CN105778987B - A kind of production method of biodiesel and bunker fuel oil - Google Patents
A kind of production method of biodiesel and bunker fuel oil Download PDFInfo
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- CN105778987B CN105778987B CN201610099494.2A CN201610099494A CN105778987B CN 105778987 B CN105778987 B CN 105778987B CN 201610099494 A CN201610099494 A CN 201610099494A CN 105778987 B CN105778987 B CN 105778987B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides the production method of a kind of biodiesel and bunker fuel oil.This method comprises the following steps：Original biomass oil or the bio-oil after hydrofinishing are added into full fraction of coal tar, is stirred for the dregs of fat are settled out, is removed the dregs of fat, obtain miscella；To the miscella hydrofinishing, then it is fractionated and obtains diesel oil and bunker fuel oil.The present invention can be with the ash content in depth removal coal tar, asphalitine, sulphur, metal impurities, the extension fixture cycle of operation.
Description
Technical field
The present invention relates to fuel manufacture field, in particular to the production of a kind of biodiesel and bunker fuel oil
Method.
Background technology
Bioenergy is always important energy source for the survival of mankind, it be only second to coal, oil and natural gas and occupy
In the world energy sources total quantity consumed energy of the 4th, occupy critical role in whole energy resource system.With coal and oil etc.
The growing tension of non-renewable fossil resource supply and the increasingly raising of environmental requirement, using reproducible biomass as feedstock portions
Fossil energy and chemicals are substituted, energy supply anxiety can be alleviated, improved the ecological environment.Therefore, many research institutions in the whole world
Bio-based petrochemical industry relation technological researching is carried out in succession.
Development of the China to bio-based petrochemical industry also gives certain policy support, starts to build bio-fuel industry
Standard criterion system, has formulated biology, forestry, agro-ecology mass-energy, the ad hoc planning of bio-fuel industry, bio-fuel production
Industry Legal System gradual perfection, the most recent layout of appearance includes：《Biomass Energy Development " 12 " is planned》、《Regenerative resource
Long-and Medium-term Development is planned》, state's laws include《Renewable Energy Law》、《Economizing energy law》、《Recycling economy promotion law》With《Greatly
Gas prevention and cure of pollution method》；Main regulation includes《Some policies for promoting biological industry to accelerate development》、《Accelerate to promote crops straw
The opinion of stalk comprehensive utilization》Deng.This creates favourable environment for the development of biological foundation stone new industry.
Bio-oil can remove oxygen therein and impurity after hydrogenation, obtain fuel oil ingredient, but due to biological
The collection of matter oil is restricted, it is impossible to realize large-scale production.Because bunker fuel oil is cheap, therefore production marine fuel
The raw material of oil is significantly limited.Coal tar, due to cheap, is that people are generally selected as bunker fuel oil
One of raw material.
Coal tar is the organic mixture based on aromatic hydrocarbon, can be processed into various chemicals, can also be processed into height
Quality fuel oil.Coal tar is the significant by-products of coking industry and coal gas chemical industry.With China's economic construction particularly steel
The development that deepens continuously of ironworker's industry, coking industry is also developed rapidly therewith, and existing China has evolved into Jiao the biggest in the world
Charcoal and coal tar production country.To the end of the year 2012 national coal tar oil yield more than 20,000,000 tons/year, and coal tar reality adds deeply
Work amount is less than 8,000,000 tons/year, serious waste of resources.With the development of coking of coal industry, the yield of coal tar is being continuously increased,
Therefore economic development of the cleaning processing of coal tar to China has profound influence.Current most domestic enterprise is directly by coal
Tar is sold, and not only added value is low, and causes very big pollution to environment.Then how tar resource is rationally utilized,
It is more and more important and more and more urgent that the economic benefit of raising enterprise becomes.Produced by raw material of coal tar using hydrogenation technique
Clean fuel oil, not only conforms with the requirement of the policies such as country's developing new energy, environmental protection, while can also be brought well for enterprise
Economic benefit.
