CN106350110A - Method for producing middle distillate oil from Fischer-Tropsch synthetic oil - Google Patents
Method for producing middle distillate oil from Fischer-Tropsch synthetic oil Download PDFInfo
- Publication number
- CN106350110A CN106350110A CN201510420352.7A CN201510420352A CN106350110A CN 106350110 A CN106350110 A CN 106350110A CN 201510420352 A CN201510420352 A CN 201510420352A CN 106350110 A CN106350110 A CN 106350110A
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction
- catalyst
- isomery
- fischer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of oil refining and discloses a method for producing middle distillate oil from Fischer-Tropsch synthetic oil. The method comprises the following steps: introducing the Fischer-Tropsch synthetic oil and a hydrogen-containing stream into a hydrofining reactor for reaction; sequentially separating and fractionating hydrofining reaction effluents to obtain a first naphtha fraction, a light diesel oil fraction and a heavy oil fraction; introducing the heavy oil fraction into a heterogeneous hydrocracking reactor for reaction; then sequentially separating and fractionating heterogeneous hydrocracking reaction effluents, wherein at least two reaction regions are arranged in the heterogeneous hydrocracking reactor; cracking activities of heterogeneous hydrocracking catalysts per unit volume in two adjacent reaction regions are sequentially reduced in a flow direction of the reaction stream. With adoption of the method provided by the invention, the selectivity and yield of the middle distillate oil can be improved when the middle distillate oil is produced through hydrogenation and quality increasing of the Fischer-Tropsch synthetic oil.
Description
Technical field
The present invention relates to refining art, in particular it relates to one kind produces intermediate oil by Fischer-Tropsch synthesis oil
Method, more particularly, to a kind of by hydrogenation of Fischer-Tropsch synthesis oil upgrading produce intermediate oil method.
Background technology
With the fast development of national economy, China's oil consumption assumes zooming trend.Same with this
When, increasingly strict with environmental requirement, to the composition of engine fuel, impurity content and the course of processing
The discharge of middle pollutant proposes more stringent requirement.However, oil is as the non-renewable energy,
It is faced with increasingly exhausted crisis, also worse and worse, the trend of in poor quality and heaviness is increasingly for the quality of oil
Substantially.Therefore, exploitation has met the new sustainable energy technology of environmental requirement and liquid fuel demand
Become the research power solving energy crisis and environmental crisis.
Fischer-Tropsch synthesis are found in nineteen twenty-three by Germanization scholar fischer and tropsch.This reaction
It is with hydrogen and carbon monoxide as raw material, generate the reaction of hydro carbons under synthetic catalyst effect.Its raw material
Can be transformed by coal, natural gas, coal bed gas, biomass etc., there is extensive source.Former
In the case that oil price lattice constantly rise, the large-scale industrial application of Fischer-Tropsch synthesis oil is carried out production section high-quality and is sent out
Motivation fuel and industrial chemicals are with a wide range of applications.The synthesis being obtained using F- T synthesis technology
Oil, has larger difference with each side such as main character in hydro carbons composition compared with conventional oil derivant,
It is a kind of mixture high containing wax content, is mainly made up of alkane and alkene, and sulfur, nitrogen content are extremely low,
But containing a certain amount of oxygen.Gasoline fraction is substantially free of sulfur and nitrogen, but due to the alkene in its composition and
The alkane overwhelming majority is straight chain, therefore its octane number is very low；Diesel oil distillate sulfur, nitrogen and arene content are extremely low,
Cetane number is very high, but very poor, condensation point of its low temperature flowability etc. is higher.Therefore, by F- T synthesis
Each fraction needs that product obtains are hydrogenated with upgrading through corresponding, just can obtain meeting using specification
Liquid fuel.
For example, us6589415 describes a kind of method being hydrocracked Fischer-Tropsch synthesis oil, its master
Feature is wanted to be to be hydrocracked the heavy distillat of artificial oil, using the light fraction of artificial oil as being hydrocracked
The cooling logistics of reaction bed.Although this invention is also to be turned Fischer-Tropsch synthesis oil by the method being hydrocracked
Turn to light component, but be disadvantageous in that Cracking catalyst easily inactivates, in addition, the liquid of the method produces
Thing yield is low, selectivity is low.
Therefore, need a kind of method finding new processing Fischer-Tropsch synthesis oil in the art badly, to improve centre
The selectivity of distillate and obtain higher midbarrel oil yield.
Content of the invention
The purpose of the present invention be overcome prior art intermediate oil selectivity low and yield is not high
Defect, provides a kind of new method being produced intermediate oil by hydrogenation of Fischer-Tropsch synthesis oil upgrading.
To achieve these goals, the present invention provides a kind of side being produced intermediate oil by Fischer-Tropsch synthesis oil
Method, the method includes: Fischer-Tropsch synthesis oil is introduced the hydrogenation containing Hydrobon catalyst with hydrogeneous logistics
Reacted in finishing reactor, then carry out hydrofining reaction effluent successively separating and fractional distillation,
Obtain the first naphtha cut, light diesel fuel fraction and heavy oil fraction；Described heavy oil fraction is introduced containing different
Reacted in the isomery hydrocracking reactor of structure hydrocracking catalyst, then isomery is hydrocracked
Reaction effluent carries out separating and fractional distillation successively, obtains the second naphtha cut, intermediate oil and tail oil
At least partly described tail oil is optionally looped back isomery hydrocracking reactor entrance and is followed by fraction
Ring；Wherein, at least provided with two reaction zones in described isomery hydrocracking reactor, according to reaction stream
Flow direction, in two neighboring reaction zone, the cracking activity of the isomery hydrocracking catalyst of unit volume is successively
Reduce.
