CN105713661A - Preparation method and applications of drilling fluid base oil - Google Patents
Preparation method and applications of drilling fluid base oil Download PDFInfo
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- CN105713661A CN105713661A CN201410737298.4A CN201410737298A CN105713661A CN 105713661 A CN105713661 A CN 105713661A CN 201410737298 A CN201410737298 A CN 201410737298A CN 105713661 A CN105713661 A CN 105713661A
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Abstract
The invention relates to a synthesis method of drilling fluid base oil. The method comprises the following steps: step a, cutting a specific fraction product of Fischer-Tropsch synthesis into a plurality of fractions through distillation; step b, subjecting one or more of the fractions to an isomerization treatment, and controlling the isomerization degree in a range of 50 to 100% by changing the reaction conditions; step c, according to the application requirements of drilling fluid, blending the isomerized fraction oils and non-isomerized fraction oils according to a certain ratio; step d, distilling the product after blending to remove the hydro-isomerization byproducts (low carbon hydrocarbons) so as to obtain a base oil sample, which can be applied to performance tests and commercial applications.
Description
Technical field
The invention belongs to synthetic base drilling fluid base oil field, be specifically related to after Fischer-Tropsch synthetic rectification is cut by one respectively through isomerization, last on-demand mediation obtains drilling fluid base oil preparation method.
Background technology
Making a general survey of the developing history of drilling fluid last 100 years, oil base drilling fluid obtains and is increasingly widely applied and accreditation.This has high temperature resistance, salt resistance mainly due to it, lubricity is good, be conducive to wellbore stability, to advantages such as formation damage degree are less.Especially for improving mechanical separator speed, people are after 20 century 70s begin with water in oil emulsion drilling fluid mid-term, and oil base drilling fluid has consolidated oneself leading position commercially further.But traditional oils base drilling fluid is owing to taking from crude oil, inevitably contains the components such as sulfur, nitrogen, heavy metal, aromatic hydrocarbons, often the ecological environment near well site being caused during use having a strong impact on, the health of drilling implementer be will also result in injury.The rubber components of drilling equipment is also existed stronger corrosiveness by contained aromatic hydrocarbons too.In order to make up above-mentioned flaw, meet requirement to environmental conservation, particularly adapt to drilling at the sea and the demand of shale gas exploitation, the transformation of oil base drilling fluid base oil is taken seriously gradually [Drilling Fluid [M]. University of Petroleum goes out society, and 2001.].The synthetic base drilling fluid base oil occurred in recent years just in time solves the problems referred to above.
Synthetic base drilling fluid base oil is generally natural gas liquefaction or coal liquifaction, namely first natural gas or coal is converted into synthesis gas, prepares artificial oil then through F-T synthesis.The history of oil from Fischer-Tropsch synthesis can trace back to the twenties in 20th century.Nineteen twenty-three F.Fischer and H.Tropsch has invented CO heterogeneous hydrogenation and has generated the chemical reaction [DryME.TheFischer Tropschprocess:1950 2000 [J] .Catalysistoday, 2002,71 (3): 227-241.] of hydro carbons.The indirect reformer containing carbon resource such as natural gas, coal and biomass can be become oil product by application Fischer-Tropsch synthesis.Sulfur in raw material, nitrogen, metal etc. are separated in gasification synthetic gas production process so that institute's oil-producing product can meet the environmental requirement of various harshness.Another big feature of F-T synthesis is to be substantially free of aromatic hydrocarbons in product, and when particularly reaction temperature is relatively low, product is mainly based on n-alkane, and unsaturated hydrocarbons content is extremely low.Fischer-Tropsch synthesis products distribution scope is extremely wide, as it is shown in figure 1, after being separated by gaseous products, products distribution still spreads all over vapour, diesel oil distillate to solid wax etc..How to select reasonably to separate product so that it is carried out the major issue that high value added utilization has become fischer-tropsch synthesis process to research and develop.
Fischer-Tropsch synthetic is applied to oil base drilling fluid field, it is necessary to note the product cut impact on final performance.High carbon number fraction can bring the raising of base oil flash-point, emulsion-breaking voltage, shear force, but thing followed drawback is the increase of viscosity and filter loss.The increase of viscosity can make drilling tool power consumption increase, and the increase of filter loss then can cause that loss of drilling fluid is serious, promotes drilling cost.So how different fractions is rationally carried out proportioning and play vital effect.Additionally the isomerisation degree of product is also a critically important ring, determines the pour point of product.If pour point is too high, bring unnecessary trouble can to some situ of drilling well drilling fluid allotment work.
Current synthetic base drilling fluid preparation be usually by fischer-tropsch product through a simple isomery of step or without isomery directly as drilling fluid base oil use.Subsequent process need to control the performance of final products by adding various additive thus.
