CN102086411A - Method for preparing light oils from heavy oil modified with alkali under hydrothermal conditions - Google Patents
Method for preparing light oils from heavy oil modified with alkali under hydrothermal conditions Download PDFInfo
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- CN102086411A CN102086411A CN2011100047979A CN201110004797A CN102086411A CN 102086411 A CN102086411 A CN 102086411A CN 2011100047979 A CN2011100047979 A CN 2011100047979A CN 201110004797 A CN201110004797 A CN 201110004797A CN 102086411 A CN102086411 A CN 102086411A
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Abstract
The invention relates to a method for preparing light oils from heavy oil modified with alkali under hydrothermal conditions. The method comprises the following steps: firstly, mixing alkali and water to prepare heavy oil modifying alkali liquor; and secondly, mixing alkali liquor and heavy oil in a volume ratio of 1:0.5-1:10 to preheat, then sending to a hydrothermal reactor, treating at 280-480 DEG C under 10-35MPa for 0.2-8h, separating the three phases of the treated product, namely the gas phase, the aqueous phase and the oil phase, and performing distillation to the product oil to obtain light oils such as gasoline and diesel oil. Compared with the prior art, the heavy oil modifying method of the invention can be performed under subcritical and supercritical hydrothermal conditions; and by using alkali, the coking of heavy oil can be effectively avoided, the yield of light oils can be increased and the removal effect of the impurities in heavy oil is better.
Description
Technical field
The present invention relates to a kind of method for modifying of heavy oil, especially relate to and utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition.
Background technology
At present, oil is still one of irreplaceable main energy sources of human social development, along with (surpassing) heaviness of crude oil with to the lightweight oil growth of requirement, it will be one of important developing direction of 21 century China's oil refining industry that the development heavy oil degree of depth transforms, increases lightweight oil output.
The heavy oil treatment technology of having developed comprises: method or its combination procesies such as delayed coking technology, catalytic cracking technology, solvent deasphalting technology, viscosity breaking technology and heavy-oil hydrogenation technology.Wherein, but delay coking process because advantages such as strong, the low increasing output of diesel oil of cost of investment of its adaptability to raw material become main in the world heavy oil modification means.But the shortcoming of this technology is a contaminate environment, poor product quality.Eighties of last century is according to the characteristics of the homemade crude oil of China, and China adopts catalytic cracking process upgrading heavy oil (product still needs hydrofining) more, but along with the heaviness of petroleum and poor qualityization, high carbon residue and heavy metal content are faced with formidable challenges this technology.The solvent deasphalting technological operation is flexible, energy consumption is low, fails fine solution but the weak point of this technology is the outlet of by product gilsonite.And the viscosity breaking technology can only reduce the viscosity of heavy oil, can not directly obtain the product of lighting.Compare with preceding several technologies, the benefit of hydrogenation technique maximum is exactly to refine out high-quality oil product, therefore, becomes the important development direction of heavy oil lighting.
The advantages such as high temperature, high pressure water are inexpensive except having, nontoxic, non-secondary pollution, also have some unique character, as: along with changing to serially, the increase density of pressure is similar to density of liquid, relative permittivity is in low-density overcritical high-temperature zone, its numerical value has reduced an order of magnitude, at this moment supercritical water is similar to nonpolar organic solvent, and the viscosity of supercritical water is low, show the solvation feature, and spread coefficient increases, resistance to mass transfer reduces, and can dissolve each other with any ratio with nonpolar oily substance, and all gases all can dissolve each other with it.In recent years, hydrothermal technique obtains research and application with its unique advantage in a lot of fields as reaction media.
The application of relevant hydrothermal technique aspect heavy oil modification, Chinese patent CN 200610026906.6 discloses a kind of method of preparing light oil from supercritical water modified vacuum residuum, this method is compared the coking reaction of having avoided heavy oil substantially with thermally splitting, but because the hydrogen dividing potential drop is lower in the reaction system, to other inferior heavy oil handling, effect is still undesirable.
Chinese patent CN 200810228351.2 disclose a kind of under the overcritical or undercritical conditions of hydrogen supply dissolvent the method for upgrading heavy oil owing to use hydrogen supply dissolvent, production cost is higher, has reduced the feasibility of this method practical application.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of output that improves lightweight oil in order to overcome the defective that above-mentioned prior art exists, and utilizes the alkali upgrading heavy oil to prepare the method for lightweight oil under the effective hydrothermal condition of Impurity removal.