When intermediate oil is produced by hydrogenation of Fischer-Tropsch synthesis oil upgrading using the said method of the present invention, can
Improve selectivity and the yield of intermediate oil.
The said method of the present invention also has the advantage that relatively independent unifining process and isomery add
Hydrogen cracking process can obtain having different performance, meet the target product of different product specification, product side
Case is flexible；And, the said method of the present invention in the case of carrying out less change to existing apparatus flow process
Can be achieved with, greatly save the investment cost of device.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.Attached
Some auxiliary equipments of in figure such as heat exchanger, preheating furnace etc. do not mark, but this is to ordinary skill people
Member is known.In the accompanying drawings:
Fig. 1 is that the flow process of the method producing intermediate oil by Fischer-Tropsch synthesis oil that the present invention provides is illustrated
Figure.
Description of reference numerals
1 Fischer-Tropsch synthesis oil 2 hydrofining reactor
3 first high pressure hot separator 4 first cold high pressure separator
5 first thermal low-pressure separators 6 first cold low separator
The cold low point of liquid phase of 7 water 8 first
9 first hot low point of liquid phase 10 first fractionating columns
11 first naphtha cut 12 light diesel fuel fraction
First low point of gas of 13 heavy oil fraction 14
The new hydrogen of 15 circulating hydrogen compressor 16
17 circulating air 18 isomery hydrocracking reactor
19 second high pressure hot separator 20 second cold high pressure separator
21 second thermal low-pressure separators 22 second cold low separator
23 second cold low point of liquid phase 24 second low point of liquid phases of heat
25 after-fractionating tower 26 second naphtha cut
27 intermediate oil 28 tail oil fraction
The cold high score gas phase of 29 second low point of gas 30 second
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method producing intermediate oil by Fischer-Tropsch synthesis oil, the method includes:
Fischer-Tropsch synthesis oil is introduced in the hydrofining reactor containing Hydrobon catalyst with hydrogeneous logistics
Then hydrofining reaction effluent is carried out separating and fractional distillation, obtains the first Petroleum by row reaction successively
Fraction, light diesel fuel fraction and heavy oil fraction；Described heavy oil fraction is introduced and contains isomery hydrocracking catalyst
Reacted in the isomery hydrocracking reactor of agent, then by isomery hydrocracking reaction effluent successively
Carry out separating and fractional distillation, obtain the second naphtha cut, intermediate oil and tail oil fraction, optionally will
At least partly described tail oil loops back isomery hydrocracking reactor entrance and is circulated；Wherein, described different
At least provided with two reaction zones in structure hydrocracking reactor, according to the flow direction of reaction stream, two neighboring
In reaction zone, the cracking activity of the isomery hydrocracking catalyst of unit volume reduces successively.
The boiling range scope of the first naphtha cut of the present invention is c5-150 DEG C, described light diesel fuel fraction
Boiling range scope is 150-320 DEG C, and described heavy oil fraction is fraction more than 320 DEG C for the boiling range.
The boiling range scope of the second naphtha cut of the present invention is c5-150 DEG C, described intermediate oil
Boiling range scope is 150-370 DEG C, and described tail oil fraction is fraction more than 370 DEG C for the boiling range.
In method of the present invention, in described two neighboring reaction zone, the isomery hydrogenation of unit volume splits
The cracking activity changing catalyst reduces successively and refers to: under identical reaction conditions, two neighboring reaction zone
The cracking activity of the isomery hydrocracking catalyst of middle same volume reduces successively.Especially, institute of the present invention
The cracking activity of the catalyst stated can be by the preparation process of control isomery hydrocracking catalyst
Infrared acidity is realizing.
In method of the present invention, described hydrogeneous logistics is the logistics referring to provide hydrogen, including
New hydrogen, recycle hydrogen, hydrogen-rich gas and other can provide the gaseous stream of hydrogen and other can provide
Any one or more in the liquid phase stream of hydrogen.Heretofore described hydrogeneous logistics can be identical
Can be different, those skilled in the art after having understood technical scheme it can be clearly understood that
Heretofore described hydrogeneous logistics.
It was found by the inventors of the present invention that by the two neighboring reaction zone of isomery hydrocracking reactor
The catalyst loading different cracking activity levels respectively can be conducive to slowing down n-alkane and generate
Isoparaffin the secondary cracking extent of reaction, advantageously reduce light component c1-c4Hydro carbons and Petroleum evaporate
The generation dividing, to improve selectivity and the yield of intermediate oil.
And, with conventional isomery hydrocracking reactor in all load same activity isomery hydrogenation split
Change catalyst to compare, the method that the present invention provides, on the one hand reduce n-alkane and generated isomery
The secondary cracking extent of reaction of alkane, decreases light component c1-c4Hydro carbons and the generation of naphtha cut,
Improve selectivity and the yield of intermediate oil；On the other hand, anti-in the bottom of two neighboring reaction zone
Answer the relatively low isomery hydrocracking catalyst of filling activity level in area, also help control cracking anti-
The depth answered, reduces generation and the accumulation of heat, effectively promotes the quiet run of device, and can prevent
Stop isomery hydrocracking reactor outlet temperature too high and cause isomery in lower reaction zone to be hydrocracked and urge
Agent is prematurely reached the later stage and is shortened catalyst service life using temperature.
