CN109306852A - A kind of reversible transformation degreaser and the preparation method and application thereof containing amylene oxide ring - Google Patents
A kind of reversible transformation degreaser and the preparation method and application thereof containing amylene oxide ring Download PDFInfo
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- CN109306852A CN109306852A CN201710628815.8A CN201710628815A CN109306852A CN 109306852 A CN109306852 A CN 109306852A CN 201710628815 A CN201710628815 A CN 201710628815A CN 109306852 A CN109306852 A CN 109306852A
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- oil
- degreaser
- oxide ring
- reversible transformation
- amylene oxide
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- 239000013527 degreasing agent Substances 0.000 title claims abstract description 76
- 230000002441 reversible effect Effects 0.000 title claims abstract description 53
- 230000009466 transformation Effects 0.000 title claims abstract description 49
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005553 drilling Methods 0.000 claims abstract description 50
- 239000002699 waste material Substances 0.000 claims abstract description 45
- 239000002585 base Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 39
- 238000005520 cutting process Methods 0.000 claims description 36
- 239000012530 fluid Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 20
- 238000004064 recycling Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003863 metallic catalyst Substances 0.000 claims description 11
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 230000001351 cycling effect Effects 0.000 claims 2
- 230000003252 repetitive effect Effects 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 114
- 238000003756 stirring Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009963 fulling Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052699 polonium Inorganic materials 0.000 description 2
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- -1 specifically Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
- E21B21/06—Arrangements for treating drilling fluids outside the borehole
- E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The present invention provides a kind of reversible transformation degreaser and the preparation method and application thereof containing amylene oxide ring, which has structural formula shown in the formula (I) defined such as specification.Degreaser shown in formula (I) of the present invention shows as hydrophobicity under normal conditions, is converted to hydrophily after acid is added, and adds after alkali convertible time hydrophobicity again.The oil removal treatment to oil base drilling wastes is realized using the convertibility of its hydrophilic and oleophilic, specifically, oil base drilling wastes are mixed with hydrophobic oil removing conversion agent, oil can be extracted into degreaser, degreaser is converted into hydrophily again, the separable oil being obtained by extraction, then degreaser is converted back into hydrophobicity can continue on for oil removal treatment next time.
Description
Technical field
The present invention relates to a kind of degreasers and the preparation method and application thereof more particularly to a kind of containing the reversible of amylene oxide ring
Degreaser and the preparation method and application thereof is converted, oil base drilling wastes process field is belonged to.
Background technique
With the exploitation of the unconventional petroleum resources such as shale gas, the use scale of oil base drilling fluid is gradually increased.Oil base bores
Well liquid adds the medicaments such as emulsifier, wetting agent, fluid loss additive, has good stream using diesel oil or technical white oil as continuous phase
Denaturation energy, vena caval filter performance and lubricity.
In drilling process, the solid controlling circulatory system can generate a large amount of oil-based drill cuttings, and in oil-based drill cuttings, mineral oil content is reachable
20%.Drillng operation terminates, or repeatedly in the waste oil-based drilling fluid after circulation, oil content is up to 40% or more.Oil-based drill cuttings give up
In oil base drilling fluid, other than the mineral oil of high-content, the effect of the medicaments such as emulsifier causes their properties to be stablized, and processing is tired
Difficulty has been put into National Hazard waste register.Meanwhile so high oil content, there is great resource reclaim value.Directly
Entrust external unit processing, waste of resource.
Currently, the processing method of oil base drilling wastes (including oil-based drill cuttings, waste oil-based drilling fluid) mainly has both at home and abroad
Landfill, solidification, solid-liquid isolation method, extraction and heat treating process etc..Landfill, solidification method depend at separation of solid and liquid, extraction and heat
Residue after the processing separation of these methods is mainly filled or is solidified by logos.Heat treating process recycling is to directly adopt
The heat treatment methods such as distillation recycle waste oil, and this method is since the effect of heat can make the oil of recycling be affected, such as the oil quilt
For further preparing oil base drilling fluid, then oil base drilling fluid quality then will receive influence.Extraction is using extractant elder generation
Waste oil is extracted, then recycles extractant by the means such as heating or pressurization, for heat treating process recycling, no
Oil product can be destroyed, thus it is more common, but existing extractant has the following technical problems:
(1) extractant dosage is big, and extraction yield is low, and recycling is difficult, at high cost；
(2) extractant recycling needs to heat or pressurize etc. complicated means, needs to increase biggish equipment investment, is unfavorable for work
Industry application；
(3) adaptability of extractant is not strong；
(4) the problems such as low boiling point (30~40 DEG C) of extractant, safety in utilization is low.
