CN106554828A - A kind of heavy fuel fluid composition and preparation method thereof - Google Patents
A kind of heavy fuel fluid composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of heavy fuel fluid composition peculiar to vessel and preparation method thereof.The fuel oil composition of the present invention includes pitch or slurry oil, shale oil, oil waterborne and tire pyrolysis oil, and optional additive.Wherein each blending component has different polarity and polarity is complementary, therefore the stability of gained blended fuel oil is improved；And the use of tire pyrolysis oil also reduces the cost of fuel oil composition.In the preparation method of the present composition, first petroleum base and non-petroleum base component oil being concocted respectively, and petroleum base and non-petroleum base oil product being called in respectively using shale oil as middle transition component, the stability of blended fuel oil is further increased.
Description
Technical field
The present invention relates to a kind of heavy fuel fluid composition and preparation method thereof, is especially adapted for use in composition and its preparation of bunker fuel oil.
Background technology
With rapid development of economy, China has become one of topmost shipping big country in the world, thus the demand growth of bunker fuel oil is very rapid.But for a long time, domestic refinery's bunker fuel oil yields poorly, larger with market demand gap, has a strong impact on the development of China's shipping cause.Therefore, if some industrial waste oils can be mixed into bunker fuel oil using blending technology, considerable economic benefit can not only be brought for Sinopec, moreover it is possible to effectively reduce environmental pollution, is a kind of effective ways for improving petroleum-based energy utilization rate.
Although the sulphur in fuel oil, vanadium, sodium, silicon and other trace meters and asphalitine, moisture, carbon residue, colloid etc. can all increase the corrosion and abrasion of diesel engine part, final corrosion and abrasion to part is comprehensive.Therefore the cost of fuel oil is only the critical problem for determining fuel oil market.Assume that ship has life-span of 20 years, diesel engine initial cost only accounts for 5% or so in the life cycle, and oil expense accounts for more than 90%, and this causes shipowner to pay special attention to the oil consumption of diesel engine, therefore shipowner can as far as possible with cheap oil.But the problems such as inferior fuel oil can cause pipeline and filter blocking, bad, corrosive wear of burning to aggravate, it requires that foundation is adapted to Sinopec feature, adapt to the bunker fuel oil of the domestic ships oil market demand again.
The country not yet has sufficiently understanding now to the utilization of damaged tire cracked oil, and some factories and miness are directly used as fuel or rosin, do not accomplish the Maxi-mize city value of the utilization of resources.The purification techniques of damaged tire cracked oil, it is possible to achieve damaged tire maximum minimizing, obtains the fuel oil with higher Economic Value Added, had both solved increasingly serious " black pollution ", and realized the recycling of discarded object again.
101885998 A of patent CN is related to a kind of composite fuel oil, and various discarded excessive fuel consumptions are allocated to solve the problems, such as fuel oil starvation by the method.In the patent, additive is more, and is directly concocted using weight oil, it is impossible to avoids concocting the unstable state of oil product system, and does not detect the accumulating stability of each index and tempered oil of oil product.
Patent CN101781575A is related to a kind of method that coalite tar prepares high-cleanness fuel oil.The process is simple, operating cost are low.But the method adopts organic solvent as extractant, but extractant inevitably loses, and causes the increase of cost.
The content of the invention
The present invention and overcomes the deficiencies in the prior art to solve energy deficiency, proposes a kind of blending formula of heavy oil peculiar to vessel, and the heavy bunker fuel oil has low cost, and calorific value is high, and stability in storage it is good the advantages of.
The heavy fuel fluid composition peculiar to vessel that the present invention is provided, in terms of composition weight, including following components：
Pitch or slurry oil 25%～65%, pitch preferably 30% ~ 35%, slurry oil preferably 45 ~ 60%；
Shale oil 10%～25%, preferably 12% ~ 23%；
Waterborne oily 15%～35%, preferably 16% ~ 33%；
Tire pyrolysis oil 5%～20%, preferably 7%～15%.
In the heavy bunker fuel oil of the present invention, wherein 0.05 ~ 0.5%% detergent-dispersant additive can also be included.Described detergent-dispersant additive selects the typical additives of this area, such as polyisobutene succinimide, succinate and polymer etc..The addition of quiet dispersant, can prevent and treat and deposit is generated under high temperature, or prevent precipitate from getting off, and greasy filth generated under low temperature etc. can be made to be dispersed in oil, it is to avoid form high temperature carbon distribution, paint film etc. within the engine, keep engine interior cleaning.