According to method of the present invention, under preferable case, with isomery hydrocracking reaction effluent
The gross weight meter of tail oil fraction, the tail oil fraction looping back described isomery hydrocracking reactor entrance is
10-100 weight %；The tail oil fraction more preferably looping back described isomery hydrocracking reactor entrance is
50-100 weight %.
In method of the present invention, under preferable case, according to the flow direction of reaction stream, two neighboring
In reaction zone, the ratio of the cracking activity of isomery hydrocracking catalyst of unit volume is 1.1-10:1；Excellent
Elect 1.2-5:1 as.
Under preferable case, in method of the present invention, according to the flow direction of reaction stream, described isomery
Setting top reaction zone and lower reaction zone two reaction zones altogether, top reaction zone in hydrocracking reactor
With the admission space of isomery hydrocracking catalyst in lower reaction zone than for 1-4:1；Preferably 1.2-2.5:
1.
According to method of the present invention, according to the flow direction of reaction stream, described isomery hydrocracking reaction
Setting top reaction zone and lower reaction zone altogether two reaction zones in device, preferably arrange in each reaction zone to
Few beds, arrange 2-3 beds more preferably in each reaction zone.The present invention
Each beds of method preferably each reaction zone in isomery hydrocracking catalyst filling body
Long-pending identical.
According to method of the present invention, according to the flow direction of reaction stream, described isomery hydrocracking reaction
Setting top reaction zone and lower reaction zone two reaction zones altogether in device, preferably in the reaction zone of top, isomery adds
The infrared acidity of hydrogen Cracking catalyst is 0.5-1.0mmol/g, isomery hydrocracking catalyst in lower reaction zone
The infrared acidity of agent is 0.1-0.45mmol/g.In the present invention, described isomery hydrocracking catalyst
The infrared spectrometry that the method for testing of infrared acidity can be known to the skilled person, infrared spectrometry
It is one of acid process of analysis solid catalyst surface the most frequently used at present, it can be catalyzed simultaneously
The information of the type of agent surface acid, intensity and acid amount.Its ultimate principle is that the probe molecule of alkalescence is catalyzed
Agent surface acidity position is adsorbed, and the b on solid acid catalyst surface is sour and l acid acts on shape with alkaline probe molecule
Become different species, some characteristic absorption bands are produced on infrared spectrum spectrogram or original absorption band occurs
Displacement, thus can measure type, intensity and the acidity of acid.Pyridine is the most frequently used alkaline probe molecule.
In method of the present invention, in preferably described Hydrobon catalyst, contain the nothing as carrier
Setting aluminium oxide and load vib race metallic element on the carrier and/or viii race metallic element.
In the case of more preferably, in method of the present invention, in described Hydrobon catalyst,
Described vib race metallic element is mo and/or w, and described viii race metallic element is co and/or ni.
According to method of the present invention, contain as carrier in preferably described isomery hydrocracking catalyst
Amorphous silica-alumina and load active component element on the carrier.
In the case of more preferably, in method of the present invention, in described isomery hydrocracking catalyst
In, described active component element includes precious metal element and/or non-noble metal j element；Described base metal unit
Element is vib race metallic element and/or viii race metallic element.
In the case of particularly preferably, in method of the present invention, in described isomery hydrocracking catalyst
In, described vib race metallic element be mo and/or w, described viii race metallic element be co and/or
ni；Described precious metal element is pt element and/or pd element.
According to method of the present invention, the reaction condition in preferably described hydrofining reactor includes:
Hydrogen dividing potential drop is 2.0-15.0mpa, and reaction temperature is 250-400 DEG C, and hydrogen to oil volume ratio is 100-1000:1,
Volume space velocity is 0.5-8.0h-1.
According to method of the present invention, the reaction condition bag in preferably described isomery hydrocracking reactor
Include: hydrogen dividing potential drop is 2.0-15.0mpa, reaction temperature is 300-450 DEG C, hydrogen to oil volume ratio is 300-1500:
1, volume space velocity is 0.5-5.0h-1.
In method of the present invention, because in Fischer-Tropsch synthesis oil, olefin(e) centent is very high, if alkene is straight
Connect and Hydrobon catalyst haptoreaction, Jiao in a large number can be generated vigorous reaction on Hydrobon catalyst
Charcoal and lead to Hydrobon catalyst activity decrease；Typically a certain amount of gold is also contained in Fischer-Tropsch synthesis oil
Belong to, these metals are easily deposited on Hydrobon catalyst top, lead to hydrofining reactor to go out quickly
Existing pressure reduction, the metal being concurrently deposited on Hydrobon catalyst can cause the permanent of Hydrobon catalyst
Hydrogenation protecting catalyst, for ensureing the long-term operation of commercial plant, is preferably seated in hydrogenation essence by inactivation
The top of catalyst processed, thus avoid the generation of above-mentioned phenomenon.In method of the present invention, according to
The flow direction of reaction stream, loads hydrogenation protecting catalyst and institute successively in preferably described hydrofining reactor
State Hydrobon catalyst.
In method of the present invention, in described hydrofining reactor, preferably hydrogenation protecting catalysis
The admission space of agent and Hydrobon catalyst is than for 2-30:100；It is preferably 5-15:100.
According to method of the present invention, preferably described hydrogenation protecting catalyst includes carrier and is supported on
Active component element on described carrier, described active component element is vib race metallic element and/or viii
Race's metallic element.
According to method of the present invention, because isomery hydrocracking reaction has a small amount of alkene to generate, it is
Guarantee that product quality is stable, preferably urge in appropriate rear the refining of the bottom of isomery hydrocracking reactor filling
Agent, the admission space of rear catalyst for refining and isomery hydrocracking catalyst is than for 2-15:100, excellent
Elect 5-10:100 as.There is no particular limitation for the species to rear catalyst for refining for the method for the present invention, this
Skilled person can be used for the present invention using conventional use of various rear catalyst for refining in the art
Method in.
