CN101402869B - Liquefaction state dry distillation oil refining process for shale and produced shale oil thereof - Google Patents
Liquefaction state dry distillation oil refining process for shale and produced shale oil thereof Download PDFInfo
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Abstract
The invention discloses a carbonization oil refining technique of fluidized shale, which includes the following steps: a) the powder of the shale is heated to a carbonization temperature under a fluidization state; b) the powder of the shale after deoiling in the oil gas is separated; c) the oil gas is washed and cooled by water; and d) the mixture of oil, water and dust after being washed and cooled is phase-split, thus obtaining the shale oil. The invention also discloses the shale oil produced by the carbonization oil refining technique of fluidized shale. Comparing the mode of cooling the oil gas by water flushing of the carbonization oil refining technique provided by the invention with a mode of cooling the oil gas by oil flushing, the water fully washes the oil gas; the mixture of water, oil and dust can form an upper oil layer, a middle water layer and a bottom oil mud layer through standing and separation; moreover, the water in the water layer can be recycled for washing the oil gas. The mode of water flushing activates the whole technical flows, thus ensuring the carbonization oil refining technique can still stably run after continuously running for 192 hours. Therefore, the demand of continuous industry production can be met and the production efficiency is improved.
Description
Technical field
The present invention relates to the oil refining process field of shale, relate in particular to a kind of fluidization destructive distillation oil refining process of shale and the shale oil that makes of technology thus thereof.
Background technology
Along with the development of world economy, the consumption of oil increases sharply, yet petroleum resources but be becoming tight by day.Calendar year 2001, the consumption of world's crude oil is 35.106 hundred million tons, it is predicted, by 2010, the consumption of world's crude oil will reach 44.74 hundred million tons.According to the existing prospective oil of verifying, global petroleum resources can only be kept about about 40 years exploitation, therefore, seek the concern that the alternative energy has caused global various countries.
The development and utilization of resinous shale is one and well selects.Resinous shale is called oil shale, shale etc. again, the unified shale that is called among the present invention.Shale standing stock on earth are very abundant, are one of flammable mineral products.Shale can extract shale oil, and the shale oil stock number of containing in the whole world shale has 3,662 hundred million tons substantially, Duos 50% at least than traditional petroleum resources.The reserves that contain shale oil in China's shale are 29,000,000,000 tons, occupy the 4th in the world, are only second to the U.S., Brazil and the FSU.Shale is made up of organic substance and inorganic substance.Inorganic substance are common in the shale has quartz, clay, carbonate etc., also contains the compound of copper, nickel, cobalt, molybdenum, titanium, vanadium etc. sometimes.Organic substance can be divided into two types in the shale: one type female for oil, and oily mother is for becoming oil substances, and principal element consists of C, H, N, S, O etc.; Another kind of is pitch, accounts for 1% of shale organic content.The oil mother is a kind of mixture with high polymer of three-dimensional structure.Carbon among the oil mother mainly exists with aliphatics and cycloalkanes structure, and partially aromatic is also arranged.As long as, just can obtain the shale oil of similar petroleum crude oil so can extract the oily mother in the shale.General oil length is 4～20% in the shale, reaches as high as 30%, and thermal value is 4.18～16.75 * 10
6J/kg (joule/kilogram).
The destructive distillation oil refining process of shale can be divided into underground retoring oil refining process and ground destructive distillation oil refining process.The underground retoring oil refining process is meant and buries in subterranean shale without exploitation, directly manages to heat destructive distillation underground, generates shale oil, and then be transported to ground.The underground retoring oil refining process is called the ground destructive distillation again.The oil gas that underground retoring generates is prone to leak to subterranean strata, and the yield of oil is not high, and causes underground oil and gas to pollute easily.On the ground destructive distillation oil refining process is meant that shale through strip mining transformation or underground mining, delivers to ground, through crushing and screening to required granularity or lumpiness, gets into the destructive distillation of gas retort internal heating, generates shale oil gas and shale semicockes or shale ashes.Destructive distillation institute heat requirement is called the indirect heat transfer method through the method that wall imports the destructive distillation chamber into, and the method for the method heating shale that directly contacts through thermal barrier and shale is the direct heat transfer method.With respect to the indirect heat transfer method, the heat transfer rate of direct heat transfer method is very fast, heat transfer efficiency is also high.The direct heat transfer method can be divided into gaseous heat-carrier method and solid heat carrier method again.