Further, described heavy bunker fuel oil is also containing 0.03% ~ 0.5 antioxidant.Described antioxidant selects the typical additives in this area, such as double octyl group basic zinc salts of dithio dialkyl phosphonic acid zinc, sulphur phosphorus etc..The addition of antioxidant, can not only prevent oil oxidation from metal surface can also be suppressed not corroded by acidic materials.
Further, described heavy bunker fuel oil can also include 0.1% ~ 0.5% pour-point depressant.Described pour-point depressant selects the typical additives in this area, such as ethene vinyl acetate copolymer, polymethacrylates, etc..The addition of pour-point depressant can significantly improve the low temperature flow of heavy oil, and reduce the condensation point of oil product.
In the heavy fuel fluid composition of the present invention, catalytic cracked oil pulp is the residue oil that refinery catalytic cracking unit discharges, as catalyst is usually contained in slurry oil so as to cause tenor too high.When blending prepares fuel oil, slurry oil must pass through filtration treatment.So that ash content and tenor reach the demand of blending oil product.Catalytic cracked oil pulp primarily serves the effect of the viscosity and calorific value of reconciling blended fuel oil in fuel oil composition.
With decompression residuum as raw material, the asphalt component obtained after solvent de-asphalting process is black solid or semisolid sticky mass to pitch used in the present invention, and viscosity is higher, density（20℃）Generally 0.97～1.25g/cm3, net heating value is 9300～11000kcal/kg.The addition of asphalt, primarily serves the effect for adjusting heavy fuel oil viscosity.
In the present invention, like natural oil, which is rich in alkane and aromatic hydrocarbons to described shale oils, is a kind of dark brown, has the thick liquid of specific stimulation smell.The density of shale oil（20℃）Generally 0.85～0.95g/cm3, net heating value is 9500～11500kcal/kg.The net heating value of shale oil is higher, and which is up to standard for the calorific value of fuel oil composition to make than larger contribution, and its density is relatively low, plays a part of to adjust fuel oil density.
In the present invention, described oil density waterborne（20℃）For 0.91～0.99 g/cm3, net heating value is 9200～11000kcal/kg.Oil waterborne as density is less and viscosity is relatively low, to the important effect of the density and viscosity plays of blended fuel oil.
The fuel oil that heretofore described tire pyrolysis oil is waste or used plastics, produced after rubber thermal cracking, waste tyre pyrolytic oil have that calorific value is high, ash content is low, viscosity is low and the low advantage of carbon residue.Reaction pyrolysis temperature is 410 DEG C ~ 500 DEG C, and synthesis pressure is 0.01～0.04MPa.The density of tire pyrolysis oil（20℃）Generally 0.9～0.98 g/cm3Calorific value is 9000 ~ 9900kcal/kg, tire pyrolysis oil is as price is low, viscosity is little, density is placed in the middle, and arene content is higher, tire pyrolysis oil can balance the mixing of heavy blended fuel oil density weight as blending component causes the precipitation of a large amount of asphalitines, and its arene content is higher can be used as the precipitation produced as asphalitine is separated out during the molten regulation blending of organic solvent.
The heavy fuel fluid composition peculiar to vessel of the present invention, can adopt the conventional blending method of this area to be prepared：Such as whole components are added in blending tank together, product are obtained through heating and stirring.Present invention preferably employs method described below is prepared（Blending）.
Therefore, present invention also offers a kind of preparation method of above-mentioned heavy fuel fluid composition, including herein below：
（1）Petroleum-based oil product will be similar to：Pitch or slurry oil are injected in pre- blending tank with part shale oil, are gradually heated to 60～150 DEG C, are stirred 3h ~ 10h, are well mixed to the two；
（2）By the oil product of non-petroleum base：Tire pyrolysis are oily, oil waterborne and remainder shale oil are injected in another pre- blending tank, are gradually heated to 60～150 DEG C, stir 1 ~ 8h, are well mixed to the two；
（3）By step（1）With（2）Pre- blending tank in oil product inject the main tank of blending together, be heated to 60～150 DEG C, stir 1 ~ 8h, oil product is well mixed；
In the preparation method of fuel oil composition of the present invention, wherein herein below can also be included：In step（1）Afterwards, step（2）Before, toward step（1）Detergent-dispersant additive and/or pour-point depressant are added in the material of gained, and is well mixed；And/or, in step（3）After end, toward step（3）The main tank of blending in add antioxidant, be well mixed.