In method of the present invention, preferably described Fischer-Tropsch synthesis oil is to synthesize work from syrup state bed Fischer Tropsch
The synthesis light oil of skill, the full fraction of synthesis of heavy oil and synthetic wax and/or from fixed bed fischer-tropsch synthesis process
The full fraction of synthesis light oil, synthesis of heavy oil and synthetic wax.
According to a kind of preferred specific implementation method of the present invention, the method for the present invention adopts shown in Fig. 1
The method of schematic flow sheet is carried out, specifically as follows:
Fischer-Tropsch synthesis oil 1 enters hydrofining reactor 2 and is reacted, and hydrofining reactor 2 is out
Logistics enter the first high pressure hot separator 3 and carry out gas-liquid separation, the first high pressure hot separator 3 is out
Liquid phase enters the first thermal low-pressure separators 5, and the gas phase of the first high pressure hot separator 3 enters the first cold anticyclone
Separator 4 is further separated into gas phase, liquid hydrocarbon and water 7, and the first cold high pressure separator 4 is separated
Gas phase be hydrogen-rich gas, through circulating hydrogen compressor 15 boosting after with new hydrogen 16 mixed circulating air 17
Between Returning reactor entrance and bed, the liquid hydrocarbon and first that the first cold high pressure separator 4 is separated
The gas phase of thermal low-pressure separators 5 enters the first cold low separator 6 together and carries out gas-liquid separation further,
The first cold low point of liquid phase 8 that first cold low separator 6 is separated and the first thermal low-pressure separators 5
First hot low point of liquid phase 9 enters the first fractionating column 10 together, is separated into the first stone brain of hydrofinishing unit
Oil distillate 11, light diesel fuel fraction 12 and heavy oil fraction 13, the first cold low separator 6 is separated
The gas phase that gas phase and the first fractionating column 10 are separated is discharged as first low point of gas 14.Heavy oil fraction
13 enter back into isomery hydrocracking reactor 18, carry out isomery hydrocracking reaction, and isomery is hydrocracked
Reactor 18 logistics out enters the second high pressure hot separator 19 and carries out gas-liquid separation, the second thermal high
Separator 19 liquid phase out enters the second thermal low-pressure separators 21, the gas of the second high pressure hot separator 19
Mutually enter the second cold high pressure separator 20 and be further separated into gas phase and liquid phase, the second cold high pressure separator
20 the second cold high score gas phases 30 separated remove circulating hydrogen compressor 15, the second cold high pressure separator 20
The liquid phase separated enters the second cold low separator together with the gas phase of the second thermal low-pressure separators 21
22 carry out gas-liquid separation further, the second cold low point of liquid phase that the second cold low separator 22 is separated
After-fractionating tower 25 is entered together with 23 low point of liquid phases 24 hot with the second of the second thermal low-pressure separators 21,
It is separated into the second naphtha cut 26, intermediate oil 27 and the tail oil fraction of isomery Hydrocracking unit
28, the gas phase that the second cold low separator 22 is separated and the gas phase that after-fractionating tower 25 is separated
Discharge as second low point of gas 29, wherein, tail oil fraction is recycled into isomery hydrocracking reactor
18 entrance is converted further.
The said method of the present invention also has a specific advantage as follows:
(1) hydrofining reaction and the relatively independent technological process of isomery hydrocracking reaction can obtain respectively
To having different performance, meeting the purpose product of different product specification, products scheme is flexible；
(2) method that the present invention provides, on the one hand reduces n-alkane and has generated isoparaffin
The secondary cracking extent of reaction, decrease light component c1-c4Hydro carbons and the generation of naphtha cut, improve
The selectivity of intermediate oil and yield；On the other hand because isomery hydrocracking process is strongly exothermic mistake
Journey, loads the relatively low isomery hydrocracking catalyst of cracking activity level of relative in lower reaction zone, also
Beneficial to the depth controlling cracking reaction, reduce generation and the accumulation of heat, effectively promote reaction unit
Quiet run, and reactor outlet temperature can be prevented too high and cause lower catalytic agent to prematurely reach the later stage
Shorten catalyst service life using temperature；
(3) method adopting the present invention to provide, is conducive to improving the selectivity of intermediate oil further
With yield it is achieved that producing the purpose of intermediate oil to greatest extent；
(4) adopt the method that the present invention provides, can be in the feelings that existing apparatus flow process is carried out with less change
Condition is got off realization, greatlys save plant investment expense.
Hereinafter will be described the present invention by embodiment.In following examples, not especially
In the case of explanation, the various raw materials that adopted are all from commercially available.
Used in following examples and comparative example, raw oil is the full fraction of Fischer-Tropsch synthesis oil, and its property is shown in Table
Shown in 1.
Product designation rtf-1 (diameter 1.4mm) of Hydrobon catalyst, isomery is hydrocracked urges
Agent is rcf-1, cdb-44, cdb-45 and cdb-46.
Hydrogenation protecting catalyst is rgf series protective agent, is the grading loading of five kinds of guard catalysts,
According to the flow direction of reaction stream, trade names include successively rgf-20, rgf-30e, rgf-30a,
rgf-30b、rgf-1.
Product designation rtf-1 (diameter 3.4mm) of catalyst for refining afterwards.
Above catalyst is produced by China Petrochemical Corp.'s catalyst Chang Ling branch company.