There are a plurality of countries to grasp the destructive distillation oil refining process of shale in the world, the upright cylindrical furnace retorting technique of Petroleo Brasileiro SA's exploitation is for example arranged, be i.e. the Petrosix technology; Estonian Kiviter and Galoter technology; The associating oil SGR and the ToscoII retorting technique of the U.S.; The Jeseco retorting technique of Japan; The LR retorting technique of Germany; Canadian ATP technology; The Fushun stove technology of China etc.
See also Fig. 1, Fig. 1 be the present invention on stream the oil wash that utilizes of initial stage design accomplish the artwork of destructive distillation oil refining technology.As can be seen from Figure 1, get into separation column from the de-oiling reactor drum through the oil gas of separating, in separation column, utilize lightening shale oil that oil gas is washed, the fluid after the washing gets into the three phase separation jar to be separated, and after separating can obtain shale oil.Though the method for oil wash can obtain shale oil, yet the continuous cycle of operation of this technology is short, and the lower pipeline of separation column produces comparatively serious latch up phenomenon after moving about 10 hours, the cleaning so this technology must be stopped after operation for some time.
Summary of the invention
To above-mentioned defective, the technical problem that the present invention solves is that a kind of fluidization destructive distillation oil refining process of shale is provided, and this technology can be moved continuously.
In order to realize above goal of the invention, the present invention adopts following technical scheme:
A kind of destructive distillation oil refining process of shale comprises the steps:
A) shale powder is heated to pyrolysis temperature under fluidized state;
B) shale powder after the de-oiling in the middle of the separation oil and gas;
C) with water washing cooling oil gas;
D) the mixture branch of cooled water of washing and oil gas is separated and promptly obtains shale oil.
Fluidization destructive distillation oil refining process for shale provided by the present invention; What shale powder was accomplished in the step a) is pyrolytic reaction; What accomplish in the step b) is shale powder and the separating of oil gas, and what step c) was accomplished is the washing process of cooling, and what step d) was accomplished is to separate the process that obtains shale oil.
After separating shale de-oiling fine powder and oil gas; Though the oil gas after the separation has divided through overwinding and has separated; But inevitably can residual a spot of dust in the oil gas, if use oil that oil gas is separated, dust also can get in the oil so; These oil that contain dust must be used for washing the oil gas that contains low amounts of dust again through after the dedusting lock out operation.Go out dust and be difficult to and the oil that contains dust wants high efficiency separation; Separation efficiency is low, and thus, the content of the dust in the circulation cleaning oil will be accumulated; Impel greasy filth increase in the oil; Viscosity increases, and stops up the equipment pipe of condensate recovery system, causes oil wash technology after moving more than 10 hour continuously, just must stop.If using water instead washs oil gas; Water, oil, dust mixture will form top oil reservoir, middle water layer and bottom greasy filth layer through leaving standstill the phase-splitting processing; Be that dust in the oil gas mainly gets into the greasy filth layer; Dust content in the water layer is extremely low, is used for washing oil gas so the water in the water layer can circulate.The mode of washing has been got through whole process flow, makes that destructive distillation oil refining process later on still can steady running continuous operation 192 hours, can satisfy the needs of continuous industry production, has improved production efficiency.
Down in the face of carrying out detailed argumentation and introduction in each step, and provide some preferred or can the alternate technical scheme.
A) shale powder is heated to pyrolysis temperature under fluidization
Before address, this step is the step of shale powder generation scission reaction.The principle of fluidization destructive distillation oil refining process is: under suitable temperature, make organic macromolecule polymkeric substance generation scission reaction in the shale powder to generate materials such as semicoke, oil and gas, then the condensing and recycling oily substance.
In this step, the organic macromolecule polymkeric substance in the shale, it is female to be also referred to as oil, promptly pyrolytic reaction can take place more than 300 ℃; And can collect shale oil, along with the rising of temperature, the productive rate of shale oil also increases; Yet along with the rising of temperature, whole technology energy needed also improves, and along with the rising of temperature; The meeting that scission reaction is carried out is very complete, and the gas that obtains increases, so pyrolysis temperature need be controlled at a suitable scope.Through discovering of contriver, to destructive distillation oil refining process provided by the present invention, when pyrolysis temperature is 450～550 ℃; The yield of shale oil had both maintained a higher level; When pyrolysis temperature was 480～520 ℃, the yield of shale oil was higher, can reach more than 90%.For the shale in the different places of production, pyrogenous optimum temps changes slightly, and for example: the best pyrolysis temperature of Maoming shale is 470～480 ℃; The best pyrolysis temperature of Yilan shale is about 500 ℃; The pyrolysis temperature of Longkou shale is about 510 ℃.