In summary, many defects of existing oil base drilling wastes inorganic agent and processing method, this field need to develop
New oil base drilling wastes inorganic agent and new processing method, to meet real needs.
Summary of the invention
It is needed in view of reality, the reversible transformation oil removing containing amylene oxide ring that the main purpose of the present invention is to provide a kind of
Agent, the degreaser can be applied to oil base drilling wastes process field, can effectively overcome one in the defect of existing extractant
Kind is a variety of.
The preparation method of another object of the present invention is to provide the aforementioned reversible transformation degreaser containing amylene oxide ring, is adopted
The degreaser can be effectively prepared with this method.
The application of a further object of the present invention is to provide the aforementioned reversible transformation degreaser containing amylene oxide ring.
To achieve the above object, the present invention provides a kind of reversible transformation degreaser containing amylene oxide ring, with formula (I)
Shown in structural formula:
Wherein, R in formula (I)1、R2It is each independently selected methyl or ethyl.
Preferably, formula (I) is selected from:
Degreaser shown in formula (I) of the present invention shows as hydrophobicity under normal conditions, is added after acid and is converted to hydrophily, then plus
Enter after alkali convertible time hydrophobicity again.It is realized using the convertibility of its hydrophilic and oleophilic at the oil removing to oil base drilling wastes
Oil, specifically, oil base drilling wastes are mixed with hydrophobic oil removing conversion agent, can be extracted into degreaser by reason, then
Degreaser is converted into hydrophily, separates the oil content being obtained by extraction, then degreaser is converted back hydrophobicity to continue on for
Oil removal treatment next time.The degreaser handles oil base drilling wastes oil removal rate height, and oil recovery rate is more than 95%, remains after oil removing
Remaining waste water oil content is less than 5mg/L, and remaining solid residue oil content is lower than 0.3%.The degreaser has broad spectrum activity, can use extensively
In the processing of the oil-containings drilling wastes such as Petroleum & Petrochemical Enterprises difference oil base waste liquid of drilling, drilling cuttings.In addition, the degreaser itself has
There is the good rate of recovery, reusable, boiling point height is at 78 DEG C or so, the advantages that safety in utilization is good.
On the other hand, the present invention provides the preparation method of the aforementioned reversible transformation degreaser containing amylene oxide ring comprising
Ketoamine shown in formula (B) is formed using tetrahydro pyrone shown in formula (A) and organic amine condensation reaction first, repeated hydrogenation reduction should
Ketoamine is subsequently isolated out supernatant liquid and obtains the reversible transformation degreaser containing amylene oxide ring；
Specifically, this case is carried out by following route:
In above-mentioned preparation method, it is preferable that the organic amine includes one of dimethylamine, diethylamine and methyl ethylamine or more
Kind.
In above-mentioned preparation method, it is preferable that the hydrogenating reduction ketoamine is to be passed through hydrogen in the presence of metallic catalyst
Restore the ketoamine.It is highly preferred that the metallic catalyst includes one of beryllium, rhodium, nickel and palladium or a variety of.Further preferably
The mass ratio of ground, the metallic catalyst and the ketoamine is 1~100:1~800.It is highly preferred that the hydrogenating reduction ketone
It is 20~40MPa that amine, which is in Hydrogen Vapor Pressure, and temperature reacts 2~8h under the conditions of being 50~140 DEG C.Such as in 20~25MPa, temperature
2~4 are reacted under the conditions of being 50~70 DEG C.
In above-mentioned preparation method, it is preferable that the volume ratio of the tetrahydro pyrone and the organic amine is 120~150:
200~300.It is highly preferred that the condensation reaction is in 50~140 DEG C of 2~8h of reaction.