But the asphalitine and tenor in coal tar are very high, seriously constrain the cycle of operation of hydrogenation plant.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide the production method of a kind of biodiesel and bunker fuel oil, described producer
Method can not only remove ash content in coal tar, asphalitine, sulphur, metal impurities with depth, and inorganic agent cost used it is low,
Coal tar, which can be substituted, to be used to produce diesel oil and bunker fuel oil.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of production method of biodiesel and bunker fuel oil, comprises the following steps：
Original biomass oil or the bio-oil after hydrofinishing are added into full fraction of coal tar, is stirred for heavy
Drop the dregs of fat, remove the dregs of fat, obtain miscella；
To the miscella hydrofinishing, then it is fractionated and obtains diesel oil and bunker fuel oil.
Compared with prior art, the present invention is not that the impurity in coal tar is removed using mechanical systems such as press filtrations, but is adopted
Chemically, i.e., bio-oil is added into coal tar and occurs flocculation reaction, so that ash content, mechanical admixture in coal tar
And the toxic compounds such as asphalitine, sulphur, metal are settled down to bottom, finally the physical removal dregs of fat again, can so realize following skill
Art effect：First, impurity removal percentage is high, especially short grained impurity, and asphaltene removal is more than 58%, and ash content removal efficiency exists
More than 88%, mechanical admixture removal efficiency more than 80%, sulfur removal rate more than 50%, metal removal rate more than 67%, because
This substantially prolongs the cycle of operation of device；Two, bio-oil can substitute coal tar, reduce the usage amount of coal tar, both ring
Protect, cost can be reduced again；3rd, bio-oil can reduce the operating pressure of hydrofinishing, so as to reduce production cost.
It can be seen that, compared with prior art, the present invention cost, removal efficiency, in terms of the plant running cycle have significantly it is excellent
Gesture, it is most important that provide new way for the accessible replacement of non-renewable energy resources.
Original biomass oil of the present invention can be the oil of any kind, and the present invention originates to it, crop species are equal
It is not limited.
The bio-oil of process hydrofinishing of the present invention refers to above-mentioned original biomass oil carrying out hydrofinishing.
Bio-oil i.e. used in the present invention can be original or by processing, and (be hydrogenated with essence by pretreatment
System) bio-oil slagging-off effect more preferably, finally obtained diesel oil and marine fuel oil quality are also more preferable.
Aforementioned production method can also be improved further：
Preferably, the temperature during stirring is 80-150 DEG C, preferably 100-150 DEG C.
Temperature during mixing can influence the mobility of two kinds of raw materials, and typical temperature is higher, and mobility is better, but temperature mistake
Height can cause raw material to go bad, therefore, using 80-150 DEG C of mixing temperature be it is optimal, more preferably 100-150 DEG C.
Two kinds of raw materials can also in advance be heated before mixing, to improve flocculation efficiency.
Preferably, the percentage by weight of the full fraction of coal tar is no more than 70%.
This percentage refers to the proportion of coal tar when being mixed with bio-oil, and effect is removed the gred when its accounting is below 70% more
It is good.
Preferably, the method to the miscella hydrofinishing is：
It is that 5.0~8.0MPa, temperature are 320~400 DEG C in pressure in the solid-bed reactor equipped with catalyst, it is empty
Speed is 0.2~2.0h-1, hydrogen to oil volume ratio be 500~2000 under conditions of react.
The reaction condition is compared with the condition of simple coal tar, and reaction pressure has declined, and reduces the requirement to device,
Save energy consumption.More preferably：Pressure is that 5.0~7.0MPa, temperature are 320~365 DEG C, and air speed is 1.5~2.0h-1, hydrogen oil
Volume ratio is 1000~2000.
In this hydrofinishing, described catalyst includes what is be mainly made up of polyvinyl alcohol, macropore dry glue powder and auxiliary agent
Metal is impregnated with carrier, and the carrier.
The catalyst belongs to macroporous catalyst, holds amount of metal and volume carbon amounts is high, metal removal rate in a low voltage state
It is higher, can the extension fixture cycle of operation.