The raw material of using in this step---shale powder can be carried out fragmentation through crusher, and the particle diameter of shale powder is chosen as less than 3000 microns, and preferred particle diameter is 50～3000 microns.Shale powder is different from the catalyzer of using in Coal Chemical Industry and the petrochemical complex; Shale powder is fractured into flaky particle easily; Rather than the good powder raw material of sphericity, to this, the contriver finds through a large amount of experimental studies; The particle size range selection of shale powder is preferable less than 3000 microns, and the shale powder of such particle size range has promptly guaranteed the destructive distillation effect; The dust that oil gas is taken out of is few again, thereby the greasy filth amount that forms is less.And find through experimental study; Shale powder is very easy to the broken sheet powder that forms small particle size in the process of grinding; That is to say that in the process of glazing vane rock dust the sheet powder of the small particle size of formation can be higher relatively, and is more less than the shale powder of 20 microns content; Here refer to more be with respect to the powder of other kinds, the coal powder that for example grinds.In the de-oiling reactor drum to revolve branch very low for the shale powder separation efficiency less than 20 microns; Therefore this part shale powder is very easily come out from the de-oiling reactor drum with oil gas, finally forms greasy filth and is difficult to separate, if minimum grain size is brought up to more than 50 microns; So also can be more than 20 microns through the shale powder major part after the reaction; After revolving branch, separatedly get off greater than 20 microns shale powder is as easy as rolling off a log, so preferably use the grinding raw material more than 50 microns.The particle diameter upper limit of shale powder can not be too big, the too big problem that two aspects are arranged afterwards: the first, when particle diameter is big; The energy that its fluidisation is needed is bigger, and the second, when particle diameter is big; The scission reaction of shale powder can be not exclusively; Perhaps under suitable temperature, need the longer time just can make the inner oily female cracking of macrobead shale powder, and the quality of the oil of output also not necessarily can meet the requirements; The oil yield is not high yet, and the processing power of device also can't improve.This mainly be because, in the fluidization destructive distillation oil refining process of shale, in the residence time in promoting standpipe and de-oiling reactor drum; Sufficient scission reaction takes place; Can enhance productivity like this, yet also must take into account reaction depth, can not make the further cracking of oil gas that scission reaction generates and become gas; Must take into account the problem of energy expenditure in addition; In these problems, finding out a suitable selection is the comparison difficulty, and the inventor gropes through secular test, thinks that the shale powder raw material in above-mentioned particle size range is proper.
Heating described in the step a) makes that the method for shale generation pyrolytic reaction can be to utilize gaseous heat-carrier that the shale powder raw material is heated, and also can use solid thermal carriers that the shale powder raw material is heated.Gaseous heat-carrier is to utilize the gas that produces in the technological processs such as coal gas, flue gas, producer gas, because can save energy consumption.Use the situation of nitrogen for gaseous heat-carrier, because nitrogen need utilize special-purpose air separation plant etc., so employing when only being applicable to small-scale test, industrial application value is lower.Also must contain a certain amount of pressed powder in above-mentioned coal gas, flue gas, the producer gas, but content is lower.The present invention preferably uses the method for solid thermal carriers to heat the shale powder raw material, and solid thermal carriers can be to come from shale semicockes to burn carbon processing shale ashes afterwards, can heat the shale powder raw material like this, make full use of the energy of shale ashes.Why taking the solid thermal carriers heating method, also is because the rate of heat transfer of solid thermal carriers is fast, can improve heat transfer efficiency, saves technology working time, enhances productivity.The method of heating shale powder raw material can also be indirect heat transfer method, and destructive distillation institute heat requirement is called the indirect heat transfer method through the method that wall imports the destructive distillation chamber into, but the heating efficiency of this method is too low, only adopts in the laboratory at present.
B) shale powder after the de-oiling in the middle of the separation oil and gas
This step is the separating step of shale powder and oil gas.The principle of the separating step of shale semicockes powder and oil gas is different the carrying out of density according to shale semicockes powder and oil gas.
In this step; Can use cyclonic separator that the shale semicockes powder is separated with gas-oil mixture, the mixture of shale semicockes powder and oil gas enters into cyclonic separator with certain flow velocity, because oil gas is different with the density of shale semicockes powder; So the cf-that produces also is different; And the density difference of oil gas and shale semicockes powder is bigger, so the cf-that shale powder produces is bigger, and can be efficiently with shale semicockes powder and gas-oil separation.