In the case of not contrary explanation, in described hydrofining reactor, described hydrogenation protecting is urged
The admission space of agent and described Hydrobon catalyst is than for 10:100；It is hydrocracked in described isomery
In reactor, the admission space of described isomery hydrocracking catalyst and described rear catalyst for refining is than for 8:
100.
Wherein, the consisting of of described cdb-44: with the gross weight meter of described catalyst, described catalyst
In the amorphous aluminum silicate containing 32.5 weight %, the aluminium oxide of 35.0 weight %, in terms of oxide 25.0
The tungsten oxide of weight %, the nickel oxide of 7.5 weight % in terms of oxide, infrared acidity is 0.35mmol/g.
Described cdb-45 consists of: with the gross weight meter of described catalyst, contains in described catalyst
The amorphous aluminum silicate of 42.6 weight %, the aluminium oxide of 22.4 weight %, 26.8 weight % in terms of oxide
Tungsten oxide, the nickel oxide of 8.2 weight % in terms of oxide.Infrared acidity is 0.62mmol/g.
Described cdb-46 consists of: with the gross weight meter of described catalyst, contains in described catalyst
The amorphous aluminum silicate of 29.1 weight %, the aluminium oxide of 38.7 weight %, 24.9 weight % in terms of oxide
Tungsten oxide, the nickel oxide of 7.3 weight % in terms of oxide, infrared acidity is 0.28mmol/g.
In the present invention, it is well known by those skilled in the art that cracking activity energy in the method for the present invention
Enough embodied by the conversion ratio of 370 DEG C of fractions of ＞.In the present invention, described 370 DEG C of fraction conversion ratios of ＞
=(in the charging of isomery hydrocracking reactor, the content-isomery hydrocracking reactor of 370 DEG C of fractions of ＞ produces
Content × the liquid yield of 370 DEG C of fractions of ＞ in thing)/isomery hydrocracking reactor charging in 370 DEG C of ＞ evaporate
Divide content × 100%.
In method of the present invention, described intermediate oil selectivity=(isomery is hydrocracked instead
Answer corresponding in the content × liquid yield-isomery hydrocracking reactor charging of intermediate oil in device product
The content of the fraction of intermediate oil boiling range scope)/(isomery hydrocracking reactor charging in 370 DEG C of ＞
Content × the liquid yield of 370 DEG C of fractions of ＞ in the content of fraction-isomery isocrackate) × 100%.
Table 1
| Fischer-Tropsch synthesis oil raw material | |
| Density (20 DEG C)/(g/cm3) | 0.7900 |
| Oxygen content/(μ g/g) | 0.51 |
| C content/weight % | 85.24 |
| H content/weight % | 14.66 |
| D-1160/ DEG C of boiling range astm | |
| ibp | 68 |
| 50% | 389 |
| 95% | 643 |
| Tenor/(μ g/g) | |
| fe | 7.1 |
| cu | 0.1 |
| mg | 0.3 |
| na | 0.8 |
| ca | 0.2 |
| al | 0.4 |
Embodiment 1
The present embodiment is used for the method producing intermediate oil by Fischer-Tropsch synthesis oil of the present invention is described,
Specifically as follows:
Fischer-Tropsch synthesis oil raw material enters hydrofining reactor, successively with hydrogenation protecting catalyst and hydrogenation essence
Catalyst haptoreaction processed, hydrofining reaction effluent enters to separate to carry out separating with fractionating system and divides
Evaporate, obtain the first naphtha cut, light diesel fuel fraction and heavy oil fraction.Wherein heavy oil fraction enters back into and sets
It is equipped with the isomery hydrocracking reactor of top reaction zone and lower reaction zone, according to the stream of reaction stream
To described heavy oil fraction is respectively in top reaction zone and lower reaction zone and isomery hydrocracking catalyst
Rcf-1 and isomery hydrocracking catalyst cdb-46 haptoreaction, and be hydrocracked in described isomery
Catalyst for refining after the afterbody filling of reactor, isomery hydrocracking reaction effluent enters and separates and fractional distillation
System carries out separating fractional distillation, obtains the second naphtha cut, intermediate oil and tail oil fraction, wherein,
4 beds are set in isomery hydrocracking reactor, and the 1st beds and the 2nd urge
Agent bed is top reaction zone, and the 3rd beds and the 4th beds react for bottom
Area, wherein, the cracking of the cracking activity level of the rcf-1 of unit volume and the cdb-46 of unit volume
The ratio of activity level is 1.4:1；Isomery hydrocracking catalyst in top reaction zone and lower reaction zone
Admission space is than for 1.5:1.Tail oil fraction all loops back the entrance of isomery hydrocracking reactor, tool
Product property after precursor reactant condition, reactivity worth and isomery hydrocracking reaction is shown in Table 2 and table 3, its
In, the naphtha cut in table 3 is aforesaid second naphtha cut of the present invention (similarly hereinafter).
From table 3 it is observed that the selectivity of the intermediate oil of the present embodiment is 81.80%, cracking
Only 31 DEG C of the bed temperature rise of reactor, the method that this explanation present invention provides, on the one hand reduce positive structure
The secondary cracking extent of reaction of alkane and isoparaffin, decreases light component c1-c4Hydro carbons and the second stone
The generation of naphtha fraction, improves selectivity and the yield of intermediate oil；On the other hand due in bottom
The relatively low catalyst of activity level is loaded in reaction zone, is conducive to controlling reaction depth, reduces heat
Generate and build up, effectively promote the quiet run of device, and reactor outlet temperature can be prevented too high
Cause lower catalytic agent to prematurely reach the later stage and shorten catalyst service life using temperature.