One or more combinations in the metal that the catalyst is loaded preferably Ni-Mo, Co-Mo and Ni-W.
The cost of this several metallic element is low, and with different variation of valence, the quantity of d electronics and electronics form, urges
Change performance more excellent.In carried metal element, its forerunner's state can be any available compound, and relatively common is metal
Salt, the invention is not limited in this regard.
Auxiliary agent used in the catalyst is preferably sesbania powder and/or borax.
Boron-containing compound can both improve solubility, can also improve the mechanical strength of catalyst.Sesbania powder has crosslinking
And adhesive effect, the pore volume and specific surface area of catalyst can be improved.
The catalyst can using it is any can realize method be made, for example with rolling ball method, pressed disc method, kneading extrusion method or
Person's spray-on process manufactures carrier, with infusion process, spray process, redispersion, grafting carried metal, or in carrier forming process
It is added directly into metallic element and catalyst is made in a step.Hereafter only provide one of which sexual valence higher preparation method, bag
Include the following steps：
According to formula, after solvent polyethylene dissolving alcohol, it is mixed with macropore dry glue powder and auxiliary agent, then kneading extrusion,
5-6h is dried at 120-150 DEG C afterwards, 3-5h is calcined at 550-600 DEG C, carrier is made；
With hole saturation impregnating metal, 3-5h is dried at 120-150 DEG C afterwards, 20-25h is calcined at 350-450 DEG C.
Firstly, since the catalyst used in gasoline manufacture field mainly uses kneading extrusion equipment, therefore the present invention at present
Using kneading extrusion method, enterprise need not change manufacturing equipment, be easy to promote the product of the present invention.
Secondly, hole saturation is high to the utilization rate of metal, and easily forms suitable active phase, obtained catalyst quality
It is higher.
In addition, drying and being calcined extremely important to the crystal habit of carrier, it can obtain that pore volume is big, ratio using conditions above
Surface area is big, micropore evenly regular catalyst.
Preferably, the bio-oil after hydrofinishing is obtained using following methods：
Original biomass oil is imported in the solid-bed reactor equipped with catalyst, is 5.0~8.0MPa, temperature in pressure
For 280-380 DEG C, air speed is 1.0-5.0h-1, hydrogen to oil volume ratio be 500~2000 under conditions of, carry out hydrofinishing.
After being handled using the condition, the conversion ratio of fatty acid methyl ester or triglyceride in bio-oil is higher, at least can
Reach 60%-85%, or even 100%.Catalyst used in this one-step refining is any available catalyst.
Compared with prior art, beneficial effects of the present invention are：
(1) impurities removing efficiency is high；
(2) reaction pressure is low；
(3) cost of material is low；
(4) the plant running cycle is long；
(5) the appearance amount of metal of catalyst and volume carbon amounts are high.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Prepare catalyst：
Macropore dry glue powder 141.0g is taken, sesbania powder 3.0g, borax (analysis is pure) 2.5g is added, is well mixed.It is commercially available
PVA1788 powder 8.0g, are dissolved in 115mL water, dissolving is added in well mixed dry glue powder after finishing under stirring, slow heating,
After multiple kneading, a diameter of 1.5mm cylindrical bar is extruded into after standing 15 minutes, bar is extruded after being dried 5 hours at 120 DEG C,
Taken out after being calcined 3 hours at 550 DEG C, be designated as carrier a, the pore structure property of carrier is as shown in table 1.Take molybdenum oxide (AR)
4.01g, basic nickel carbonate (AR) 1.40g, concentrated phosphoric acid (AR) 0.81g, add water 100mL, the lower continuous heating backflow of stirring, band solution
Stop heating after bleach, be down to room temperature standby.Support samples a 80g are taken, are impregnated with hole saturation, dipping is finished in fume hood
In dry in the air 3 hours after, at 120 DEG C dry 3 hours, in Muffle furnace at 350 DEG C be calcined 20 hours, be designated as catalyst I.