At present; In the prior art; For the method for separating shale semicockes powder and oil gas in the destructive distillation oil refining process of shale powder all is the follow conventional lines oil gas cyclonic separator dust removal design thinking of oil fluid catalytic cracking process and burning device of circulating fluidized bed of experience according to the past basically; Adopt many group two stage cyclone separator series connection even organize the three-stage cyclone separator serial operation more for reaching the ideal dust removing effects; Really, operation can realize separating of shale semicockes powder and oil gas like this, yet; This design is not but noticed the shale powder particle in the shale semicockes powder of destructive distillation oil refining process process and the characteristic of oil gas, as breakage properties, adhesivity etc. to separate, flow, the influence of discharge.How in the form of sheets for example shale is broken easily, and material when broken.In above-mentioned two stage cyclone separator or three-stage cyclone separator series design scheme, the mixture of shale semicockes powder and oil gas through separators at different levels, is derived from the final stage separator successively at last; Most shale powder are captured, return via dipleg in first step cyclonic separator, and remaining sub-fraction particle further separates in the second stage, third stage cyclonic separator; Be the identical tolerance of processing of cyclonic separators at different levels; But the shale powder amount of carrying in the air-flow is then fewer and feweri; Grain diameter is also more and more littler, and isolating difficulty is also increasing, in order to improve the separating power of back primary cyclone; The gas flow rate of the inlet of cyclonic separator must improve step by step, and the pressure drop of consequent cyclonic separator also is to increase step by step.This just makes the bigger energy of cyclonic separator consumption of plural serial stage.And; High inlet gas flow velocity can significantly increase the broken and wearing and tearing of particulate, is unfavorable for separating, and high cyclonic separator pressure drop will cause separator dipleg negative pressure; Can increase the difficulty of dipleg discharge, smooth perhaps obstruction of dipleg discharge will influence separating effect greatly.
The present invention also improves cyclonic separation, and the contriver discovers that the shale opaque of destructive distillation is crisp, frangible, and small particle size shale semicockes powder proportion increases specific surface area increase, adhesivity enhancing, mobile variation; And the inlet gas flow velocity of cyclonic separator should hang down unsuitable high, and shale semi-coke powder end is broken serious under the high gas speed, and separation efficiency is not high on the contrary as a result; Therefore to be controlled at certain limit comparatively suitable for the segregation rate of cyclonic separator.
The separation efficiency of cyclonic separator is preferably more than 85%, more preferably more than 95%.
In this separating step; It is comparatively suitable that sepn process is at high temperature carried out under the state, if separate at low temperatures, oil gas can condensation; Therefore the liquid composition in shale powder and the gas-oil mixture can increase; Easily with the shale semicockes powder bonded together, sepn process will become difficult like this, and can make the dipleg discharge freely perhaps not stop up.
C) with water washing cooling oil gas;
What this step was accomplished is water washing process.Water washing process is a very important step among the present invention, utilizes the method for washing, has got through whole fluidization destructive distillation oil refining process, makes the fluidization destructive distillation oil refining process to carry out smoothly continuously.
After separating shale powder and oil gas, though the oil gas after the separation has passed through high efficiency separation, inevitably can residual a spot of dust in the oil gas; If use oil wash that oil gas is separated, dust also can get in the oil so, and these oil that contain dust are through after the oily dirt lock out operation; Again the oil that is used for washing oil gas and contains dust wants high efficiency separation and goes out dust and be difficult to, and separation efficiency is low, thus; The content of the dust in the oil that recycles will be accumulated, and impels greasy filth content increase in the oil, and viscosity increases; Equipment pipe in the easy blocking destructive distillation industry causes oil wash technology after moving about 10 hours continuously, just must stop.If use water instead oil gas is carried out thorough washing; Water, oil, dust are handled oil reservoir, intermediary water layer and the bottom greasy filth layer that will form top through standing separation; Be that dust in the oil gas mainly gets into the greasy filth layer; Dust content in the water layer is extremely low, so the water in the water layer can recycle be used for washing oil gas.The mode of washing has been got through whole process flow, makes that destructive distillation oil refining process later on still can steady running continuous operation 192 hours, can satisfy the needs of continuous industry production, has improved production efficiency.
Water washs the method for cooling oil gas, normally with water atomisation spray washing oil gas.Be equivalent to drip washing from top to down through isolating oil gas; Oil gas temperature under the drip washing of water reduces, and condensation becomes water and mixture oily and that remain some unsegregated dust, and such mixture can be delivered in the slurry tank through pipeline; Leaving standstill for some time just can be divided into oil reservoir, water layer and greasy filth layer; Wherein oil reservoir is in the top, and in the middle of water layer was positioned at, the greasy filth layer was the lowest layer.Oil reservoir is the desired finished product that obtains of destructive distillation oil refining process.Water layer can recycle.The greasy filth layer can continue to separate again, and the separating of oil back of coming out of major part is obtained energy to the residue sludge burning.