From table 3 it is observed that the second naphtha cut is mainly made up of n-alkane and isoparaffin,
It is preferable steam crack material, the Cetane number of intermediate oil is 78, and sulfur, nitrogen content are all very low,
Can be used as high cetane number diesel oil blending component.
Embodiment 2
The present embodiment is used for the method producing intermediate oil by Fischer-Tropsch synthesis oil of the present invention is described,
Specifically as follows:
Fischer-Tropsch synthesis oil raw material enters hydrofining reactor, successively with hydrogenation protecting catalyst and hydrogenation essence
Catalyst haptoreaction processed, hydrofining reaction effluent enters to separate to carry out separating with fractionating system and divides
Evaporate, obtain the first naphtha cut, light diesel fuel fraction and heavy oil fraction.Wherein heavy oil fraction enters back into and sets
It is equipped with the isomery hydrocracking reactor of top reaction zone and lower reaction zone, according to the stream of reaction stream
To described heavy oil fraction is respectively in top reaction zone and lower reaction zone and isomery hydrocracking catalyst
Rcf-1 and isomery hydrocracking catalyst cdb-44 haptoreaction, and be hydrocracked in described isomery
Catalyst for refining after the afterbody filling of reactor, isomery hydrocracking reaction effluent enters and separates and fractional distillation
System carries out separating fractional distillation, obtains the second naphtha cut, intermediate oil and tail oil fraction, wherein,
4 beds are set in isomery hydrocracking reactor, and the 1st beds and the 2nd urge
Agent bed is top reaction zone, and the 3rd beds and the 4th beds react for bottom
Area, wherein, the cracking of the cracking activity level of the rcf-1 of unit volume and the cdb-44 of unit volume
The ratio of activity level is 1.2:1；Isomery hydrocracking catalyst in top reaction zone and lower reaction zone
Admission space is than for 1.2:1.Tail oil fraction all loops back the entrance of isomery hydrocracking reactor, tool
Product property after precursor reactant condition, reactivity worth and isomery hydrocracking reaction is shown in Table 2 and table 3.
From table 3 it can be seen that the selectivity of the intermediate oil of the present embodiment is 80.93%, cracking is anti-
The bed temperature rise answering device is 33 DEG C, this also illustrates the method that the present invention provides, on the one hand reduces positive structure
The secondary cracking extent of reaction of alkane and isoparaffin, decreases light component c1-c4Hydro carbons and Petroleum
The generation of fraction, improves selectivity and the yield of intermediate oil；On the other hand due to reacting in bottom
The relatively low catalyst of activity level is loaded in area, is conducive to controlling reaction depth, reduces the generation of heat
And accumulation, effectively promote the quiet run of device, and can prevent that reactor outlet temperature is too high to be caused
Lower catalytic agent is prematurely reached the later stage and is shortened catalyst service life using temperature.
From table 3 it can be seen that the second naphtha cut is mainly made up of n-alkane and isoparaffin, it is
Preferably steam crack material, the Cetane number of intermediate oil is 80, and sulfur, nitrogen content are all very low, can
As high cetane number diesel oil blending component.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that:
Four beds of isomery hydrocracking reactor all load same catalyst rcf-1.This
The concrete reaction condition of comparative example, reactivity worth and product property are shown in Table 2 and table 3.
From table 3 it can be seen that compared with Example 1, when 370 DEG C of fraction conversion ratios of ＞ are close, this
The intermediate oil selectivity of comparative example is low 3.57 percentage points, intermediate oil in fluid product distribution
Yield is low 3.33 percentage points, and the beds overall temperature rise of isomery hydrocracking reactor exceeds 6 DEG C,
The two reaction zones of this explanation isomery hydrocracking reactor load same catalyst it is impossible to slow down positive structure
The secondary cracking extent of reaction of alkane and isoparaffin, increased light component c1-c4Hydro carbons and Petroleum
The generation probability of fraction, correspondingly reduces selectivity and the yield of intermediate oil；On the other hand also unfavorable
In controlling reaction depth, increased generation and the accumulation of heat, cause that bed temperature rise is higher, this is unfavorable
Quiet run and the service life extending catalyst in device.
Comparative example 2
This comparative example is carried out using the method similar to comparative example 1, except that:
Four beds of isomery hydrocracking reactor all load same catalyst cdb-46.
The concrete reaction condition of this comparative example, reactivity worth and product property are shown in Table 2 and table 3.
From table 3 it can be seen that compared with Example 1, when 370 DEG C of fraction conversion ratios of ＞ are close, this
The intermediate oil selectivity of comparative example is low 3.16 percentage points, intermediate oil in fluid product distribution
Yield is low 3.47 percentage points, and the beds overall temperature rise of isomery hydrocracking reactor exceeds 5 DEG C,
The two reaction zones of this explanation isomery hydrocracking reactor load same catalyst it is impossible to slow down positive structure
The secondary cracking extent of reaction of alkane and isoparaffin, increased light component c1-c4Hydro carbons and Petroleum
The generation probability of fraction, correspondingly reduces selectivity and the yield of intermediate oil；On the other hand also unfavorable
In controlling reaction depth, increased generation and the accumulation of heat, cause that bed temperature rise is higher, this is unfavorable
Quiet run and the service life extending catalyst in device.