Specific embodiment as above-mentioned preparation method comprising following steps:
(1) 500mL three-necked flask 1 is taken, is put into heating mantle, room temperature, the addition of 120~150mL tetrahydro pyrone is weighed
In flask, start to stir；
(2) 200~300mL organic amine is added simultaneously, continues to stir, sufficiently dissolves；
(3) 7~10h is reacted；
(4) solution after reacting is transferred in the reaction kettle of 1000mL, is passed through H2, 0.2g metallic catalyst is added, 20~
Under the conditions of 25MPa pressure and 50~70 DEG C, 2~4h is reacted；
(5) supernatant liquid isolated is reversible transformation degreaser of the target product containing amylene oxide ring；
1 kind or 2 kind of the organic amine in dimethylamine, diethylamine and methyl ethylamine；
1 kind or 2 kind of the metallic catalyst in beryllium, polonium and palladium.
On the other hand, the present invention provides the aforementioned reversible transformation degreaser containing amylene oxide ring as extractant in oil recovery
The application of oil in base drilling cuttings.
On the other hand, the present invention provides a kind of method for handling oil-based drill cuttings comprising following steps:
(1) the reversible transformation degreaser by aforementioned containing amylene oxide ring is sufficiently mixed with the oil-based drill cuttings, and water is added；
(2) acid is added in the liquid obtained by step (1)；
(3) liquid obtained by step (2) is stood, then separates and recovers the oil on upper layer；
(4) it is added alkali in the remaining liq after step (3) extract oil, stratification is isolated containing amylene oxide ring
Reversible transformation degreaser.
Preferably, it is carried out after step (4) with the reversible transformation degreaser circulating repetition containing amylene oxide ring that it is obtained
Step (1) is to step (3).
Preferably, the oil content of the oil-based drill cuttings is 5~30%.
The method of above-mentioned processing oil-based drill cuttings the step of in (1), it is preferable that the reversible transformation containing amylene oxide ring
The mass ratio of degreaser and the oil-based drill cuttings, water is 2:1~4:1.
In the method for above-mentioned processing oil-based drill cuttings, it is preferable that described in acid described in step (2) and step (1)
The molar ratio of reversible transformation degreaser containing amylene oxide ring is 1:5~2:1.It is highly preferred that the acid includes hydrogen chloride, sulphur
One of acid, phosphoric acid are a variety of.It is further preferred that the acid is added in form of an aqueous solutions.Such as it is with mass fraction
36% hydrochloric acid.
In the method for above-mentioned processing oil-based drill cuttings, it is preferable that described in alkali described in step (4) and step (1)
The molar ratio of reversible transformation degreaser containing amylene oxide ring is 1:2~3:1.It is highly preferred that the alkali includes sodium hydroxide, hydrogen
One of potassium oxide, calcium hydroxide are a variety of.It is further preferred that the alkali is added in form of an aqueous solutions.Such as with matter
Measure the sodium hydroxide that score is 10%.
On the other hand, it is useless in recycling as extractant to provide the aforementioned reversible transformation degreaser containing amylene oxide ring by the present invention
The application of oil in oil base drilling fluid.
On the other hand, the present invention provides a kind of method for handling waste oil-based drilling fluid comprising following steps:
(1) the reversible transformation degreaser by aforementioned containing amylene oxide ring is sufficiently mixed with the waste oil-based drilling fluid, is added
Water；
(2) acid is added in the liquid obtained by step (1)；
(3) liquid obtained by step (2) is stood, then separates and recovers the oil on upper layer；
(4) alkali is added in the remaining liq after step (3) extract oil, stratification is isolated described containing oxinane
The reversible transformation degreaser of ring.
Preferably, it is carried out after step (4) with the reversible transformation degreaser circulating repetition containing amylene oxide ring that it is obtained
Step (1) is to step (3).
The method of above-mentioned processing waste oil-based drilling fluid the step of in (1), it is preferable that oil-containing in the waste oil-based drilling fluid
Rate is 20~75%.
The method of above-mentioned processing waste oil-based drilling fluid the step of in (1), it is preferable that described containing the reversible of amylene oxide ring
The mass ratio of degreaser and the waste oil-based drilling fluid, water is converted as 1:1~3:1.