Preferably, during with the water atomisation, use the washer of venturi-shaped.Being shaped as of venturi tube is middle little, and two is big, the promptly middle position that has a collection to contract; Therefore, through after the atomizer of venturi-shaped, water smoke contracts through a collection; A release is arranged again; The process that has a urgency to blow on the one hand can further make the water atomization degree improve on the other hand again, is used for washing refrigerative efficient like this and also is improved.
Preferably, the temperature of washing is below 60 ℃, more preferably 50～60 ℃.Described herein below 60 ℃, be to be understood that TR, because water has become ice in 0 ℃, so should be above freezing for being a sealing.But the contriver discovers, the temperature of the water that is used for washing should not be selected too lowly, too low after, water forms the mixture of emulsified state easily in the process of washing oil gas, separating effect is not as the separating effect of temperature in the time of 50～60 ℃.
D) the mixture branch of cooled water of washing and oil gas is separated and promptly obtains shale oil.
This step is to separate the process that obtains shale oil.This step is fairly simple in operation, generally uses the method for standing separation to get final product.That is to say, the mixture of washing cooled water, oil and dirt is delivered in a jar or the still, utilize the different phase-splittings of density isolating, according to the density of the resulting light oil of destructive distillation oil refining process provided by the present invention at 0.92g/cm
3About (gram/cubic centimetre), the density of water is 1g/cm
3, the density of greasy filth is 1.2g/cm
3About.Therefore be easy to reach three phase separation.
Oil gas temperature after the washing drops to 80～120 ℃, makes it pass through a secondary heat exchanger, makes it further be cooled to 40 ℃; Like this; Lightening shale oil in the middle of the oil gas is separated, separate some natural gas liquid in the gas behind the lightening shale oil, this part oil accounts for the 5-10% that shale aluminium is discriminated oil length; Therefore must further separate, this technology is to carry out isolating through the electric fishing device.
Reclaim the noncondensable gas behind the natural gas liquid through electric fishing, can generate electricity or, in the pilot plant of this technology, handle, avoid environmental pollution through carrying out ignition after the torch surge tank as gas.
Above several key steps involved in the present invention have been done detailed explanation, and also proposed some innovative approachs, the step that possibly relate in the face of other is down made some explanations.
After step d), from the greasy filth that the standing separation jar comes, the content of oil wherein can further reduce, and in order to make full use of the resource and the energy, so preferably it is carried out centrifugal treating again, isolates a certain amount of shale oil.At this moment isolated shale oil proportion can be bigger, belongs to the heavy oil scope.
After step b), can also comprise a step b11)---step b) is separated the shale semicockes utilization burning carbon device that obtains burn the carbon processing.Separate the shale semicockes that obtain from step b), wherein contain fixed carbon, can burn carbon and obtain heat; And the shale ashes through burning carbon are mixed with the shale powder of coming from feed pot; Heat shale powder, further utilize the heat of shale ashes, form a partial circulating in the technology.
It is comparatively suitable that burning carbon treatment temperature is chosen in more than 650 ℃.Burning carbon treatment temperature will be higher than the temperature of shale powder dry distillation reactor, after mixing with the raw material shale powder, can obtain the temperature of shale powder dry distillation reactor like this.
The present invention also provides a kind of technology thus prepared shale oil except the destructive distillation oil refining process that a kind of shale is provided.
Destructive distillation oil refining process provided by the present invention is washing cooling oil gas mode fluidization destructive distillation oil refining process; Compare with oil wash cooling oil gas mode fluidization destructive distillation oil refining process; Water carries out thorough washing to oil gas, and water, oil, dust are handled through standing separation will form oil reservoir, water layer and greasy filth layer, and promptly the dust in the oil gas mainly gets into the greasy filth layer; Dust content in the water layer is extremely low, so the water in the water layer can recycle be used for washing oil gas.The mode of washing has been got through whole process flow, makes that destructive distillation oil refining process later on still can steady running continuous operation 192 hours, can satisfy the needs of continuous industry production, has improved production efficiency.
Description of drawings
Fig. 1 be the present invention on stream the oil wash that utilizes of initial stage design accomplish the artwork of destructive distillation oil refining technology.
Fig. 2 is first kind of concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
Fig. 3 is second kind of concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
Fig. 4 is the third concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
Embodiment
For those skilled in the art can understand technical scheme provided by the present invention better, further set forth below in conjunction with specific embodiment.
Embodiment 1
See also Fig. 2, Fig. 2 is first kind of concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
In the present embodiment, the basic process of shale is:
(1) shale becomes the shale powder below 3000 microns through crusher in crushing, separates the shale powder below 50 microns then, carries out subsequent use in the entering feed pot.