Wherein detergent-dispersant additive and pour-point depressant purpose concoct the viscosity of oil product for the precipitation and reduction that reduce blended fuel oil sediment during blending, it is therefore desirable to add before the mixing of different component oil product.Antioxidant is mainly for preventing oil product in high temperature and the oxidation using process, therefore need to be eventually adding.
Wherein shale oil belongs to contained petroleum resources in shale series of strata, and shale oil is due to constituting more similar to natural oil, so similar oil base class component can be divided into, but in shale oil, presence of unsaturates is high and non-hydrocarbon compound content is high.Therefore shale oil can also be divided into the oil product of non-petroleum base class with its distinctive property.Petroleum-based oil product is finally mixed with the oil product of non-petroleum base, additive is added after being well mixed, and using shale oil as transition component, it is added separately in two kinds of oil product, solves the problems, such as that the different oil product of attribute is easily caused Precipitation as component structure is different from property in mixing.
In step（1）The shale oil of middle addition accounts for the 30%～50% of whole shale oil consumptions, and preferably 35%～45%.
The bunker fuel oil that blending is obtained is through spot test（ASTM D4740-04）The compatibility between its component oil is detected, by unstability parameter（ASTM D7061-2006）Whether occur being separated between component oil after experiment detection blending.And the tempered oil obtained by the present invention is detected through fast storage stability experiment, the difference of viscosity, density, acid number and total sediment of the levels of tempered oil is measured.
Slurry oil in the present invention filters out the impurity and catalyst fines in slurry oil, heavy corrosion and the fouling of internal combustion engine is caused when solving the problems, such as conventional oil product using slurry oil by filtration treatment.
The bunker fuel oil that the present invention is obtained obtains stigmatic image figure through spot test, and the result of stigmatic image is 1 grade, meets the use of fuel oil.And the unstability parameter of bunker fuel oil is obtained, the unstability parameter of oil product is less than 10, illustrate that the fuel oil after blending is not allowed to be also easy to produce phase separation, good stability.The difference of the measured levels viscosity for concocting oil product, density, acid number and total sediment is less, illustrates that the accumulating stability of oil product is fine.
Compared with prior art, the invention has the advantages that：
1st, tire pyrolysis oil is used in the present invention first as blending component, the density of the component oils such as shale oil, oil waterborne is lighter, and the density of the component oil such as pitch, slurry oil is larger, addition middle transition component oil-tire pyrolysis oil, weight oil can be avoided directly to mix the colloform texture of destruction mink cell focus, colloform texture is caused to destroy, asphalitine is separated out.So as to cause the problem of the mixed system bad stability of heavy oil.Therefore addition tire pyrolysis oil, can prevent pitch or slurry oil when oil waterborne with light oil and shale oil mix as intermediate species, cause asphalitine to separate out.
2nd, " same sex is compatible, and the opposite sex is repelled each other " rule of the present invention using molecular polarity, the polarity of component oil are different, can cause the layering between fuel oil ingredient.Pitch is longer due to its carbochain, and many side chains are all carried in each carbochain, and polarity is stable compared with weak structure.In slurry oil, the content of the aromatic hydrocarbon with short-side chain is very high, while saturated hydrocarbons and colloid also occupy certain ratio, therefore the polarity of slurry oil is weaker higher.Oily paraffin waterborne and total arene content are more or less the same, and polarity is placed in the middle.The paraffinicity of shale oil is very high, but the heteroatomic compound content such as its nitrogen, sulphur, oxygen is higher, and polarity is very strong.The arene content of tire pyrolysis oil is higher, and its ethylenic unsaturation hydrocarbon content is also very high, and asphalt content is relatively low, therefore polarity is also stronger.Two kinds of very big oil products of different polarities occur substantial amounts of precipitation after being mixed, therefore employ the complementary above-mentioned petroleum products blending of polarity and concocted, and the stability of fuel oil is improved.
3rd, the present invention has considered the categorical attribute of each blending component oil, petroleum base and non-petroleum base component oil are concocted respectively, and petroleum base and non-petroleum base oil product are called in respectively using shale oil as middle transition component, so as to increased the stability of blended fuel oil.
Description of the drawings
Stigmatic image figures of the Fig. 1 for 1 resulting composition of embodiment.
Stigmatic image figures of the Fig. 2 for 2 resulting composition of embodiment.
Stigmatic image figures of the Fig. 3 for 3 resulting composition of embodiment.
Micro-structure diagrams of the Fig. 4 for 1 resulting composition of embodiment.