Table 2
Table 3
Embodiment 3
The present embodiment is carried out using method similar to Example 1, except for the difference that:
In the present embodiment, with the gross weight meter of the tail oil fraction in isomery hydrocracking reaction effluent, follow
The tail oil fraction of isomery hydrocracking reactor entrance described in loopback is 40 weight %.Remaining all with implement
Identical in example 1.Product property after concrete reaction condition, reactivity worth and isomery hydrocracking reaction is shown in
Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 81.36%, and cracking is anti-
The bed temperature rise answering device is 33 DEG C.
As can be seen from Table 5, the Cetane number of intermediate oil is 79, and sulfur, nitrogen content are all very low, can
As high cetane number diesel oil blending component.
Embodiment 4
The present embodiment is carried out using method similar to Example 2, except for the difference that:
In the present embodiment, in lower reaction zone, the isomery hydrocracking catalyst of filling is cdb-45, its
In, the cracking activity level of rcf-1 catalyst with the ratio of the cracking activity level of cdb-45 catalyst is
1.1:1.Remaining is all in the same manner as in Example 2.Concrete reaction condition, reactivity worth and isomery hydrogenation split
Change reacted product property and be shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 79.06%, and cracking is anti-
The bed temperature rise answering device is 36 DEG C.
As can be seen from Table 5, the Cetane number of intermediate oil is 80, and sulfur, nitrogen content are all very low, can
As high cetane number diesel oil blending component.
Embodiment 5
The present embodiment is carried out using method similar to Example 1, except for the difference that:
In the present embodiment, the filling body of isomery hydrocracking catalyst in top reaction zone and lower reaction zone
Long-pending ratio is 3:1.Remaining is all in the same manner as in Example 1.Concrete reaction condition, reactivity worth and isomery add
Product property after hydrogen cracking reaction is shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 81.55%, and cracking is anti-
The bed temperature rise answering device is 33 DEG C.
As can be seen from Table 5, the Cetane number of intermediate oil is 78, and sulfur, nitrogen content are all very low, can
As high cetane number diesel oil blending component.
Embodiment 6
The present embodiment is carried out using method similar to Example 5, except for the difference that:
In the present embodiment, the filling body of isomery hydrocracking catalyst in top reaction zone and lower reaction zone
Long-pending ratio is 4:1.Remaining is all in the same manner as in Example 5.Concrete reaction condition, reactivity worth and isomery add
Product property after hydrogen cracking reaction is shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 81.07%, and cracking is anti-
The bed temperature rise answering device is 35 DEG C.
As can be seen from Table 5, the Cetane number of intermediate oil is 77, and sulfur, nitrogen content are all very low, can
As high cetane number diesel oil blending component.
Table 4
Table 5
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Apply the detail in mode, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible compound modes.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of method producing intermediate oil by Fischer-Tropsch synthesis oil, the method includes: Fischer-Tropsch is closed
Become oily and hydrogeneous logistics to be introduced in the hydrofining reactor containing Hydrobon catalyst to be reacted, so
Afterwards hydrofining reaction effluent is carried out successively separating and fractional distillation, obtain the first naphtha cut, light bavin
Oil distillate and heavy oil fraction；The described heavy oil fraction isomery containing isomery hydrocracking catalyst for the introducing is added
Reacted in hydrogen cracker, then by isomery hydrocracking reaction effluent successively carry out separate and
Fractional distillation, obtains the second naphtha cut, intermediate oil and tail oil fraction, optionally by least part of institute
State tail oil and loop back isomery hydrocracking reactor entrance and be circulated；Wherein, described isomery is hydrocracked
At least provided with two reaction zones in reactor, according to the flow direction of reaction stream, single in two neighboring reaction zone
The cracking activity of the isomery hydrocracking catalyst of position volume reduces successively.
2. method according to claim 1, wherein, with isomery hydrocracking reaction effluent
Tail oil fraction gross weight meter, the tail oil fraction looping back described isomery hydrocracking reactor entrance is
10-100 weight %；It is preferably 50-100 weight %.
3. method according to claim 1, wherein, according to the flow direction of reaction stream, adjacent two
In individual reaction zone, the ratio of the cracking activity of isomery hydrocracking catalyst of unit volume is 1.1-10:1；
It is preferably 1.2-5:1.
4. the method according to any one in claim 1-3, wherein, according to reaction stream
Flow direction, setting top reaction zone and lower reaction zone in described isomery hydrocracking reactor, top is reacted
In area and lower reaction zone, the admission space of isomery hydrocracking catalyst is than for 1-4:1；It is preferably
1.2-2.5:1.
5. method according to claim 4, wherein, in the reaction zone of top, isomery is hydrocracked and urges
The infrared acidity of agent is 0.5-1.0mmol/g, and in lower reaction zone, isomery hydrocracking catalyst is infrared
Acidity is 0.1-0.45mmol/g.
6. the method according to any one in claim 1-3, wherein, described hydrofinishing is urged
The amorphous alumina as carrier and load vib race metal on the carrier is contained in agent
Element and/or viii race metallic element, described vib race metallic element is mo and/or w, described viii
Race's metallic element is co and/or ni.
7. the method according to any one in claim 1-3, wherein, described isomery hydrogenation splits
Change in catalyst containing as the amorphous silica-alumina of carrier and load active component on the carrier
Element；Described active component element includes precious metal element and/or non-noble metal j element；Described base metal
Element is vib race metallic element and/or viii race metallic element；
Preferably described vib race metallic element is mo and/or w, and described viii race metallic element is co
And/or ni；Described precious metal element is pt element and/or pd element.