Said shale is Heilungkiang Yilan County resinous shale, and the volume of the said feed pot of pilot scale is 21 cubic metres; Feed pot can have the buffered effect, can be used for storing a certain amount of shale powder raw material, when interrupting when breaking down in the broken step of shale, can also make technology uninterrupted, continuous operations; When equipment or the technology in its back goes wrong, the process step before the feed pot that also can not stop.
(2) the shale powder in the feed pot is transported to mutually in the heat carrier pipeline that burns carbon reactor through the reinforced secret of impeller and mixes with thermal barrier, adopts coal mine gas to promote this mixed powder, gets in the de-oiling reactor drum through promoting standing tube reactor.
Close conveying density of carrying mutually is big, can enhance productivity.From the temperature of the thermal barrier that burns carbon reactor at 680～720 ℃.Pyrolytic reaction takes place rapidly in mixed powder in promoting standing tube reactor and de-oiling reactor drum; The temperature of reaction is about 500 ℃; Be provided with efficient cyclone separator in the de-oiling reactor head, separation efficiency is about 85%, and cyclonic separator carries out cyclonic separation with oil gas and shale powder.
(3) oil gas that cyclonic separator is separated from the de-oiling reactor drum gets into washing tower, is provided with the atomization of water current device in the washing tower, sprays water smoke from top to bottom with washing cooling oil gas.
The temperature of said current is 50 ℃.The temperature that said oil gas gets into the oil gas inlet of washing tower is 450～500 ℃.
The mixture of the oil that (4) produces after the washing, water, dirt gets into slurry tank, in slurry tank, leaves standstill phase-splitting, is divided into upper, middle and lower-ranking, and it is that water layer (phenol water layer), lower floor are the greasy filth layer for oil reservoir, middle level at the middle and upper levels.Oil reservoir can be delivered to water that oil tank obtains shale oil product, water layer and can flow to through pumped back and continue to be used as bath water in the separation column.Lower floor's greasy filth separates, and the oil of separating is sent into oil tank; Water turns back to washing tower; The oil-containing body refuse with deliver to power plant's combustion power generation after coal dust mixes.
Other processing:
(A) get into secondary coolers through the oil gas after the washing, the gas-liquid that the cooling back produces gets in the three phase separation jar mutually, after noncondensable gas further reclaims natural gas liquid through electric fishing, sends to generating or as town gas or as industrial chemicals.Pilot plant is not built follow up device in order to reduce investment at present, through carrying out ignition process after the torch surge tank, reduces atmospheric pollution.
(B) from the de-oiling reactor drum, be treated as lightening shale oil through the isolating oil gas process of efficient cyclone separator; And the shale semicockes after the de-oiling also need further to handle and utilize; Specifically can its burning carbon through burning carbon device be handled; With the burning of the fixed carbon in the shale semicockes, temperature of combustion is about 680～720 ℃, and the shale ashes part of production is as thermal barrier.The design temperature that burns the carbon reaction is 700 ℃.
Embodiment 2
See also Fig. 3, Fig. 3 is second kind of concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
Present embodiment is that improvements are to the improvement of embodiment 1:
Horizontal slurry tank is set, oil, water, the dirt mixture of discharging in the washing tower carried out standing separation, see also the right side of Fig. 3; Oil, water, dirt mixture get into slurry tank, through sedimentation after a while, make the greasy filth component drop to the bottom of slurry tank; Lower floor is a greasy filth; The middle level contains phenol water for some, and the upper strata also has the part wet goods, also has some other impurity.Greasy filth through the whizzer centrifugal treating is referred to as body refuse, also contains organic constituentses such as some heavy oil in the body refuse, can be sent to the power station and be used for generating.
Through the sedimentation once more of slurry tank and the centrifugal treating of whizzer, can also therefrom isolate a part of shale oil, improved the utilization ratio of shale.Calorific value through analyzing the greasy filth before not passing through centrifugal treating is 3590kcal/kg (kcal/kg), is 1460kcal/kg through the calorific value in the body refuse after the centrifugal treating.The body refuse calorific value is very low, and the effect that spinning is described is good.
Embodiment 3
See also Fig. 4, Fig. 4 is the third concrete process flow sheet of the destructive distillation oil refining process of shale provided by the present invention.
Present embodiment is that improvements are to the improvement of embodiment 2:
Improve burning carbon technology.In burning carbon technology, the temperature of burning the carbon device is higher, and about 700 ℃, high like this temperature heat leakage is comparatively serious, and burning carbon device is connected with external warmer, utilizes the heat that burns in the carbon device.