CN1761734A discloses the method being prepared base oil by Fischer-Tropsch synthetic, including: it is intermediate oil scope and less fraction (i) that expense one is ask sintetics to be separated into boiling point by (a), heavy ends (iii), and the intermediate base oil precursor fraction (ii) that boiling point is between fraction (i) and fraction (iii)；B () makes base oil precursor fraction (ii) experience catalytic hydroisomerisation and WITH CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades；C () makes heavy ends (iii) experience step of converting, to produce the boiling point fraction (iv) lower than heavy ends (iii)；(d) high boiling fraction (v) making fraction (iv) experiences catalytic hydroisomerisation and WITH CATALYTIC DEWAXING TECHNIQUE, to produce one or more base oil grades.
CN1761734A proposes and is prepared base oil by Fischer-Tropsch synthetic, although this base oil can be used for the preparation of drilling fluid, but owing to the application scenarios that drilling fluid following is different exists different demands, it is therefore desirable to the base oil that performance indications are different.And for the F-T synthesis route that process conditions are determined, in product, the carbon number distribution ratio of a certain component determines that.And due to factory's service condition restriction, can not quick more catalyst changeout or change the process conditions such as reaction temperature frequently, although so different grades of base oil can be obtained by (b) and (c) step in CN1761734A, but the index such as flash-point, viscosity cannot modulation on a large scale, at present not a kind of method enough allocating base oil flexibly.Meanwhile ii fraction is all carried out hydroisomerization or catalytic dewaxing by CN1761734A, economically considers not to be optimum, and we can process for wherein very small part completely, reaches same even outstanding effect.
The present invention is aiming at what the problems referred to above proposed, after the midbarrel of Fischer-Tropsch raw material carried out further distillation cutting into different fractions, first at least one of which fraction is carried out isomerization process, then the several fractions processing through isomery and processing without isomery obtained is in harmonious proportion in proportion, make drilling fluid base oil can meet the demand of different application occasion by controlling harmonic proportion, therefore prepare the premium drilling fluid base oil that can meet various condition flexibly.The present invention also widens the product purpose of fischer-tropsch product, adds fischer-tropsch product added value.
Summary of the invention
The invention aims to overcome Fischer-Tropsch synthetic can not meet, in the carbon number distribution of corresponding fraction, the problem that drilling fluid base oil performance indications require.Reduce product isomery processing capacity simultaneously, use manpower and material resources sparingly, reach to reduce energy consumption, reduce the purpose of cost.
For this, the preparation method that the present invention provides a kind of synthetic base drilling fluid base oil, comprise the steps:
1. it is midbarrel and less fraction and heavy ends that Fischer-Tropsch synthetic is separated into boiling point, and midbarrel boiling point is between less fraction and heavy ends；
2. the information such as the flash-point of various pure component hydro carbons, pour point, viscosity, shear force, filter loss are obtained by ASPEN software or experiment.According to the drilling fluid final application scenarios demand to base oil, design a kind of base oil component (target components) reached that is easier to by aforementioned fraction process, and determine the degree and final harmonic proportion that need that above-mentioned midbarrel is distilled the isomery of the number of components cut into, each component.Here harmonic proportion can be different according to the mass ratio that the different of practical application scene and each component are original in Fischer-Tropsch synthetic.
3. pair 1 gained midbarrel is distilled according to the result of calculation of 2 and is cut into several fractions；
4. at least one result of calculation according to 2 in pair several fractions cut into carries out isomerization process, and controls isomerisation degree 50～100%；
5. the application requirement according to drilling fluid, the midbarrel processing through isomery and processing without isomery obtained is in harmonious proportion in proportion, owing to distillation cutting step 3 and isomerization steps 4 can not be fully achieved the designing requirement of 2 steps, so need herein by 4 each components of gained use method of least square determine can be in harmonious proportion prepare target components optimum harmonic proportion, in this ratio and 2, the ratio of first calculated can disagree；
6. after pair mediation, product distills, and is removed by hydroisomerizing by-product low-carbon (LC) hydro carbons, obtains product.
Wherein, the fraction of the specific fraction product of described F-T synthesis is preferably 150～400 DEG C, more preferably 180～380 DEG C, and the best is 200～345 DEG C, n-alkane accounting example > 90%.
Described reaction temperature is 300～400 DEG C, reaction pressure is 7～10MPa, reaction sky is in 0.5～2h-1, hydrogen-oil ratio be 100～500:1.
According to GB-T256, sample motion viscosity being tested, all samples kinematic viscosity is respectively less than 3mm2/ s.According to GB-T261, sample flash-point being tested, all samples flash-point is all higher than 80 DEG C.According to SH/T0604, sample rate being tested, sample rate is all at 0.6～1.0g/cm3Between.