In the method for above-mentioned processing waste oil-based drilling fluid, it is preferable that described in acid described in step (2) and step (1)
The reversible transformation degreaser containing amylene oxide ring molar ratio be 1:5~2:1.It is highly preferred that the acid includes hydrogen chloride, sulphur
One of acid, phosphoric acid are a variety of.It is further preferred that the acid is added in form of an aqueous solutions.Such as it is with mass fraction
36% hydrochloric acid.
In the method for above-mentioned processing waste oil-based drilling fluid, it is preferable that described in alkali described in step (4) and step (1)
The reversible transformation degreaser containing amylene oxide ring molar ratio be 1:2~3:1.It is highly preferred that the alkali include sodium hydroxide,
One of potassium hydroxide, calcium hydroxide are a variety of.It is further preferred that the alkali is added in form of an aqueous solutions.Such as with
The sodium hydroxide that mass fraction is 10%.
In summary, invention broadly provides a kind of reversible transformation degreaser and preparation method thereof containing amylene oxide ring
With application, have the advantages that
(1) deoiling effect is good.After oil removing extraction processing, the oil-based drill cuttings of 20% or more oil content, residue after processing
Oil content slightly mentions oily 97% or more oil content less than 0.3%.
(2) it can reuse, way of recycling is simple, and the rate of recovery is high.By the way that acid or alkali effect is added, degreaser can be made to exist
It is constantly converted under hydrophilic-hydrophobic state, facilitates carry out recycling and reusing, 95% or more the rate of recovery.It is used with current extractant
The mode that heating, pressurization are recycled is compared, safer, it is easier to operate.
(3) broad spectrum activity is strong.Degreaser has well adapting to property, can be widely used for different oil field blocks, different oil contents
The oil-containings drilling wastes such as waste liquid of drilling, drilling cuttings oil removing.
(4) boiling point is high, safe to use.Overcome general extractant low boiling point (30~40 DEG C), inflammable and explosive risk
The deficiencies of, improve the safety and use condition of degreaser.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction with specific implementation
Example and technical solution of the present invention is carried out described further below, it should be understood that these examples be merely to illustrate the present invention rather than
It limits the scope of the invention.In embodiment, each Starting reagents material is commercially available, test method without specific conditions
For conventional method known to fields and normal condition, or according to condition proposed by apparatus manufacturer.
Room temperature of the present invention refers to 18~30 DEG C.
Embodiment 1
This implementation provides degreaser shown in offer formula (I-1) and preparation method thereof, and the preparation method includes following step
It is rapid:
(1) 500mL three-necked flask 1 is taken, is put into heating mantle, room temperature, weighing 120mL tetrahydro pyrone, (No. CAS is
It 29943-42-8) is added in flask, starts to stir；
(2) 200mL dimethylamine is added simultaneously, continues to stir, sufficiently dissolve；
(3) 7h is reacted；
(4) solution after reacting is transferred in the reaction kettle of 1000mL, is passed through H2, 0.2g metallic catalyst beryllium is added,
Under the conditions of 20MPa pressure and 50 DEG C, 2h is reacted；
(5) supernatant liquid isolated is that the reversible transformation containing amylene oxide ring shown in target product formula (I-1) removes
Finish tests its boiling point by GB/T 616-2006 " chemical reagent ebulliometry universal method ", and acquired results are as described in Table 1.
Embodiment 2
This implementation provides degreaser shown in offer formula (I-2) and preparation method thereof, and the preparation method includes following step
It is rapid:
(1) 500mL three-necked flask 1 is taken, is put into heating mantle, room temperature, weighing 135mL tetrahydro pyrone, (No. CAS is
It 29943-42-8) is added in flask, starts to stir；
(2) 260mL diethylamine is added simultaneously, continues to stir, sufficiently dissolve；
(3) 8.5h is reacted；
(4) solution after reacting is transferred in the reaction kettle of 1000mL, is passed through H2, 0.2g metallic catalyst polonium is added,
Under the conditions of 22MPa pressure and 60 DEG C, 3h is reacted；
(5) supernatant liquid isolated is that the reversible transformation containing amylene oxide ring shown in target product formula (I-2) removes
Finish tests its boiling point by GB/T 616-2006 " chemical reagent ebulliometry universal method ", and acquired results are as described in Table 1.
Embodiment 3
This implementation provides degreaser shown in offer formula (I-3) and preparation method thereof, and the preparation method includes following step
It is rapid:
(1) 500mL three-necked flask 1 is taken, is put into heating mantle, room temperature, weighing 150mL tetrahydro pyrone, (No. CAS is
It 29943-42-8) is added in flask, starts to stir；
(2) 300mL methyl ethylamine is added simultaneously, continues to stir, sufficiently dissolve；
(3) 10h is reacted；
(4) solution after reacting is transferred in the reaction kettle of 1000mL, is passed through H2, 0.2g metallic catalyst palladium is added,
Under the conditions of 25MPa pressure and 70 DEG C, 4h is reacted；
(5) supernatant liquid isolated is the reversible transformation oil removing shown in target product (I-3) containing amylene oxide ring
Agent tests its boiling point by GB/T 616-2006 " chemical reagent ebulliometry universal method ", and acquired results are as described in Table 1.
Degreaser performance evaluation obtained by embodiment
(1) deoiling effect evaluation method of the reversible transformation degreaser to oil-based drill cuttings
(1.1) 20mL reversible transformation degreaser and 40.0g oil-based drill cuttings are sufficiently mixed, after fulling shake, 20mL is added
Pure water；
(1.2) 5mLHCl solution (36%) will be added dropwise while stirring in (1.1) liquid, until mixed liquor bottom is clarified and had big
Oil droplet of going here and there occurs；At this time degreaser from it is hydrophobic be changed into it is hydrophilic；
(1.3) after liquid obtained by (1.2) being stood 15 minutes, the oil on upper layer is separated and recovered；
(1.4) by (1.2) remaining liq after extract oil, 5mLNaOH aqueous solution (40%) is added while stirring, until liquid
It is layered, degreaser becomes hydrophobic again at this time, can carry out oil removing extraction processing to new oil-based drill cuttings again.
(2) deoiling effect evaluation method of the reversible transformation degreaser to waste oil-based drilling fluid
(2.1) 20mL reversible transformation degreaser and 20.0g waste oil-based drilling fluid are sufficiently mixed, after fulling shake, are added
20mL pure water；
(2.2) 5mL HCl solution (36%) will be added dropwise while stirring in (2.1) liquid, until mixed liquor bottom is clarified and had
Big string oil droplet occurs；At this time degreaser from it is hydrophobic be changed into it is hydrophilic；
(2.3) after liquid obtained by (2.2) being stood 15 minutes, the oil on upper layer is separated and recovered；
(2.4) by (2.2) remaining liq after extract oil, 5mL NaOH aqueous solution (40%) is added while stirring, until liquid
Body is layered, and degreaser becomes hydrophobic again at this time, can carry out oil removing extraction processing to new waste oil-based drilling fluid again.
(3) oil removal rate calculation method
(3.1) oil content for slightly mentioning oil, calculation formula are calculated are as follows:
Oil content (mass percent)
W in formula --- sample quality, g；
Vw--- distillate water volume, mL；
ρw--- the density of water, g/mL.
Wf--- filter residue quality, g.
(3.2)
W in formulaoe--- slightly mention oil quality, g；
Poe--- slightly propose oily oil content (mass percent)；
Wom--- oil-based drill cuttings quality, g；
Pom--- oil-based drill cuttings oil content (mass percent)；
(3.3) residue oil content detection method
The measurement of residue oil content uses CJ/T 221-2005 municipal sewage after oil-based drill cuttings and oil removal from waste oil-base drilling fluid
The measurement infrared spectrophotometer for the treatment of plant's sludge method of inspection mineral oil
(3.4) reversible transformation degreaser rate of recovery detection method
It is aqueous that the hydrophobic liquid recycled after reversible transformation process is detected using GB 260-77 oil product aquametry
Amount.
(3.5) embodiment product evaluation result
Choosing certain shale gas block oil-based drill cuttings that oil content is 20.25% is research object, to embodiment product evaluation
It the results are shown in Table 1.
1 embodiment product of table evaluates the deoiling effect of oil-based drill cuttings and recycling
Choosing certain shale gas block waste oil-based drilling fluid that oil content is 64.3% is research object, is commented embodiment product
Valence the results are shown in Table 2.
2 embodiment product of table evaluates the deoiling effect of waste oil-based drilling fluid and recycling
By Tables 1 and 2 it is found that the boiling point of degreaser obtained by 3 embodiments of the present invention is at 78 DEG C or so, the boiling point is significant
Higher than existing extractant.Using the processing oil-based drill cuttings of degreaser obtained by the present invention and waste oil-based drilling fluid, oily oil content is slightly mentioned
97% or more, oil removal rate is 97% or more, and handle drilling cuttings as a result, residue oil content is respectively less than 0.3%, the degreaser rate of recovery
95% or more, the oil and the good rate of recovery of degreaser itself having the advantages that in good recycling oil-based drill cuttings are shown.
Finally, it is stated that: above embodiments are merely to illustrate implementation process and feature of the invention, rather than limit this hair
Bright technical solution, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art answer
Work as understanding: it is still possible to modify or equivalently replace the present invention, without departing from the spirit and scope of the present invention any
Modification or part replacement, should all cover in protection scope of the present invention.
Claims (23)
1. a kind of reversible transformation degreaser containing amylene oxide ring, with structural formula shown in formula (I):
Wherein, R in formula (I)1、R2It is each independently selected methyl or ethyl.
2. the reversible transformation degreaser according to claim 1 containing amylene oxide ring, wherein formula (I) is selected from:
3. the preparation method of the reversible transformation degreaser of any of claims 1 or 2 containing amylene oxide ring comprising use first
Tetrahydro pyrone shown in formula (A) and organic amine condensation reaction form ketoamine shown in formula (B), and repeated hydrogenation restores the ketoamine, with
Supernatant liquid is isolated afterwards obtains the reversible transformation degreaser containing amylene oxide ring；
4. preparation method according to claim 3, wherein the organic amine includes in dimethylamine, diethylamine and methyl ethylamine
It is one or more.
5. preparation method according to claim 3 or 4, wherein the hydrogenating reduction ketoamine is deposited in metallic catalyst
The hydrogen reducing ketoamine is passed through under.
6. preparation method according to claim 5, wherein the metallic catalyst includes one of beryllium, rhodium, nickel and palladium
Or it is a variety of.
7. preparation method according to claim 6, wherein the mass ratio of the metallic catalyst and the ketoamine is 1~
100:1~800.
8. preparation method according to claim 7, wherein the hydrogenating reduction ketoamine be in Hydrogen Vapor Pressure be 20~
40MPa, temperature react 2~8h under the conditions of being 50~140 DEG C.
9. preparation method according to claim 3, wherein the volume ratio of the tetrahydro pyrone and the organic amine is
120~150:200~300；Preferably, which is in 50~140 DEG C of 2~8h of reaction.
10. the reversible transformation degreaser of any of claims 1 or 2 containing amylene oxide ring is as extractant in recycling oil-based drill cuttings
In oil application.
11. a kind of method for handling oil-based drill cuttings comprising following steps:
(1) the reversible transformation degreaser by of any of claims 1 or 2 containing amylene oxide ring and the oil-based drill cuttings are sufficiently mixed
It closes, water is added；
(2) acid is added in the liquid obtained by step (1)；
(3) liquid obtained by step (2) is stood, then separates and recovers the oil on upper layer；
(4) alkali is added in the remaining liq after step (3) extract oil, stratification is isolated containing the reversible of amylene oxide ring
Convert degreaser.
12. the method for processing oil-based drill cuttings according to claim 11, wherein contain four after step (4) with what it was obtained
The reversible transformation degreaser repetitive cycling of hydrogen pyranoid ring carries out step (1) to step (3).
13. it is according to claim 11 processing oil-based drill cuttings method, wherein the oil content of the oil-based drill cuttings be 5~
30%.