Purpose of the present invention can be achieved through the following technical solutions:
Utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition, it is characterized in that, this method may further comprise the steps:
(1) with the alkali heavy oil modification alkali lye that makes soluble in water;
(2) then alkali lye and heavy oil are mixed and preheating by 1: 0.5～1: 10 volume ratio;
(3) mixture after the preheating is sent in the hydrothermal reactor, and controlled temperature is 280～480 ℃, and pressure is 10～35MPa, handles 0.2～8h;
(4) product after handling is separated, comprise gaseous fraction, water component and oil ingredient, the hydrogen recovery utilization that comprises in the gaseous fraction;
(5) water component carries out fractionation to oil ingredient and handles with after oil ingredient separates, and obtains clean or white.
Described alkali is Ca (OH)
2, NaOH or KOH.
The concentration of described heavy oil modification alkali lye is 0.1～2.5mol/L.
Described heavy oil is one or more in heavy former (thick) oil, oil-sand, oil shale or the residual oil.
Described hydrothermal reactor is high pressure tank reactor or Continuous Flow tubular reactor.
Compared with prior art, the present invention has the following advantages:
(1) under hydrothermal condition, water can produce hydrogen with the coke reaction that produces in the reaction system, but should reaction required energy is more, and the participation of alkali can significantly reduce the Δ H value of this reaction, helps the carrying out of this reaction.Under the 298K, the standard Δ H data of the water carbon reaction that water carbon and alkali participate in as follows (Data Source: David R Lide, CRC Handbook of Chemistry and Physics, 80th ed, 1999-2000):
C+H
2O＝CO+H
2 ΔH
298＝+131.3kJ/mol (1)
2C(s)+2NaOH(aq)+3H
2O(g)＝Na
2CO
3(aq)+4H
2(g)+CO
2(g)
ΔH
298＝+114.8kJ/mol (2)
C(s)+2NaOH(aq)+H
2O(g)＝Na
2CO
3(aq)+2H2(g) ΔH
298＝+24.7kJ/mol (3)
Can find out that from these standard thermodynamic data alkali produces H-H reaction to water carbon significant promoter action.Therefore, the adding of alkali has reduced the required temperature of product H-H reaction under the hydrothermal condition, has improved the dividing potential drop of hydrogen in the reaction system, has promoted the raising of lightweight oil output.
(2) the residual oil decarbonization process will reduce the H/C ratio of a part of raw material, inevitably will produce the smaller condensation product of a part of carburet hydrogen and H/C one coke and residual oil, thereby makes the yield of light oil of carbon rejection process can be very not high.And residual oil hydro-thermal alkali modifying process can utilize carbon contained in the residual oil to improve liquid product yield well, and quality product is increased, and can handle the residual oil of high-sulfur, medium relatively metal content and carbon residue content.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
The alkali lye of preparation 1.0mol/L mixes 10mL alkali lye and 5mL residual oil by 1: 0.5 volume ratio, puts into autoclave reactor, uses helium purge, displaces the air in the reactor.After the preheating, the fused salt of putting into 320 ℃ reacts, and reactor pressure reacts after 5 hours and takes out, with being water-cooled to room temperature about 14～17MPa at this moment.Open reactor, collect unreacted hydrogen in the reactor, recycle with gas extractor.Liquid product carries out four proximate analyses and ultimate analysis after collecting.Analytical results sees Table 1.
Embodiment 2
The alkali lye of preparation 2.0mol/L mixes 2mL alkali lye and 13mL residual oil by 1: 6 volume ratio, puts into autoclave reactor, uses helium purge, displaces the air in the reactor.After the preheating, the fused salt of putting into 320 ℃ reacts, and reactor pressure reacts after 5 hours and takes out, with being water-cooled to room temperature about 14～17MPa at this moment.Open reactor, collect unreacted hydrogen in the reactor, recycle with gas extractor.Liquid product carries out four proximate analyses and ultimate analysis after collecting.Analytical results sees Table 1.
Embodiment 3
Implementation step is with embodiment 1, and temperature of reaction is 450 ℃, and reactor pressure reacted 2 hours about 20～23MPa.Analytical results sees Table 1.
Embodiment 4
Implementation step is with embodiment 2, and temperature of reaction is 450 ℃, and reactor pressure reacted 2 hours about 20～23MPa.Analytical results sees Table 1.
Embodiment 5
This example is a comparative example, and implementation step is identical with embodiment 4, only uses pure water to replace alkaline solution, and analytical results sees Table 1.
Embodiment 6
Use continuous hydro-thermal device to realize the upgrading of heavy oil.The alkali lye of preparation 1.0mol/L, get 1L alkali lye respectively and 1L residual oil is put into feed containers, under identical input speed, use high pressure plunger pump that alkali lye and residual oil are sent into mixing tank respectively, raw material through mix, preheating is laggard goes into the hydrothermal reactor reaction, 320 ℃ of temperature of reaction, successive reaction system internal pressure is controlled at about 20MPa by back pressure valve, and the residence time of reaction mixture is used sleeve pipe recirculated water cooling cooling at the continuous conduit end after reaction finishes after being 0.2 hour.Liquid product carries out four proximate analyses and ultimate analysis after collecting.Analytical results sees Table 2.