After sample is made drilling fluid according to common drilling fluid composition, its 50 DEG C, 180 DEG C emulsion-breaking voltages are all higher than 500V, and 180 DEG C of high temperature and high pre ssure filtration HTHP30 are respectively less than 25ml.
After fischer-tropsch product is first cut by the present invention by fraction, take and wherein certain several component that performance impact is maximum are carried out isomery process, design harmonic proportion according still further to final application scenarios afterwards to be in harmonious proportion, improve base oil flash-point, emulsion-breaking voltage, shear force performance simultaneously with this, take into account the performances such as drilling base oil viscosity, filter loss, pour point.The present invention " preparation method of a kind of synthetic base drilling fluid base oil of environmental protection flexibly " is to base oil performance requirement from final products, selects suitable process route, cuts hop count, the selection of isomery fraction, isomery degree, harmonic proportion including raw material.
For producing the process of drilling fluid base oil, whole raw materials need not be carried out together isomery, and it is just passable to have only to that the part of wherein most critical carries out isomery, effect can be better, and the manpower and materials of consumption are few, the amplitude that condensation point reduces is also big, compared to not splitting this step of direct isomery, the condensation point of base oil can be made to reduce amplitude bigger.
For this, the present invention can solve base oil performance issue and motility is high, index is better, for F-T synthesis, same catalyst or same plant produced product out, corresponding midbarrel section, carbon number distribution is certain, and this is that fischer-tropsch synthetic catalyst is determined.Carrying out isomery and change his this index of condensation point only by control isomerisation degree, the impact such as index for example flash-point, viscosity etc. for relying on carbon number distribution is only small.So strictly speaking, the application scenarios of drilling fluid is just affected.Have need high-flash application scenarios we can not go by change factory catalyst meet.Expend huge because factory changes catalyst manpower and materials.If but it is in harmonious proportion again after this part is cut, determine harmonic proportion according to required scene, not only meet a new application scenarios, and the range of application of product is wider.
Accompanying drawing explanation
Fig. 1 is the non-gaseous product quality scattergram of a typical Fischer-Tropsch synthesis used by the present invention.
Detailed description of the invention
Material involved in the present invention comprises but the material that is not limited in following example.
The typical Fischer-Tropsch synthesis product carbon number distribution of embodiment 1:
Adopt Co catalyst based, synthesis gas H2: CO=2, pressure 2MPa, temperature 200 DEG C, air speed 1000h-1When, carries out Fischer-Tropsch and becomes reaction, obtains the Mass Distribution of non-gaseous product as shown in Figure 1.
Fig. 1 is the non-gaseous product quality scattergram of a typical Fischer-Tropsch synthesis used by the present invention.It can be seen that the carbon number distribution of product is very wide in figure, major part product integrated distribution is at C5～C15 fraction simultaneously, is not completely superposed with fraction needed for drilling fluid.Above 2 factors make directly Fischer-Tropsch synthetic to be applied to drilling fluid base oil can not practical requirement.
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 three each 5L of fraction section, and 280～320 DEG C of fraction section are carried out hydroisomerizing.Reaction pressure is at 8MPa, temperature 340 DEG C, hydrogen-oil ratio 300:1, air speed 1h-1When, control isomerization rate more than 90%.Afterwards by not isomerized fraction 170～230 DEG C, 230～280 DEG C with after isomerized fraction 280～320 DEG C is in harmonious proportion according to 2:6:2 ratio, again carries out the components before distillation excision 170 DEG C, obtain product.
This sample motion viscosity is less than 3mm2/ s, flash-point more than 80 DEG C, pour point is less than 0 DEG C.Sulfur, nitrogen content are respectively less than 1ppm, it is possible to meet general area drilling well needs and major part environmental requirement.
Embodiment 3: the preparation method of drilling fluid base oil
Fischer-Tropsch synthetic obtains into 200～280 DEG C by separated, 280～320 DEG C two each 5L of fraction section, respectively it is carried out hydroisomerizing.Reaction pressure between 8MPa, temperature 315～335 DEG C, hydrogen-oil ratio 300:1, air speed 1h-1When, control isomerization rate and be respectively greater than 75% and 85%.After afterwards 200～280 DEG C and 280～320 DEG C two fractions of two kinds of isomerized products being in harmonious proportion according to 7:3 ratio, again carry out the component before distillation excision 200 DEG C, obtain product.
This sample motion viscosity is less than 3mm2/ s, flash-point more than 90 DEG C, pour point is less than-35 DEG C.Sulfur, nitrogen content are respectively less than 1ppm, it is possible to meet extremely cold area and operation on the sea drilling well needs.