In addition, from burning the shale ashes through burning carbon that the carbon device is discharged, temperature is higher, through just being discharged into blow-down drum after the cooling of discharge water cooler.The discharge interchanger carries out the refrigerative process to waste material, also is the process that discharge water cooler and waste material carry out heat exchange, improves HU.
The destructive distillation oil refining process of the shale that is provided among the embodiment 1～3 can move more than 192 hours continuously, and still keeps stable running status.
The comparative example 4
See also Fig. 1, Fig. 1 for the present invention on stream the oil wash that utilizes of initial stage design accomplish the artwork of fluidization destructive distillation oil refining technology.
In this skill comparative example; Under the situation of other term harmonizations, some is extracted out by pump and just change into the lightweight oil in the three phase separation jar, returns separation column top as trim the top of column; The control tower top temperature is about 200 ℃, and another part is collected into the light oil jar.The heavy oil that separation column comes out is delivered in the settling tank, and through getting into heavy oil tank after the clarifying treatment, the heavy oil that comes from heavy oil tank is used for washing from the next oil gas of de-oiling reactor drum.
The oil wash technology that is provided among this comparative example is after carrying out 10 hours 37 minutes, because greasy filth blocking pipe and out of service.
Can find out from the comparison of embodiment 1～3 described washing destructive distillation oil refining process and comparative example's 4 oil wash technology; The washing destructive distillation oil refining process is stable and the time is long; Can realize the continuous industry operation, solve the difficult problem that puzzlement shale fluidization destructive distillation oil refining process flow process can not be got through for a long time.
Washing fluidization destructive distillation oil refining process has not only been got through whole shale fluidization destructive distillation oil refining process flow process, and the quality of the shale oil of producing improves a lot.Each item index for the lightening shale oil that is provided technology to produce by 3 of embodiment is as shown in table 1.
Table 1
| Boiling range | Cut content | The mensuration project | Measure the result |
| Before 160 ℃ | 10％ | Calorific value | 49MJ/kg (cylinder) |
| Before 184 ℃ | 20％ | Density | 0.8910g/cm 3 |
| Before 200 ℃ | 28％ | Flash-point | 54 ℃ (opening middle agar diffusion method) |
| Before 220 ℃ | 38％ | Kinematic viscosity (50 ℃) | 1.84m 2/s |
| Before 240 ℃ | 48％ | Moisture | 0.05％ |
| Before 243 ℃ | 50％ | Over point | 90℃ |
| Before 260 ℃ | 57％ | ||
| Before 280 ℃ | 64％ | ||
| Before 300 ℃ | 69％ | ||
| Before 320 ℃ | 73％ | ||
| Before 340 ℃ | 78％ | ||
| Before 342 ℃ | 80％ |
At present, shown in the index table 2 of Arabic high-quality oil.
Table 2
| The mensuration project | Measure the result | Boiling range | Cut content |
| Before 300 ℃ | 31％ | Density in the time of 20 ℃ | 0.883g/cm 3 |
| Before 320 ℃ | 36％ | Viscosity (50 ℃) | 10.75mm 2/s |
| 340℃ | 38％ | Flash-point | 24℃ |
| 360℃ | 40％ | Calorific value | 45.3MJ/kg |
| Over point | 124℃ |
Through contrast table 1 and table 2, can find out that the lightening shale oil that utilizes the destructive distillation oil refining process of shale provided by the present invention to produce is called for short shale oil, each item index obviously is superior to Arabic high-quality oil, can obtain the fine lightweight oil.
The destructive distillation oil refining process of the shale that embodiment 3 is provided, final carbon residue is 0.32%, is fine building materials raw materials.
The destructive distillation oil refining process of the shale that embodiment 3 is provided, employing be the recycle measure of water, therefore, have only the generation of a small amount of waste water, through waste water is handled, do not have waste water to efflux.
The destructive distillation oil refining process of the shale that embodiment 3 is provided does not detect SO in the flue gas
2, can prove that this technology is environmental protection.
The destructive distillation oil refining process of the shale that embodiment 3 is provided, oil yield are very high, and for aluminium is discriminated 90.15% of dry distillation, and the technology shale oil productive rate of external more advanced Brazilian gas retort reaches 87.5%～90%.。
Shale retorting oil refining process provided by the present invention can move more than 192 hours continuously, and the prepared resinous shale each item of technology performance index are excellent thus, and multiple use is arranged in industry, have industrial applicibility.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (16)
1. a carbonization oil refining technique of fluidized shale comprises the steps:
A) shale powder is heated to pyrolysis temperature under fluidized state;
B) shale powder after the de-oiling in the middle of the separation oil and gas;
C) with water washing cooling oil gas, the temperature of said water is 50 ~ 60 ℃;
D) the mixture branch of cooled water of washing and oil is separated and promptly obtains shale oil; Oil gas temperature after the washing is dropped to 80 ~ 120 ℃, make it pass through a secondary heat exchanger, make it further be cooled to 40 ℃, pass through electric fishing device separating treatment again.