Micro-structure diagrams of the Fig. 5 for 2 resulting composition of embodiment.
Micro-structure diagrams of the Fig. 6 for 3 resulting composition of embodiment.
Specific embodiment
The present invention is further described with reference to embodiment.In embodiment and comparative example, if no special instructions, the percentage being related to is percetage by weight.
Embodiment 1
The fuel oil composition of the present embodiment, including pitch 32.9%, shale oil 20%, tire pyrolysis oil 14.95% and waterborne oily 31.9%, detergent-dispersant additive 0.1%, pour-point depressant 0.1% and antioxidant 0.05%.
It is prepared using conventional method, process is as follows：By various component oils by a certain percentage, the main tank of blending is injected separately into regardless of order, concoct main tank temperature and be increased to 70 DEG C, 180# bunker fuel oils are obtained after stirring with 90 revs/min of speed.
Embodiment 2
The composition of the fuel oil composition of the present embodiment is with embodiment 1.
It is prepared using the method for the present invention.Pitch 32.9%, density are 1.0236 g/cm3（20 DEG C, it is at 20 DEG C with lower density and is measured）, rotary viscosity is 43.2Pas（50 DEG C, following viscosity is at 50 DEG C and measures）, shale oil 8%, density are 0.8974 g/cm3, adverse flow kinematic viscosity is 9.28 mm2/s.Inject in pre- blending tank, tank temperature is increased to 90 DEG C, in blending tank with 90 revs/min of speed stirring 3h after, add 0.1 detergent-dispersant additive and 0.1% pour-point depressant, mixing speed improved to 200-300 rev/min, stirring 2h.By non-petroleum base oil product tire pyrolysis oil 14.95%, density is 0.984 g/cm3, adverse flow kinematic viscosity is 25.34 mm2/ s, and waterborne oily 31.9%, as oily unstable component content waterborne is higher, therefore Jing after the colloid mill high speed shear dispersion post processing in laboratory, carry out blending experiment.Its density is 0.9397g/cm3, adverse flow kinematic viscosity is 22.57 mm2/ s and shale oil 12% mix after injecting another blending tank, tank temperature is gradually risen to 60 DEG C, after 70 revs/min of speed stirring 3h, by the main tank of oil product injection blending in above-mentioned two blending tank, the temperature of main tank is risen to after 70 DEG C, after 90 revs/min of speed stirring 1h, the antioxidant of addition 0.05%, after with 90 revs/min of speed stirring 2h, 180# bunker fuel oils are obtained.
Embodiment 3
The fuel oil composition of the present embodiment, is included on the basis of weight：Slurry oil 52.9%, shale oil 12%, tire pyrolysis oil 14.95%, waterborne oily 19.9%, detergent-dispersant additive 0.1%, pour-point depressant 0.1% and antioxidant 0.05%.
It is prepared using the method for the present invention.Slurry oil 52.9%, the filter screen of slurry oil Jing 200-800 mesh, and after being heated to 150 DEG C, filtered using air pressure 0.1-0.4MPa, density is 1.0636 g/cm3, adverse flow kinematic viscosity is 829.06 mm2/ s, shale oil 5%, density are 0.8974 g/cm3, adverse flow kinematic viscosity is 9.28 mm2/s.Inject in pre- blending tank, tank temperature is increased to 80 DEG C, stir detergent-dispersant additive and the pour-point depressant that 0.1% is added after 3h in pre- blending tank with 90 revs/min of speed, mixing speed is improved to 200-300 rev/min, 2h is stirred.By non-petroleum base oil product tire pyrolysis oil 14.95%, density is 0.984 g/cm3, kinematic viscosity is 25.34 mm2/ s, and waterborne oily 19.9%, density is 0.9397 g/cm3, adverse flow kinematic viscosity is 22.57mm2/ s and shale oil 7% mix after injecting another pre- blending tank, tank temperature is gradually risen to 60 DEG C, after 70 revs/min of speed stirring 3h, by the main tank of oil product injection blending in above-mentioned two pre- blending tank, the temperature of main tank is risen to after 70 DEG C, after 90 revs/min of speed stirring 1h, the antioxidant of addition 0.05%, after with 90 revs/min of speed stirring 2h, 180# bunker fuel oils are obtained.
After each embodiment blending, the index of sample is shown in Table 1, and the storage stability result of gained sample is listed in table 2.As illustrated in the accompanying drawings from 1 to 3, micro-structure diagram is as Figure 4-Figure 6 for the stigmatic image figure of fuel oil composition obtained by each embodiment.
Can be seen that from table 1-2 and Fig. 1-6, the heavy fuel fluid composition peculiar to vessel that the embodiment of the present invention 1,2 and 3 is provided, the indices such as total sediment, acid number, pour point comply with the national standard requirements, and stability test result shows that the storage stability of oil product is preferable, unstability parameter value illustrates that asphalitine will not be flocculated in this case between 5-10.With the rising of stability parameter, unstability is gradually lowered, and easily flocculates so as to be easily caused asphalitine.Can be seen that the stability of oil product is also preferable from spot test and microscope microstructure.But can be seen that from the comparing result of embodiment 1 and 2, fuel oil composition prepared by the method recommended using the present invention, density and polarity due to having taken into full account each blending component, and the method processed using substep carries out the blending and preparation of product, 2 gained marine fuel fluid composition of embodiment has more preferable unstability parameter, and can be seen that the storage stability of embodiment 2 is more preferable from the comparing result of microscope microstructure and spot test.
Claims (15)
1. a kind of heavy fuel fluid composition peculiar to vessel, including following components in terms of composition weight：
Pitch or slurry oil 25%～65%；
Shale oil 10%～25%；
Waterborne oily 15%～35%；
Tire pyrolysis oil 5%～20%.
2. according to the composition described in claim 1, it is characterised in that including following components in terms of composition weight：
Pitch 30%～35%, or slurry oil 45～60%；
Shale oil 12%～23%；
Waterborne oily 16%～33%；
Tire pyrolysis oil 7%～15%.
3. according to the composition described in claim 1 or 2, it is characterised in that the density of described pitch is 0.97～1.25g/cm3, net heating value is 9300～11000kcal/kg.
4. according to the composition described in claim 1 or 2, it is characterised in that the density of described shale oil is 0.85～0.95g/cm3, net heating value is 9500～11500kcal/kg.
5. according to the composition described in claim 1 or 2, it is characterised in that the density of the oil waterborne is 0.91～0.99 g/cm3, net heating value is 9200～11000kcal/kg.
6. according to the composition described in claim 1 or 2, it is characterised in that the density of described tire pyrolysis oil is 0.9～0.98 g/cm3, calorific value is 9000～9900kcal/kg.
7. according to the composition described in claim 1 or 2, it is characterised in that in composition described by weight also including 0.05 ~ 0.5%% detergent-dispersant additive, and/or 0.1%～0.5% pour-point depressant.
8. according to the composition described in claim 7, it is characterised in that described detergent-dispersant additive is selected from one or more in polyisobutene succinimide, succinate and polymer.
9. according to the composition described in claim 7, it is characterised in that described pour-point depressant is selected from ethene vinyl acetate copolymer and/or polymethacrylates.
10. according to the composition described in claim 1,2 or 7, it is characterised in that the antioxidant in composition described by weight also including 0.03% ~ 0.5.
11. according to the composition described in claim 10, it is characterised in that described antioxidant is selected from such as dithio dialkyl phosphonic acid zinc and/or the double octyl group basic zinc salts of sulphur phosphorus.
The preparation method of the arbitrary described composition of 12. claims 1-6, including herein below：
（1）Pitch or slurry oil are injected in pre- blending tank with part shale oil, 60～150 DEG C is heated to, is stirred 3h ~ 10h, be well mixed to the two；
（2）Tire pyrolysis oily, waterborne oil and remainder shale oil are injected in another pre- blending tank, 60～150 DEG C are heated to, 1 ~ 8h is stirred, is well mixed to the two；
（3）By step（1）With（2）Pre- blending tank in oil product inject the main tank of blending together, be heated to 60～150 DEG C, stir 1 ~ 8h, oil product is well mixed.
13. in accordance with the method for claim 12, it is characterised in that in step（1）The shale oil of middle addition accounts for 30 wt%～50 wt % of whole shale oil consumptions.
14. in accordance with the method for claim 13, it is characterised in that described slurry oil is carrying out filtration treatment in advance using front.
15. according to the arbitrary described method of claim 12-14, it is characterised in that in step（1）Afterwards, step（2）Before, toward step（1）Detergent-dispersant additive and/or pour-point depressant are added in the material of gained, and is well mixed；And/or, in step（3）After end, toward step（3）The main tank of blending in add antioxidant, be well mixed.
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| US20240174934A1 (en) * | 2022-11-15 | 2024-05-30 | Innospec Fuel Specialties Llc | Compositions, methods and uses |
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