The carrier a properties of table 1
| Index | Numerical value |
| Specific surface area/(m2/g) | 257 |
| Pore volume/(mL/g) | 0.963 |
To bio-oil hydrofinishing：
Carry out bio-oil hydrogenation first on fixed bed hydrogenation experimental rig, bio-oil is Xinjiang cottonseed oil, and it is led
Property is wanted to be shown in Table 2.Hydrogenation catalyst uses business Hydrobon catalyst FHUDS5.
Hydroprocessing conditions are:Pressure 7.0MPa, 320 DEG C of reaction temperature, air speed 5.0h-1, hydrogen to oil volume ratio 1000.
Hydrofinishing is carried out to Xinjiang cottonseed oil under the operating conditions, cottonseed oil hydrofined oil is obtained, its property
It is shown in Table 3.
The Xinjiang cottonseed oil nature of table 2
The Xinjiang cottonseed oil hydrofinishing oil nature of table 3
| 20 DEG C of density/(kg/m3) | 0.825 |
| C content/% | 81.1 |
| H content/% | 13.7 |
| O content/% | 5.2 |
| S contents/ppm | <1 |
| Cut yield/% | |
| <520℃ | 65.5 |
| >520℃ | 34.5 |
As can be seen that Xinjiang cottonseed oil is after hydrofinishing, its<The yield of 520 DEG C of product oil is 65.5%, and raw material
Cut is above 520 DEG C, and this represents that the conversion ratio of triglycerides in raw material is 65.5%.
Two kinds of oil mixing：
The first step is tested to obtained bio-oil hydrofined oil with full fraction of coal tar according to mass ratio 5:5 100
It is sufficiently mixed under conditions of DEG C, and settles out bottom residual oil, top obtains the miscella of coal tar and biomass hydrofined oil.
Table 4 gives the property of coal tar raw material and the property of miscella.
The coal tar raw material of table 4 and pix carbonis praeparsta property
| Coal tar raw material | Mix oil nature | |
| 20 DEG C of density/(kg/m3) | 1.058 | 0.942 |
| Asphalt content/% | 10.2 | 4.3 |
| Ash content/% | 0.17 | 0.02 |
| Mechanical admixture/% | 0.05 | <0.01 |
| S contents/ppm | 1600 | 800 |
| Tenor/μ g/g | ||
| Fe | 106 | 35 |
| Ca | 133 | 43 |
| Na | 36 | 13 |
From table 4, it can be seen that after coal tar is mixed with the hydrofined oil of cottonseed oil, the miscella obtained after sedimentation it is miscellaneous
Matter content is below coal tar with cottonseed oil hydrofined oil according to 1:1 mixed calculated value, especially ash content, machine are miscellaneous obtains
Significantly reduce.Because after cottonseed oil hydrofined oil is mixed with coal tar, by precipitating product in the residual oil of bottom
Most mechanical admixtures, ash content, and part metals are gathered.So that the property of miscella is substantially improved, also subsequently add for it
Hydrogen provides relatively good raw material.
The hydrofinishing of miscella：
The miscella hydrofinishing obtained by second step is carried out on fixed bed hydrogenation experimental rig, hydrogenation catalyst is used
Foregoing self-control macroporous catalyst I.
Hydroprocessing conditions are:Pressure 7.0MPa, 365 DEG C of reaction temperature, air speed 2.0h-1, hydrogen to oil volume ratio 1000.At this
The hydrofinishing oil nature obtained under operating condition is shown in Table 5.
The hydrofinishing oil nature of table 5
| 20 DEG C of density/(kg/m3) | 0.861 |
| H content/% | 13.2 |
| O content/% | <0.2 |
| S contents/ppm | 153 |
| Boiling range/DEG C | |
| Initial boiling point | 98 |
| 10% distillates a little | 230 |
| 50% distillates a little | 296 |
| 70% distillates a little | 332 |
| 90% distillates a little | 404 |
| 95% distillates a little | 461 |
Fractionation：
Hydrofined oil described in table 5 is fractionated, naphtha cut, diesel oil distillate and marine fuel oil distillate is obtained,
The property of wherein diesel oil distillate and marine fuel oil distillate is shown in Table 6.
Table 6 is fractionated obtained diesel oil and marine fuel oil nature
As can be seen from Table 6, diesel oil density, sulfur content, flash-point, Cetane number and the boiling range obtained by this method is full
Sufficient state V diesel oil standards requirement.Bunker fuel oil indices also meet No. 4 fuel oil requirements of ship.
Embodiment 2
Prepare catalyst：
Macropore dry glue powder 141.0g is taken, sesbania powder 3.0g, borax (analysis is pure) 2.5g is added, is well mixed.It is commercially available
PVA1788 powder 8.0g, are dissolved in 115mL water, dissolving is added in well mixed dry glue powder after finishing under stirring, slow heating,
After multiple kneading, a diameter of 1.5mm cylindrical bar is extruded into after standing 15 minutes, bar is extruded after being dried 6 hours at 150 DEG C,
Taken out after being calcined 5 hours at 600 DEG C, be designated as carrier b.Take molybdenum oxide (AR) 4.01g, basic nickel carbonate (AR) 1.40g, dense phosphorus
Acid (AR) 0.81g, add water 100mL, the lower continuous heating backflow of stirring, stops heating after band solution went clear, is down to room temperature standby.
Support samples b80g is taken, is impregnated with hole saturation, after dipping is finished and dried in the air in fume hood 3 hours, in being dried 3 hours at 150 DEG C,
It is calcined 20 hours at 450 DEG C in Muffle furnace, is designated as catalyst II.
To bio-oil hydrofinishing：
Carry out bio-oil hydrogenation first on fixed bed hydrogenation experimental rig, bio-oil is Xinjiang cottonseed oil, and it is led
Property is wanted to be shown in Table 2.Hydrogenation catalyst uses business Hydrobon catalyst FHUDS5.
Hydroprocessing conditions are:Pressure 5.0MPa, 280 DEG C of reaction temperature, air speed 1.0h-1, hydrogen to oil volume ratio 2000.
Hydrofinishing is carried out to Xinjiang cottonseed oil under the operating conditions, cottonseed oil hydrofined oil is obtained, its property
It is shown in Table 7.
The Xinjiang cottonseed oil hydrofinishing oil nature of table 7
| 20 DEG C of density/(kg/m3) | 0.831 |
| C content/% | 82.3 |
| H content/% | 13.9 |
| O content/% | 4.9 |
| S contents/ppm | <1 |
| Cut yield/% | |
| <520℃ | 66.3 |
| >520℃ | 33.7 |
As can be seen that Xinjiang cottonseed oil is after hydrofinishing, its<The yield of 520 DEG C of product oil is 66.3%, and raw material
Cut is above 520 DEG C, and this represents that the conversion ratio of triglycerides in raw material is 66.3%.
Two kinds of oil mixing：
The first step is tested to obtained bio-oil hydrofined oil with full fraction of coal tar according to mass ratio 3:7 at 80 DEG C
Under conditions of be sufficiently mixed, and settle out bottom residual oil, top obtains the miscella of coal tar and biomass hydrofined oil.Table
8 give the property of coal tar raw material and the property of miscella.
The coal tar raw material of table 8 and pix carbonis praeparsta property
| Coal tar raw material | Mix oil nature | |
| 20 DEG C of density/(kg/m3) | 1.058 | 0.99 |
| Asphalt content/% | 10.2 | 3.9 |
| Ash content/% | 0.17 | 0.019 |
| Mechanical admixture/% | 0.05 | <0.01 |
| S contents/ppm | 1600 | 790 |
| Tenor/μ g/g | ||
| Fe | 106 | 34 |
| Ca | 133 | 39 |
| Na | 36 | 9 |
As can be seen from Table 8, after coal tar is mixed with the hydrofined oil of cottonseed oil, the miscella obtained after sedimentation it is miscellaneous
Matter content is below coal tar with cottonseed oil hydrofined oil according to 7:3 mixed calculated values, especially ash content, machine are miscellaneous obtains
Significantly reduce.Because after cottonseed oil hydrofined oil is mixed with coal tar, by precipitating product in the residual oil of bottom
Most mechanical admixtures, ash content, and part metals are gathered.So that the property of miscella is substantially improved, also subsequently add for it
Hydrogen provides relatively good raw material.
The hydrofinishing of miscella：
The miscella hydrofinishing obtained by second step is carried out on fixed bed hydrogenation experimental rig, hydrogenation catalyst is used
Foregoing self-control macroporous catalyst II.
Hydroprocessing conditions are:Pressure 5.0MPa, 320 DEG C of reaction temperature, air speed 2.0h-1, hydrogen to oil volume ratio 2000.At this
The hydrofinishing oil nature obtained under operating condition is shown in Table 9.
The hydrofinishing oil nature of table 9
| 20 DEG C of density/(kg/m3) | 0.853 |
| H content/% | 14.5 |
| O content/% | <0.2 |
| S contents/ppm | 137 |
| Boiling range/DEG C | |
| Initial boiling point | 95 |
| 10% distillates a little | 224 |
| 50% distillates a little | 285 |
| 70% distillates a little | 330 |
| 90% distillates a little | 396 |
| 95% distillates a little | 449 |
Fractionation：
Hydrofined oil described in table 9 is fractionated, naphtha cut, diesel oil distillate and marine fuel oil distillate is obtained,
The property of wherein diesel oil distillate and marine fuel oil distillate is shown in Table 10.
Table 10 is fractionated obtained diesel oil and marine fuel oil nature
As can be seen from Table 10, diesel oil density, sulfur content, flash-point, Cetane number and the boiling range obtained by this method is equal
Meet state V diesel oil standard requirements.Bunker fuel oil indices also meet No. 4 fuel oil requirements of ship.
Embodiment 3
To bio-oil hydrofinishing：
Carry out bio-oil hydrogenation first on fixed bed hydrogenation experimental rig, bio-oil is Xinjiang cottonseed oil, and it is led
Property is wanted to be shown in Table 2.Hydrogenation catalyst uses business Hydrobon catalyst FHUDS5.
Hydroprocessing conditions are:Pressure 8.0MPa, 380 DEG C of reaction temperature, air speed 5.0h-1, hydrogen to oil volume ratio 500.
Hydrofinishing is carried out to Xinjiang cottonseed oil under the operating conditions, cottonseed oil hydrofined oil is obtained, its property
It is shown in Table 11.
The Xinjiang cottonseed oil hydrofinishing oil nature of table 11
| 20 DEG C of density/(kg/m3) | 0.812 |
| C content/% | 80.9 |
| H content/% | 14.6 |
| O content/% | 4.7 |
| S contents/ppm | <1 |
| Cut yield/% | |
| <520℃ | 66.1 |
| >520℃ | 33.9 |
As can be seen that Xinjiang cottonseed oil is after hydrofinishing, its<The yield of 520 DEG C of product oil is 66.1%, and raw material
Cut is above 520 DEG C, and this represents that the conversion ratio of triglycerides in raw material is 66.1%.
Two kinds of oil mixing：
The first step is tested to obtained bio-oil hydrofined oil with full fraction of coal tar according to mass ratio 7:3 150
It is sufficiently mixed under conditions of DEG C, and settles out bottom residual oil, top obtains the miscella of coal tar and biomass hydrofined oil.
Table 12 gives the property of coal tar raw material and the property of miscella.
The coal tar raw material of table 12 and pix carbonis praeparsta property
As can be seen from Table 12, after coal tar is mixed with the hydrofined oil of cottonseed oil, the miscella obtained after sedimentation
Impurity content is below coal tar with cottonseed oil hydrofined oil according to 3:7 mixed calculated values, especially ash content, machine are miscellaneous to be obtained
To significantly reducing.Because after cottonseed oil hydrofined oil is mixed with coal tar, by precipitating in the residual oil of bottom
Most mechanical admixtures, ash content, and part metals are gathered.So that the property of miscella is substantially improved, it is also follow-up for its
Hydrogenation provides relatively good raw material.
The hydrofinishing of miscella：
The miscella hydrofinishing obtained by second step is carried out on fixed bed hydrogenation experimental rig, hydrogenation catalyst is used
Foregoing self-control macroporous catalyst I.
Hydroprocessing conditions are:Pressure 8.0MPa, 400 DEG C of reaction temperature, air speed 0.2h-1, hydrogen to oil volume ratio 500.At this
The hydrofinishing oil nature obtained under operating condition is shown in Table 13.
The hydrofinishing oil nature of table 13
Fractionation：
Hydrofined oil described in table 13 is fractionated, naphtha cut, diesel oil distillate and marine fuel oil distillate is obtained,
The property of wherein diesel oil distillate and marine fuel oil distillate is shown in Table 14.
Table 14 is fractionated obtained diesel oil and marine fuel oil nature
As can be seen from Table 14, diesel oil density, sulfur content, flash-point, Cetane number and the boiling range obtained by this method is equal
Meet state V diesel oil standard requirements.Bunker fuel oil indices also meet No. 4 fuel oil requirements of ship.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (9)
1. the production method of a kind of biodiesel and bunker fuel oil, it is characterised in that comprise the following steps：
The bio-oil after hydrofinishing is added into full fraction of coal tar, is stirred for the dregs of fat are settled out, removes the dregs of fat,
Obtain miscella；
To the miscella hydrofinishing, then it is fractionated and obtains diesel oil and bunker fuel oil；
The temperature during stirring is 80-150 DEG C；
The percentage by weight of the full fraction of coal tar is no more than 70%.
2. the production method of biodiesel according to claim 1 and bunker fuel oil, it is characterised in that the stirring
When temperature be 100-150 DEG C.
3. the production method of biodiesel according to claim 1 and bunker fuel oil, it is characterised in that to described mixed
The method for closing oily hydrofinishing is：
It is that 5.0-8.0MPa, temperature are 320-400 DEG C in pressure, air speed is in the solid-bed reactor equipped with catalyst
0.2-2.0h- 1, hydrogen to oil volume ratio be 500-2000 under conditions of react.
4. the production method of biodiesel according to claim 3 and bunker fuel oil, it is characterised in that to described mixed
When closing oily hydrofinishing, pressure is that 5.0-7.0MPa, temperature are 320-365 DEG C, and air speed is 1.5-2.0h- 1, hydrogen oil volume
Than for 1000-2000.
5. the production method of biodiesel according to claim 3 and bunker fuel oil, it is characterised in that the catalysis
Agent includes the main carrier being made up of polyvinyl alcohol, macropore dry glue powder and auxiliary agent, and is impregnated with metal on the carrier.
6. the production method of biodiesel according to claim 5 and bunker fuel oil, it is characterised in that the metal
For Ni-Mo, one or more combinations in Co-Mo and Ni-W.
7. the production method of biodiesel according to claim 5 and bunker fuel oil, it is characterised in that the auxiliary agent
For sesbania powder and/or borax.
8. the production method of biodiesel according to claim 5 and bunker fuel oil, it is characterised in that the catalysis
The preparation method of agent is：
According to formula, after solvent polyethylene dissolving alcohol, it is mixed with macropore dry glue powder and auxiliary agent, then kneading extrusion, afterwards
5-6h is dried at 120-150 DEG C, 3-5h is calcined at 550-600 DEG C, carrier is made；
With hole saturation impregnating metal, 3-5h is dried at 120-150 DEG C afterwards, 20-25h is calcined at 350-450 DEG C.
9. the production method of biodiesel according to claim 1 and bunker fuel oil, it is characterised in that the process
Bio-oil after hydrofinishing is obtained using following methods：
Original biomass oil is imported in the solid-bed reactor equipped with catalyst, is that 5.0-8.0MPa, temperature are in pressure
280-380 DEG C, air speed is 1.0-5.0h- 1, hydrogen to oil volume ratio be 500-2000 under conditions of, carry out hydrofinishing.
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