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, 280～345 DEG C three each 5L of fraction section, and to 230～280 DEG C, 280～345 DEG C of two fraction section carry out hydroisomerizing.Reaction pressure is at 7MPa, temperature 300～340 DEG C, hydrogen-oil ratio 100:1, air speed 2h-1When, control isomerization rate and be respectively greater than 65% and 90%.Afterwards by not isomerized fraction 200～230 DEG C and isomerized fraction 230～280 DEG C, 280～345 DEG C be in harmonious proportion according to 2:5:3 ratio after, again carry out the components before distillation excision 200 DEG C, obtain product.
This sample motion viscosity is less than 3mm2/ s, flash-point more than 80 DEG C, pour point is less than～10 DEG C.Sulfur, nitrogen content are respectively less than 1ppm, it is possible to meet general area drilling well needs and major part environmental requirement.
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 three each 5L of fraction section, and to 280～345 DEG C, 345～400 DEG C of two fraction section carry out hydroisomerizing.Reaction pressure is at 10MPa, temperature 310～400 DEG C, hydrogen-oil ratio 500:1, air speed 0.5h-1When, control isomerization rate and be respectively greater than 50% and 99%.Afterwards by not isomerized fraction 150～230 DEG C, 230～280 DEG C with isomerized fraction 2280～345 DEG C, 345～400 DEG C be in harmonious proportion according to 1:3:4:2 ratio after, again carry out distillation excision 150 DEG C before components, obtain product.
This sample motion viscosity is less than 3mm2/ s, flash-point more than 80 DEG C, pour point is less than～10 DEG C.Sulfur, nitrogen content are respectively less than 1ppm, it is possible to meet general area drilling well needs and major part environmental requirement.
Embodiment 6: the mediation formula of emulsion-breaking voltage, high temperature and high pre ssure filtration measured by drilling fluid.
Using drilling fluid base oil preparation method in the present invention to obtain variety classes drilling fluid base oil, carry out drilling fluid property test after preparing drilling fluid according to the following formulation, formula is as follows: 240ml drilling fluid base oil, 6% emulsifying agent, 60mlCaCl220% solution, 2% organoclay, 2%CaO, 4% fluid loss additive, 666g barite, configured drilling fluid oil-water ratio 4:1, and density is 2.0g/cm3.It is carried out emulsion-breaking voltage, high temperature and high pre ssure filtration test, distribution of carbon value used and corresponding final performance as shown in Table 1:
Table one test prepares property of drilling fluid index
Contrast experiment: hydroisomerizing reduces the effectiveness comparison of base oil pour point
Use 174-400 DEG C of fraction section of Fischer-Tropsch synthetic (pour point is 12 DEG C), be respectively adopted two kinds of process conditions, compare the change of its pour point.
(1) 174-400 DEG C of fraction section carrying out overall isomery, control isomerisation degree 52.8%, product pour point is-2 DEG C.
(2) only wherein 280-400 DEG C of fraction section is carried out isomery, control isomerisation degree 87.3%, be in harmonious proportion according to original ratio with the 174-280 DEG C of fraction section not carrying out isomery, product pour point-31 DEG C.
The main purpose of fischer-tropsch product hydroisomerizing is reduced condensation point exactly, can be seen that (2) step processing capacity significantly reduces, but key component is processed, and the effect reached but is better than out and away all components is carried out general process, and pour point value significantly reduces.
Claims (5)
1. a preparation method for drilling fluid base oil, comprises the steps:
A., it is midbarrel and less fraction and heavy ends that Fischer-Tropsch synthetic is separated into boiling point, and midbarrel boiling point is between less fraction and heavy ends；
B. gained midbarrel distillation is cut into several fractions；
C. at least one isomerization in the several fractions cut into is processed, and isomerisation degree is controlled 50～100%；
D. the application requirement according to drilling fluid, is in harmonious proportion in proportion by the midbarrel processing through isomery and processing without isomery obtained；
E. product after being in harmonious proportion is distilled, hydroisomerizing by-product low-carbon (LC) 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 midbarrel of described Fischer-Tropsch synthetic 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 midbarrel of described Fischer-Tropsch synthetic is 180～380 DEG C.
4. the preparation method of drilling fluid base oil according to claim 3, it is characterised in that: the midbarrel of described Fischer-Tropsch synthetic 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: described isomerization reaction temperature is 300～400 DEG C, isomerization reaction pressure is 7～10MPa, isomerization reaction air speed is 0.5～2h-1, isomerization hydrogen-oil ratio be 100～500:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| US20040173502A1 (en) * | 1998-10-05 | 2004-09-09 | Sasol Technology (Pty) Ltd. | Production of biodegradable middle distillates |
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| US11499408B1 (en) | 2021-12-09 | 2022-11-15 | Halliburton Energy Services, Inc. | On-site conversion of a flammable wellbore gas to an oleaginous liquid |
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