Embodiment 7
This example is a comparative example, and implementation step is identical with embodiment 6, only uses pure water to replace alkaline solution, and analytical results sees Table 2.
The analytical results of table 1 raw material and embodiment product
The analytical results of table 2 raw material and embodiment product
Embodiment 8
Utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition, its technical process may further comprise the steps as shown in Figure 1:
(1) with Ca (OH)
2Soluble in water, making concentration is 0.1mol/L heavy oil modification alkali lye 1;
(2) then alkali lye 1 and residual oil 2 is mixed in mixing tank 3 by 1: 0.5 volume ratio and through preheater 4 preheatings;
(3) mixture after the preheating is sent in the hydrothermal reactor 5, and employed hydrothermal reactor 5 is the high pressure tank reactor, and controlled temperature is 280 ℃, and pressure is 35MPa, handles 8h;
(4) product after handling is separated by separator 6, isolate gaseous fraction, water component and oil ingredient, the hydrogen that comprises in the gaseous fraction is collected in the hydrogen storage device 7 and is reclaimed;
(5) water component and oil ingredient are after water-and-oil separator 8 separates, and water component is collected in the wastewater disposal basin 9, and oil ingredient places separation column 10 to carry out fractionation and handles, and obtains lighting product 11.
Embodiment 9
Utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition, may further comprise the steps:
(1) NaOH is soluble in water, making concentration is 2.5mol/L heavy oil modification alkali lye;
(2) then alkali lye and heavy former (thick) oil is mixed and preheating by 1: 10 volume ratio;
(3) mixture after the preheating is sent in the Continuous Flow tubular reactor, and controlled temperature is 480 ℃, and pressure is 10MPa, handles 0.2h;
(4) product after handling is separated by separator, isolate gaseous fraction, water component and oil ingredient, the hydrogen that comprises in the gaseous fraction is collected in the hydrogen storage device and is reclaimed;
(5) water component and oil ingredient are after water-and-oil separator separates, and water component is collected in the wastewater disposal basin, and oil ingredient places separation column to carry out fractionation and handles, and obtains clean or white.
Claims (5)
1. utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a hydrothermal condition, it is characterized in that this method may further comprise the steps:
(1) with the alkali heavy oil modification alkali lye that makes soluble in water;
(2) then alkali lye and heavy oil are mixed and preheating by 1: 0.5～1: 10 volume ratio;
(3) mixture after the preheating is sent in the hydrothermal reactor, and controlled temperature is 280～480 ℃, and pressure is 10～35MPa, handles 0.2～8h;
(4) product after handling is separated, comprise gaseous fraction, water component and oil ingredient, the hydrogen recovery utilization that comprises in the gaseous fraction;
(5) water component carries out fractionation to oil ingredient and handles with after oil ingredient separates, and obtains clean or white.
2. utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition according to claim 1, it is characterized in that, described alkali is Ca (OH)
2, NaOH or KOH.
3. utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition according to claim 1, it is characterized in that, the concentration of described heavy oil modification alkali lye is 0.1～2.5mol/L.
4. utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition according to claim 1, it is characterized in that, described heavy oil is one or more in heavy former (thick) oil, oil-sand, oil shale or the residual oil.
5. utilize the alkali upgrading heavy oil to prepare the method for lightweight oil under a kind of hydrothermal condition according to claim 1, it is characterized in that, described hydrothermal reactor is high pressure tank reactor or Continuous Flow tubular reactor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849461A (en) * | 2015-06-11 | 2018-03-27 | 艾格耐特能量资源有限公司 | Modify residue, heavy oil and plastics |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948754A (en) * | 1974-05-31 | 1976-04-06 | Standard Oil Company | Process for recovering and upgrading hydrocarbons from oil shale and tar sands |
| CN101724450A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for modifying heavy oil |
-
2011
- 2011-01-11 CN CN2011100047979A patent/CN102086411A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948754A (en) * | 1974-05-31 | 1976-04-06 | Standard Oil Company | Process for recovering and upgrading hydrocarbons from oil shale and tar sands |
| CN101724450A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for modifying heavy oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849461A (en) * | 2015-06-11 | 2018-03-27 | 艾格耐特能量资源有限公司 | Modify residue, heavy oil and plastics |
| CN113150813A (en) * | 2015-06-11 | 2021-07-23 | 莱斯拉控股有限公司 | Upgrading residues, heavy oils and plastics |
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Application publication date: 20110608 |