8. the method according to any one in claim 1-3, wherein, described hydrofinishing is anti-
The reaction condition in device is answered to include: hydrogen dividing potential drop is 2.0-15.0mpa, reaction temperature is 250-400 DEG C, hydrogen
For 100-1000:1, volume space velocity is 0.5-8.0h to oil volume ratio-1；
Reaction condition in preferably described isomery hydrocracking reactor includes: hydrogen dividing potential drop is
2.0-15.0mpa, reaction temperature is 300-450 DEG C, and hydrogen to oil volume ratio is 300-1500:1, and volume is empty
Speed is 0.5-5.0h-1.
9. method according to claim 1, wherein, according to the flow direction of reaction stream, described plus
Hydrogenation protecting catalyst and described Hydrobon catalyst, hydrogenation protecting is loaded successively in hydrogen finishing reactor
The admission space of catalyst and Hydrobon catalyst is than for 2-30:100；
Preferably described hydrogenation protecting catalyst includes carrier and load active component on the carrier
Element, described active component element is vib race metallic element and/or viii race metallic element.
10. method according to claim 1, wherein, described Fischer-Tropsch synthesis oil is from slurry bed system
The synthesis light oil of fischer-tropsch synthesis process, the full fraction of synthesis of heavy oil and synthetic wax and/or be derived from fixed bed Fischer-Tropsch
The full fraction of the synthesis light oil, synthesis of heavy oil and synthetic wax of synthesis technique.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510420352.7A CN106350110B (en) | 2015-07-16 | 2015-07-16 | A method of intermediate oil is produced by Fischer-Tropsch synthesis oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510420352.7A CN106350110B (en) | 2015-07-16 | 2015-07-16 | A method of intermediate oil is produced by Fischer-Tropsch synthesis oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106350110A true CN106350110A (en) | 2017-01-25 |
| CN106350110B CN106350110B (en) | 2018-11-02 |
Family
ID=57842227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510420352.7A Active CN106350110B (en) | 2015-07-16 | 2015-07-16 | A method of intermediate oil is produced by Fischer-Tropsch synthesis oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106350110B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437788A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil processing technology |
| CN114752411A (en) * | 2022-03-29 | 2022-07-15 | 中国神华煤制油化工有限公司 | Multipurpose fuel oil and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106467A1 (en) * | 2003-05-12 | 2004-12-09 | Chevron U.S.A. Inc. | Process for upgrading fischer-tropsch products using dewaxing and hydrofinishing |
| CN1854265A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil |
| CN103059959A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Technological method for producing low sulfur gasoline |
| CN104611029A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel hydroconversion method |
-
2015
- 2015-07-16 CN CN201510420352.7A patent/CN106350110B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106467A1 (en) * | 2003-05-12 | 2004-12-09 | Chevron U.S.A. Inc. | Process for upgrading fischer-tropsch products using dewaxing and hydrofinishing |
| CN1854265A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil |
| CN103059959A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Technological method for producing low sulfur gasoline |
| CN104611029A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel hydroconversion method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437788A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil processing technology |
| CN114437788B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil processing technology |
| CN114752411A (en) * | 2022-03-29 | 2022-07-15 | 中国神华煤制油化工有限公司 | Multipurpose fuel oil and preparation method thereof |
| CN114752411B (en) * | 2022-03-29 | 2023-09-05 | 中国神华煤制油化工有限公司 | Multipurpose fuel oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106350110B (en) | 2018-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100389181C (en) | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil | |
| CN104611040B (en) | A kind of method for hydrogen cracking | |
| CN103013559A (en) | Hydrocracking method for selective increasing of aviation kerosene yield | |
| CN100389180C (en) | Integrated Fischer-Tropsch synthetic oil hydrogenation purification | |
| CN105802665B (en) | A kind of method for hydrogen cracking and reaction unit of maximum volume production heavy naphtha | |
| CN102453535B (en) | Hydrocracking method for reforming material yield increase | |
| CN102399586A (en) | A mid-pressure hydrocracking method for producing jet fuel | |
| CN107987879A (en) | A kind of and method for hydrogen cracking of production heavy naphtha and tail oil | |
| CN104611021B (en) | A kind of hydrocracking process | |
| CN102344828B (en) | Processing method of inferior residual oil | |
| CN101230291B (en) | Low consumption energy method for processing fischer-tropsch synthesis | |
| CN103059986B (en) | Hydrocracking method for producing chemical materials | |
| CN100395315C (en) | Hydrogenation purifying combined process for Fischer-Tropsch synthetic substance | |
| CN101177623A (en) | Hydro-cracking method for Fisher-Tropsch synthesis fuels | |
| CN106350110B (en) | A method of intermediate oil is produced by Fischer-Tropsch synthesis oil | |
| CN110643391B (en) | Method for converting coal tar/heavy oil into liquefied gas, naphtha and diesel oil | |
| CN102344829A (en) | Combination method for residue hydrotreatment, catalytic cracking heavy oil hydrogenation and catalytic cracking | |
| CN107033954B (en) | A kind of method of hydrogenation of Fischer-Tropsch synthesis oil upgrading | |
| CN100510022C (en) | Low-hydrogenloss hydrogenation of high-output qulified diesel oil | |
| CN103773413A (en) | Method for producing base oil of lubricating oil | |
| CN106398762B (en) | A method of intermediate oil is produced by hydrogenation of Fischer-Tropsch synthesis oil | |
| CN100419044C (en) | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil | |
| CN109207197A (en) | A kind of method for processing wax oil raw material and the system for processing wax oil raw material | |
| CN104560186B (en) | Catalytic conversion method capable of realizing maximum gasoline production | |
| CN102807898B (en) | Hydrocracking method for increasing production of high-quality middle distillates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |