CN105713661B - The preparation method and application of drilling fluid base oil - Google Patents
The preparation method and application of drilling fluid base oil Download PDFInfo
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- CN105713661B CN105713661B CN201410737298.4A CN201410737298A CN105713661B CN 105713661 B CN105713661 B CN 105713661B CN 201410737298 A CN201410737298 A CN 201410737298A CN 105713661 B CN105713661 B CN 105713661B
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Abstract
The present invention relates to a kind of preparation method of synthetic base drilling fluid base oil, comprise the following steps：A, the specific cut product of F- T synthesis is cut into several fractions by distillation；B, isomerization processing is carried out to one or more of cuts in gained several fractions, isomerisation degree is controlled between 50~100% by changing reaction condition；C, according to the application requirement of drilling fluid, will obtain being reconciled in proportion with the several fractions oil handled without isomery by isomery processing；D, product after mediation is distilled, hydroisomerizing accessory substance low-carbon hydro carbons is removed, obtains the base oil samples for performance test and commercial applications.
Description
Technical field
The invention belongs to synthetic base drilling fluid base oil field, and in particular to after a kind of cutting by Fischer-Tropsch synthetic rectifying
Respectively by isomerization, finally reconcile on demand and obtain drilling fluid base oil preparation method.
Background technology
The developing history of drilling fluid last 100 yearses is made a general survey of, oil base drilling fluid has obtained more and more extensive application and accreditation.This
Have that high temperature resistance, salt resistance, lubricity are good, are advantageous to wellbore stability, are smaller to formation damage degree mainly due to it
The advantages that.Especially for improve mechanical separator speed, people the 1970s mid-term start to use water in oil emulsion drilling fluid
Afterwards, oil base drilling fluid has further consolidated oneself leading position commercially.But traditional oil base drilling fluid is due to taking from
Crude oil, often the ecological environment near well site is made inevitably containing components such as sulphur, nitrogen, heavy metal, aromatic hydrocarbons, during use
Into having a strong impact on, injury will also result in the health of drilling implementer.Contained aromatic hydrocarbons is similarly deposited to the rubber components of drilling equipment
In stronger corrosiveness.In order to make up above-mentioned flaw, meet the requirement to environmental protection, particularly adapt to drilling at the sea and
The demand of shale gas exploitation, the transformation to oil base drilling fluid base oil are gradually taken seriously [Drilling Fluid [M] oil
University goes out society, and 2001.].The synthetic base drilling fluid base oil occurred in recent years just in time solves above mentioned problem.
Synthetic base drilling fluid base oil is generally natural gas liquefaction or coal liquifaction, i.e., natural gas or coal first is converted into synthesis
Gas, then artificial oil is made through F- T synthesis.The history of oil from Fischer-Tropsch synthesis can trace back to the 1920s.Nineteen twenty-three
F.Fischer and H.Tropsch invented CO heterogeneous hydrogenations generation hydro carbons chemical reaction [Dry M E.The Fischer-
Tropsch process:1950–2000[J].Catalysis today,2002,71(3):227-241.].Closed using Fischer-Tropsch
Can be by the indirect reformer containing carbon resource such as natural gas, coal and biomass into oil product into reaction.Sulphur, nitrogen, metal in raw material etc. are in gas
Change in synthetic gas production process and be separated so that institute's oil-producing product can meet various harsh environmental requirements.F- T synthesis it is another
Big feature is that aromatic hydrocarbons is substantially free of in product, and when particularly reaction temperature is relatively low, product is mainly based on n-alkane, insatiable hunger
It is extremely low with hydrocarbon content.Fischer-Tropsch synthesis product distribution is extremely wide, as shown in figure 1, after gaseous products are separated, product distribution
Still spread all over vapour, diesel oil distillate to solid wax etc..How to select reasonably to separate product to have carried out high value added utilization to it
Into a major issue of fischer-tropsch synthesis process research and development.
Fischer-Tropsch synthetic is applied to oil base drilling fluid field, it is necessary to pay attention to influence of the product cut to final performance.
The drawbacks of high carbon number fraction can bring the raising of basic oil flash point, emulsion-breaking voltage, shear force, but following is viscosity and leak-off
The increase of amount.The increase of viscosity can make drilling tool power consumption increase, and the increase of filter loss can then cause loss of drilling fluid serious, lifting
Drilling cost.So how different fractions are rationally carried out with proportioning is played vital effect.The isomerization journey of other product
Degree and a critically important ring, determine the pour point of product.If pour point is too high, some situ of drilling well drilling fluids can be given to adjust
Unnecessary trouble is brought with work.
It is usually that fischer-tropsch product is passed through into the simple isomery of a step or straight without isomery that at present prepared by synthetic base drilling fluid
Connect and used as drilling fluid base oil.Thus subsequent process need to control the property of final products by adding various additives
Energy.
CN1761734A discloses the method that base oil is prepared by Fischer-Tropsch synthetic, including：(a) will take a support synthesis production
Product be separated into boiling point be intermediate oil scope and lower cut (i), heavy ends (iii), and boiling point between cut (i) and
Intermediate base oil precursor cut (ii) between cut (iii)；(b) base oil precursor fraction (ii) is made to undergo catalytic hydrogenation isomery
Change and CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades；(c) heavy ends (iii) are made to undergo step of converting, with
Produce the cut (iv) that boiling point is less than heavy ends (iii)；Make the high boiling fraction (v) of cut (iv) undergo catalysis to add (d)
Hydrogen isomerization and CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades.
CN1761734A proposes prepares base oil by Fischer-Tropsch synthetic, although the base oil can be used for drilling fluid
Preparation, but because different demands be present in the different application scenarios of drilling fluid following, it is therefore desirable to the different basis of performance indications
Oil.And for the F- T synthesis route that process conditions determine, the carbon number distribution ratio of a certain component is to determine in product.
And due to factory's service condition limitation, it is impossible to quick more catalyst changeout frequently changes the process conditions such as reaction temperature,
So although different grades of base oil, flash-point, viscosity etc. can be obtained by (b) and (c) step in CN1761734A to refer to
Mark can not modulation on a large scale, the method for allotment base oil flexible enough not a kind of at present.At the same time
CN1761734A all carries out hydroisomerization or catalytic dewaxing to ii cuts, economically come consider be not it is optimal, I
Can be handled completely for wherein very small part, reach same even more outstanding effect.
The present invention proposes aiming above mentioned problem, is cut by the way that the midbarrel of Fischer-Tropsch raw material further to be carried out to distillation
After being cut into different fractions, isomerization processing is carried out to wherein at least one cut first, then will obtain handling by isomery
Several fractions with being handled without isomery are reconciled in proportion, by controlling harmonic proportion come drilling fluid base oil energy
Meet the needs of different application occasion, therefore the flexible obtained premium drilling fluid base oil that can meet various conditions.This hair
The bright product purpose for also widening fischer-tropsch product, adds fischer-tropsch product added value.
The content of the invention
The invention aims to overcome Fischer-Tropsch synthetic to meet drilling fluid in the carbon number distribution of corresponding cut
The problem of base oil performance indications requirement.Product isomery processing capacity is reduced simultaneously, is used manpower and material resources sparingly, reaches and reduces energy consumption, drop
The purpose of low cost.
Therefore, the present invention provides a kind of preparation method of synthetic base drilling fluid base oil, comprise the following steps：
1. it is midbarrel and lower cut and heavy ends that Fischer-Tropsch synthetic is separated into boiling point, midbarrel is boiled
Point is between lower cut and heavy ends；
2. by ASPEN softwares or test the flash-point for obtaining various pure component hydro carbons, pour point, viscosity, shear force, filter loss etc.
Information.Demand according to drilling fluid final application scene to base oil, design is a kind of to be reached by foregoing cut compared with easy processing
Base oil component (target components), and determine need by above-mentioned midbarrel distillation cut into number of components, each component it is different
The degree of structure and final harmonic proportion.Here harmonic proportion is according to the difference of practical application scene with each component in Fischer-Tropsch
Original mass ratio can be with different in sintetics.
3. pair 1 gained midbarrel cuts into several fractions according to 2 result of calculation distillation；
4. at least one of pair several fractions cut into carry out isomerization processing according to 2 result of calculation, and will be different
Structure extent control is 50~100%；
5. according to the application requirement of drilling fluid, the midbarrel handled by isomery with being handled without isomery that will be obtained
Reconciled in proportion, the design requirement of 2 steps can not be fully achieved due to distilling cutting step 3 and isomerization steps 4, so
Need herein by 4 gained each components using least square method determine can reconcile preparation target components optimal harmonic proportion, this compare
The ratio of example and first calculated in 2 can disagree；
6. product distills after pair mediation, hydroisomerizing accessory substance low-carbon hydro carbons is removed, obtains product.
Wherein, the cut of the specific cut product of the F- T synthesis is preferably 150~400 DEG C, more preferably 180~380
DEG C, most preferably 200~345 DEG C, n-alkane accounting example>90%.
The reaction temperature is 300~400 DEG C, reaction pressure is 7~10MPa, empty reaction is in 0.5~2h-1, hydrogen-oil ratio
For 100~500:1.
Sample motion viscosity is tested according to GB-T 256, all samples kinematic viscosity is respectively less than 3mm2/s.According to
GB-T 261 is tested sample flash-point, and all samples flash-point is all higher than 80 DEG C.Sample rate is carried out according to SH/T0604
Test, sample rate is in 0.6~1.0g/cm3Between.
After sample is made into drilling fluid according to common drilling fluid composition, its 50 DEG C, 180 DEG C of emulsion-breaking voltages are all higher than
500V, 180 DEG C of high temperature and high pre ssure filtration HTHP30 are respectively less than 25ml.
After the present invention is first cut fischer-tropsch product by cut, take and wherein certain maximum several component of performance impact are entered
The processing of row isomery, is reconciled according still further to final application Scenario Design harmonic proportion afterwards, and basic oil flash point, broken is improved with this
Newborn voltage, shear force performance simultaneously, take into account the performances such as drilling base oil viscosity, filter loss, pour point.The present invention is " a kind of flexible
The preparation method of environmentally friendly synthetic base drilling fluid base oil " is suitable to base oil performance requirement, selection from final products
Process route, including raw material cutting hop count, the selection of isomery cut, isomery degree, harmonic proportion.
For producing the process of drilling fluid base oil, isomery need not be carried out together to whole raw materials, and only need to it
The part of middle most critical carries out isomery can, and effect can be more preferable, and the manpower and materials consumed are few, the amplitude that condensation point reduces
Greatly, compared to direct isomery is not split the step for, the condensation point reduction amplitude of base oil can be made bigger.
Therefore, the present invention can solve base oil performance issue and flexibility height, index are more preferable, come for F- T synthesis
Say, the product that same catalyst or same plant produced come out, corresponding midbarrel section, carbon number distribution be it is certain,
This is that fischer-tropsch synthetic catalyst determines.Progress isomery can only this refers to by controlling isomerisation degree to change his condensation point
Mark, for rely on carbon number distribution index for example flash-point, viscosity etc. influence very little.So strictly speaking, the application of drilling fluid
Scene is just affected.Some need high-flash application scenarios we can not possibly go to expire by changing the catalyst of factory
Foot.Because it is huge that factory changes a catalyst manpower and materials consuming.But if reconciled again after being cut to this part, according to
Required scene determines harmonic proportion, not only meets a new application scenarios, and the application of product is wider.
Brief description of the drawings
Fig. 1 is the non-gaseous product quality distribution map of a typical Fischer-Tropsch synthesis used in the present invention.
Embodiment
Material involved in the present invention includes but is not limited to the material in following examples.
Embodiment 1：One typical Fischer-Tropsch synthesis product carbon number distribution
Using Co base catalyst, synthesis gas H2:CO=2, pressure 2MPa, 200 DEG C of temperature, air speed 1000h-1Under conditions of enter
Row Fischer-Tropsch and into reaction, the Mass Distribution for obtaining non-gaseous product is as shown in Figure 1.
Fig. 1 is the non-gaseous product quality distribution map of a typical Fischer-Tropsch synthesis used in the present invention.Can in figure
To find out, the carbon number distribution of product is very wide, while most of product integrated distribution is in C5~C15 cuts, with drilling fluid needed for evaporate
Divide and not fully overlap.2 factors of the above make it that Fischer-Tropsch synthetic directly is applied into drilling fluid base oil to meet
Actual demand.
Embodiment 2：The preparation method of drilling fluid base oil
Fischer-Tropsch synthetic obtains 170~230 DEG C, 230~280 DEG C by separated, 280~320 DEG C of three cuts
Each 5L of section, hydroisomerizing is carried out to 280~320 DEG C of fraction sections.Reaction pressure is in 8MPa, 340 DEG C of temperature, hydrogen-oil ratio 300:1, it is empty
Fast 1h-1Under conditions of, control isomerization rate is more than 90%.Afterwards by 170~230 DEG C, 230~280 DEG C of the cut of non-isomerization
280~320 DEG C of the cut with isomerization is according to 2:6:After 2 ratios are reconciled, the group before 170 DEG C of distillation excision is carried out again
Point, obtain product.
The sample motion viscosity is less than 3mm2/ s, flash-point are less than 0 DEG C more than 80 DEG C, pour point.Sulphur, nitrogen content are respectively less than
1ppm, general regional drilling well needs and most of environmental requirement can be met.
Embodiment 3：The preparation method of drilling fluid base oil
Fischer-Tropsch synthetic obtains into 200~280 DEG C, 280~320 DEG C of two each 5L of fraction section by separated, point
It is other that hydroisomerizing is carried out to it.Reaction pressure is between 8MPa, 315~335 DEG C of temperature, hydrogen-oil ratio 300:1, air speed 1h-1Bar
Under part, control isomerization rate is respectively greater than 75% and 85%.Afterwards by two kinds of 200~280 DEG C and 280~320 DEG C of isomerized products
Two cuts are according to 7:After 3 ratios are reconciled, the component before 200 DEG C of distillation excision is carried out again, obtains product.
The sample motion viscosity is less than 3mm2/ s, flash-point are less than -35 DEG C more than 90 DEG C, pour point.Sulphur, nitrogen content are respectively less than
1ppm, extremely cold area and operation on the sea drilling well needs can be met.
Embodiment 4：The preparation method of drilling fluid base oil
Fischer-Tropsch synthetic obtains into 200~230 DEG C, 230~280 DEG C by separated, and 280~345 DEG C three evaporate
Each 5L is segmented, to 230~280 DEG C, 280~345 DEG C of two fraction sections carry out hydroisomerizing.Reaction pressure is in 7MPa, temperature 300
~340 DEG C, hydrogen-oil ratio 100:1, air speed 2h-1Under conditions of, control isomerization rate is respectively greater than 65% and 90%.Afterwards will be not different
200~230 DEG C of the cut of structure is with 230~280 DEG C of the cut of isomerization, 280~345 DEG C according to 2:5:3 ratios are reconciled
Afterwards, the component before 200 DEG C of distillation excision is carried out again, obtains product.
The sample motion viscosity is less than 3mm2/ s, flash-point are less than~10 DEG C more than 80 DEG C, pour point.Sulphur, nitrogen content are respectively less than
1ppm, general regional drilling well needs and most of environmental requirement can be met.
Embodiment 5：The preparation method of drilling fluid base oil
Fischer-Tropsch synthetic obtains into 150~230 DEG C, 230~280 DEG C by separated, 280~345 DEG C, 345~
400 DEG C of three each 5L of fraction section, to 280~345 DEG C, 345~400 DEG C of two fraction sections carry out hydroisomerizing.Reaction pressure exists
10MPa, 310~400 DEG C of temperature, hydrogen-oil ratio 500:1, air speed 0.5h-1Under conditions of, control isomerization rate is respectively greater than 50% He
99%.Afterwards by 150~230 DEG C of the cut of non-isomerization, 230~280 DEG C with 2280~345 DEG C of the cut of isomerization, 345~
400 DEG C according to 1:3:4:After 2 ratios are reconciled, the component before 150 DEG C of distillation excision is carried out again, obtains product.
The sample motion viscosity is less than 3mm2/ s, flash-point are less than~10 DEG C more than 80 DEG C, pour point.Sulphur, nitrogen content are respectively less than
1ppm, general regional drilling well needs and most of environmental requirement can be met.
Embodiment 6：Drilling fluid measurement emulsion-breaking voltage, the mediation formula of high temperature and high pre ssure filtration.
Variety classes drilling fluid base oil is obtained using drilling fluid base oil preparation method in the present invention, is made according to the following formulation
Drilling fluid property test is carried out after obtaining drilling fluid, formula is as follows：240ml drilling fluid base oils, 6% emulsifying agent, 60ml
CaCl220% solution, 2% organoclay, 2%CaO, 4% fluid loss additive, 666g barites, have configured drilling fluid oil-water ratio 4:1,
Density is 2.0g/cm3.Emulsion-breaking voltage, high temperature and high pre ssure filtration test are carried out to it, distribution of carbon value used and correspondence are most
Whole performance is as shown in Table 1：
Property of drilling fluid index is made in the experiment of table one
Contrast experiment：The effect that hydroisomerizing reduces base oil pour point compares
Using 174-400 DEG C of fraction section of Fischer-Tropsch synthetic (pour point is 12 DEG C), two kinds of process conditions are respectively adopted, compare
Its pour point changes.
(1) overall isomery is carried out to 174-400 DEG C of fraction section, for control isomerisation degree 52.8%, product pour point is -2
℃。
(2) only carry out isomery to wherein 280-400 DEG C of fraction section, control isomerisation degree 87.3%, with do not carry out it is different
174-280 DEG C of fraction section of structure is reconciled according to original ratio, -31 DEG C of product pour point.
Main purpose to fischer-tropsch product hydroisomerizing is exactly to reduce condensation point, it can be seen that (2) step processing capacity substantially subtracts
It is few, but key component is handled, the effect reached is but better than far away carries out general processing, pour point to all components
Value significantly reduces.
Claims (5)
1. a kind of preparation method of drilling fluid base oil, comprises the following steps：
A. Fischer-Tropsch synthetic is separated into midbarrel and lower cut and heavy ends, midbarrel boiling point is between lower
Cut and heavy ends between；
B. according to drilling fluid application scenarios to basic oil flash point, pour point, viscosity, shear force, the demand of fluid loss performance and various pure
A kind of base oil component of performance design of component hydro carbons, and determine to need by the midbarrel number of components that cuts into of distillation with
And the degree of isomery afterwards；C. several fractions are cut into gained midbarrel distillation according to step b result；
D. according to step b result at least two difference isomerization processing in the several fractions that are cut into step c, and will
Isomerisation degree is controlled 50~100%；
E. according to the application requirement of drilling fluid, will obtain by isomery handle with without the midbarrel that isomery is handled by than
Example is reconciled, and during mediation, being handled by isomery for obtaining uses least square with the midbarrel handled without isomery
Method determine can reconcile preparation target components optimal harmonic proportion；
F. product after mediation is distilled, hydroisomerizing accessory substance low-carbon hydro carbons is removed, obtains product.
2. the preparation method of drilling fluid base oil according to claim 1, it is characterised in that：The Fischer-Tropsch synthetic
Midbarrel is 150~400 DEG C, n-alkane accounting example>90%.
3. the preparation method of drilling fluid base oil according to claim 2, it is characterised in that：The Fischer-Tropsch synthetic
Midbarrel is 180~380 DEG C.
4. the preparation method of drilling fluid base oil according to claim 3, it is characterised in that：The Fischer-Tropsch synthetic
Midbarrel is 200~345 DEG C.
5. the preparation method of the drilling fluid base oil according to any one of Claims 1 to 4, it is characterised in that：The isomery
Change reaction temperature is 300~400 DEG C, isomerization reaction pressure is 7~10MPa, isomerization reaction air speed is 0.5~2h-1, isomery
It is 100~500 to change hydrogen-oil ratio:1.
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| CN110964564A (en) * | 2018-09-29 | 2020-04-07 | 内蒙古伊泰煤基新材料研究院有限公司 | Fischer-Tropsch synthesis based drilling fluid base oil and preparation method thereof |
| US11499408B1 (en) | 2021-12-09 | 2022-11-15 | Halliburton Energy Services, Inc. | On-site conversion of a flammable wellbore gas to an oleaginous liquid |
Citations (4)
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|---|---|---|---|---|
| CN1425052A (en) * | 1999-12-22 | 2003-06-18 | 切夫里昂美国公司 | Synthesis of narrow lube cuts from fischer-tropsch products |
| CN1761734A (en) * | 2003-07-04 | 2006-04-19 | 国际壳牌研究有限公司 | Process to prepare base oils from a fisher-tropsch synthesis product |
| CN101415807A (en) * | 2006-03-31 | 2009-04-22 | 新日本石油株式会社 | Polyfunctional hydrocarbon oil composition |
| CN102015984A (en) * | 2008-03-13 | 2011-04-13 | 雪佛龙美国公司 | Process for improving lubricating qualities of lower quality base oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1835011A1 (en) * | 1998-10-05 | 2007-09-19 | Sasol Technology (Pty) Ltd | Biodegradable middle distillates and production thereof |
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2014
- 2014-12-05 CN CN201410737298.4A patent/CN105713661B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425052A (en) * | 1999-12-22 | 2003-06-18 | 切夫里昂美国公司 | Synthesis of narrow lube cuts from fischer-tropsch products |
| CN1761734A (en) * | 2003-07-04 | 2006-04-19 | 国际壳牌研究有限公司 | Process to prepare base oils from a fisher-tropsch synthesis product |
| CN101415807A (en) * | 2006-03-31 | 2009-04-22 | 新日本石油株式会社 | Polyfunctional hydrocarbon oil composition |
| CN102015984A (en) * | 2008-03-13 | 2011-04-13 | 雪佛龙美国公司 | Process for improving lubricating qualities of lower quality base oil |
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