2. fluidization destructive distillation oil refining process according to claim 1 is characterized in that, the particle diameter of shale powder described in the step a) is less than 3000 microns.
3. fluidization destructive distillation oil refining process according to claim 2 is characterized in that, the particle diameter of shale powder described in the step a) is greater than 50 microns and less than 3000 microns.
4. fluidization destructive distillation oil refining process according to claim 1 is characterized in that, the method for the heating described in the step a) heats as thermal barrier for utilizing the shale ashes powder.
5. fluidization destructive distillation oil refining process according to claim 1 is characterized in that, the pyrolysis temperature described in the step a) is 450～550 ℃.
6. fluidization destructive distillation oil refining process according to claim 5 is characterized in that, the pyrolysis temperature described in the step a) is 480～520 ℃.
7. want its 1 described fluidization destructive distillation oil refining process according to right, it is characterized in that, the method for the shale powder after the de-oiling in the step b) in the middle of the separation oil and gas is separated for using cyclonic separator.
8. fluidization destructive distillation oil refining process according to claim 7 is characterized in that, the method for the shale powder after the de-oiling in the step b) in the middle of the separation oil and gas is separated for using the cyclonic separator secondary.
9. according to claim 7 or 8 described fluidization destructive distillation oil refining process, it is characterized in that the separation efficiency of said cyclonic separator is more than 85%.
10. destructive distillation oil refining process according to claim 9 is characterized in that, the separation efficiency of said cyclonic separator is more than 95%.
11. destructive distillation oil refining process according to claim 1 is characterized in that, specifically being embodied as water atomisation spray washing oil gas with washing cooling oil gas described in the step c).
12. destructive distillation oil refining process according to claim 11 is characterized in that, described in the step c) with the water atomisation time, use the washer of venturi-shaped.
13. require 1 described destructive distillation oil refining process, it is characterized in that the isolating method of the phase-splitting described in the step d) is a standing separation according to power.
14. destructive distillation oil refining process according to claim 1 is characterized in that, after step d), also comprises the steps:
E) the isolated greasy filth of phase-splitting in the step d) is carried out centrifugal treating.
15. destructive distillation oil refining process according to claim 1 is characterized in that, after step b), also comprises the steps:
B11) step b) is separated the shale semicockes utilization burning carbon device that contains fixed carbon that obtains and burn the carbon processing.
16. destructive distillation oil refining process according to claim 15 is characterized in that, said burning carbon treatment temperature is more than 650 ℃.
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| CN102153262B (en) * | 2010-12-13 | 2013-12-25 | 华东理工大学 | Method and device for grading reclamation and concentration of oil sludge of oil shale dry distillation system |
| CN103131446B (en) * | 2011-12-05 | 2014-04-30 | 中国石油化工股份有限公司 | Method and device for fluid-bed destructive distillation of oil shale |
| CN103131448B (en) * | 2011-12-05 | 2014-04-30 | 中国石油化工股份有限公司 | Method and device for fluid-bed destructive distillation of oil shale |
| CN103131445A (en) * | 2011-12-05 | 2013-06-05 | 中国石油化工股份有限公司 | Destructive distillation method and device for fluidized bed oil shale |
| CN103131450B (en) * | 2011-12-05 | 2014-06-18 | 中国石油化工股份有限公司 | Method and device for destructive distillation of oil shale |
| CN104946282B (en) * | 2015-06-15 | 2017-05-31 | 宋军 | A kind of handling process of smalls |
| CN109385288B (en) * | 2018-12-13 | 2024-03-22 | 上海博申工程技术有限公司 | Comprehensive utilization method and device for oil sand and oil sludge |
| CN109628160A (en) * | 2019-01-30 | 2019-04-16 | 中国科学院广州能源研究所 | A kind of high humidity biomass gasification method and system |
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| CN1621493A (en) * | 2003-11-27 | 2005-06-01 | 王守峰 | Process for dry distillation and decarburization of oil shales on fluidized bed |
| CN101113344A (en) * | 2007-05-09 | 2008-01-30 | 东北电力大学 | Kerosene shale comprehensive utilization process |
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| CN101113344A (en) * | 2007-05-09 | 2008-01-30 | 东北电力大学 | Kerosene shale comprehensive utilization process |
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