14. the method for oil-based drill cuttings is handled described in any one of 1~13 according to claim 1, wherein described in step (1)
The mass ratio of reversible transformation degreaser and the oil-based drill cuttings, water containing amylene oxide ring is 2:1~4:1.
15. the method for oil-based drill cuttings is handled described in any one of 1~13 according to claim 1, wherein described in step (2)
The molar ratio of acid and the reversible transformation degreaser containing amylene oxide ring described in step (1) is 1:5~2:1；Preferably, described
Acid includes one of hydrogen chloride, sulfuric acid, phosphoric acid or a variety of.
16. the method for oil-based drill cuttings is handled described in any one of 1~13 according to claim 1, wherein described in step (4)
The molar ratio of reversible transformation degreaser containing amylene oxide ring described in alkali and step (1) is 1:2~3:1；Preferably, described
Alkali includes one of sodium hydroxide, potassium hydroxide, calcium hydroxide or a variety of.
17. the reversible transformation degreaser of any of claims 1 or 2 containing amylene oxide ring is bored as extractant in recycling waste oil base
The application of oil in well liquid.
18. a kind of method for handling waste oil-based drilling fluid comprising following steps:
(1) the reversible transformation degreaser by as claimed in claim 1 or 2 containing amylene oxide ring and the waste oil-based drilling fluid are sufficiently mixed
It closes, water is added；
(2) acid is added in the liquid obtained by step (1)；
(3) liquid obtained by step (2) is stood, then separates and recovers the oil on upper layer；
(4) alkali is added in the remaining liq after step (3) extract oil, stratification is isolated containing the reversible of amylene oxide ring
Convert degreaser.
19. the method for processing waste oil-based drilling fluid according to claim 18, wherein obtained after step (4) with it
Reversible transformation degreaser repetitive cycling containing amylene oxide ring carries out step (1) to step (3).
20. the method for processing waste oil-based drilling fluid according to claim 18, wherein oil-containing in the waste oil-based drilling fluid
Rate is 20~75%.
21. the method for waste oil-based drilling fluid is handled described in any one of 8~20 according to claim 1, wherein described to contain tetrahydro
The reversible transformation degreaser and the waste oil-based drilling fluid of pyranoid ring, the mass ratio of water are 1:1~3:1.
22. the method for waste oil-based drilling fluid is handled described in any one of 8~20 according to claim 1, wherein in step (2)
The molar ratio of the acid and the reversible transformation degreaser containing amylene oxide ring described in step (1) is 1:5~2:1；Preferably,
The acid includes one of hydrogen chloride, sulfuric acid, phosphoric acid or a variety of.
23. according to claim 1 described in 8 or 19 handle waste oil-based drilling fluid method, wherein alkali described in step (4) with
The molar ratio of reversible transformation degreaser described in step (1) containing amylene oxide ring is 1:2~3:1；Preferably, the alkali packet
Include one of sodium hydroxide, potassium hydroxide, calcium hydroxide or a variety of.
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| CN201710628815.8A CN109306852B (en) | 2017-07-28 | 2017-07-28 | Reversible conversion degreasing agent containing tetrahydropyrane ring and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223660A (en) * | 1960-05-27 | 1965-12-14 | Nopco Chem Co | Stabilization of vinyl resins with tetrahydropyrans and organic metal salts |
| CN102888215A (en) * | 2012-10-30 | 2013-01-23 | 蒋官澄 | Oil removing agent for oily cuttings in drilling fluid of oil base and preparation method |
| CN106732399A (en) * | 2016-12-22 | 2017-05-31 | 北京师范大学 | Sorbing material and its controlled preparation process with oil spill thing function in removal water body |
-
2017
- 2017-07-28 CN CN201710628815.8A patent/CN109306852B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223660A (en) * | 1960-05-27 | 1965-12-14 | Nopco Chem Co | Stabilization of vinyl resins with tetrahydropyrans and organic metal salts |
| CN102888215A (en) * | 2012-10-30 | 2013-01-23 | 蒋官澄 | Oil removing agent for oily cuttings in drilling fluid of oil base and preparation method |
| CN106732399A (en) * | 2016-12-22 | 2017-05-31 | 北京师范大学 | Sorbing material and its controlled preparation process with oil spill thing function in removal water body |
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