeding quantity |
| Embodiment 1 | Slurry is uniform | 5d rear surface is soft | Nothing | Seriously | It is more |
| Embodiment 2 | Slurry is uniform | 5d rear surface is soft | Nothing | Seriously | On a small quantity |
| Embodiment 3 | Slurry is uniform | 5d rear surface is soft | Nothing | Slightly | It is more |
| Embodiment 4 | Slurry is more uniform | 5d rear surface is soft | Nothing | Slightly | On a small quantity |
| Embodiment 5 | Slurry is more uniform | The hardening of 5d rear surface | 0.15MPa | Nothing | Nothing |
| Embodiment 6 | Slurry is more uniform | The hardening of 5d rear surface | 0.2MPa | Nothing | Nothing |
Embodiment 7
According to volume be 65 parts of HAS, curing agent A2 is made in 21 parts of steel-making slag powders, 7 parts of quick limes；
20 parts of A2 curing agent, 5 parts of normal sand, 5 parts of molysite is added again to be added in the drilling well spare that volume is 75 parts,
Water-solid ratio is 0.5.
Embodiment 8
Curing agent A2 is prepared according to embodiment 7, then adds 30 parts of A2 curing agent, 5 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 65 parts, water-solid ratio 0.5.
Embodiment 9
Curing agent A2 is prepared according to embodiment 7, then adds 35 parts of A2 curing agent, 5 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 60 parts, water-solid ratio 0.5.
Embodiment 10
Curing agent A2 is prepared according to embodiment 7, then adds 35 parts of A2 curing agent, 7 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 58 parts, water-solid ratio 0.5.
Embodiment 11
Curing agent A2 is prepared according to embodiment 7, then adds 35 parts of A2 curing agent, 10 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 55 parts, water-solid ratio 0.5.
Embodiment 12
Curing agent A2 is prepared according to embodiment 7, then adds 35 parts of A2 curing agent, 15 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 50 parts, water-solid ratio 0.5.
Embodiment 13
Curing agent A2 is prepared according to embodiment 7, then adds 40 parts of A2 curing agent, 5 parts of normal sand, 5 parts of molysite and adds
Enter in the drilling well spare that volume is 55 parts, water-solid ratio 0.5.
7~13 experimental result of embodiment is as shown in table 4.
The solidification effect of 4 curing agent A2 of table
Leaching experiment is carried out to embodiment 7~13, it is that 2:1 and pure water are mixed that leaching liquor, which uses the concentrated sulfuric acid and concentrated nitric acid mass ratio,
It closes, the pH value of mixed solution is 3.15~3.25.Leaching test leaches nitric acid-sulfuric acid referring to solid waste toxicity
Method (HJ/T299-2007) method carries out.Measurement rapid-digestion point of the measurement of COD referring to water chemical oxygen demand in leachate
Light photometry (HJ/T399-2007) method carries out；Cadmium detrmination method is referring to inductively coupled plasma mass spectrometry (ICP-MS)
Method carries out.
Present inventors have unexpectedly found that 28 day age solidified body leachate pH is not exceeded.COD, cadmium leaching rate are shown in corresponding age
Fig. 1 and Fig. 2.With the growth of age, the leaching rate of COD is gradually decreased.Illustrate solidification effect with the increase of curing agent volume
Gradually improve.Reducing substances in spare can be fixed in solidified body by curing agent, reduce the leaching of cadmium.Embodiment 7~
13 solidified body COD leaching rates with age changing rule relatively.COD leaching rate is greatly reduced when 7d, 14d age, 28d age
The COD leaching rate of phase reduces more gentle.Main reason is that hydration reaction is active when 7d age, most of reproducibility in spare
Substance is consolidated, therefore it is big to reduce amplitude；Hydration reaction tends to complete when to 28d age, and reaction carries out slowly, therefore 28d age
COD leaching rate reduces more gentle.What wherein the leaching rate of COD was minimum is embodiment 13, and worst is embodiment 12.
Claims (10)
1. a kind of oilfield drilling spare solidifies medicament, it is characterised in that: consolidate including what is be made of HAS, steel-making slag powder and quick lime
Agent.
2. a kind of oilfield drilling spare according to claim 1 solidifies medicament, it is characterised in that: the curing agent by with
Lower content of component composition:
65~80 parts of HAS；
15~21 parts of steel-making slag powder；
5~7 parts of quick lime.
3. a kind of oilfield drilling spare according to claim 1 or 2 solidifies medicament, it is characterised in that: the oil gas field
It further includes molysite and normal sand that drilling well spare, which solidifies medicament,.
4. a kind of oilfield drilling spare according to claim 3 solidifies medicament, it is characterised in that: the normal sand quality
It is the 12.5~50% of curing agent quality.
5. solidifying medicament according to a kind of oilfield drilling spare that claim 4 is stated, it is characterised in that: the dioxy of the normal sand
SiClx content > 96wt%, clay content are less than 0.2wt%, and loss on ignition is less than 0.04wt%, and particle size range is 0.08~2mm.
6. a kind of oilfield drilling spare according to claim 3 solidifies medicament, it is characterised in that: the quality of the molysite
It is the 10~30% of curing agent quality.
7. a kind of oilfield drilling spare solidification medicament according to claim/6, it is characterised in that: the molysite is chlorine
Change iron.
8. the application that a kind of described in any item oilfield drilling spares of claim 1~7 solidify medicament, it is characterised in that: use
In oilfield drilling spare curing process.
9. the application that a kind of oilfield drilling spare according to claim 8 solidifies medicament, it is characterised in that: by drilling well mud
Bits and solidification medicament and water after mixing evenly, are stood, maintenance.
10. the application that a kind of oilfield drilling spare according to claim 8 solidifies medicament, it is characterised in that: drilling well mud
Bits are 55~80:20~45 with the mass ratio for solidifying medicament；
The additional amount of water is 0.25~0.45mg:1mL metering with mixed system solid-to-liquid ratio.
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