CN103805271A - Processing method of ethylene cracking equipment byproduct - Google Patents
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- CN103805271A CN103805271A CN201210442629.2A CN201210442629A CN103805271A CN 103805271 A CN103805271 A CN 103805271A CN 201210442629 A CN201210442629 A CN 201210442629A CN 103805271 A CN103805271 A CN 103805271A
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Abstract
The invention discloses a processing method of an ethylene cracking equipment byproduct. The method is as follows: fractionating ethylene tar into a light fraction and a heavy fraction, mixing the heavy fraction with a conventional coking raw material, conducting delayed coking to obtain coker gasoline, coker diesel oil, and coker wax oil, successively performing prehydrofining and hydrofining on the coker gasoline and an ethylene cracking C5 fraction, mixing the coker diesel oil with the coker wax oil and the light fraction, subjecting the mixture to hydrotreating, and separating the obtained hydrotreating product together with the hydrofining product to obtain the C5 fraction, a gasoline fraction and a diesel oil fraction. Directed at the characteristics of high content of aromatic hydrocarbons, colloid, carbon residues and asphaltene in the ethylene tar, the method provided in the invention fractionates the ethylene tar into the light fraction and the heavy fraction, and adopts different processing processes, thus not only enhancing the utilization rate and the additional value of the ethylene tar, increasing the yields of gasoline and diesel oil, improving the product quality of light fuel oil, enabling the equipment to run smoothly for a long period, also providing a raw material for the ethylene cracking equipment, and increasing the yield of ethylene.
Description
Technical field
The present invention relates to a kind of method of producing clean fuel oil, specifically a kind of delayed coking of ethylene cracker by-product C5 and ethylene bottom oil and combined technical method of hydrogenation processed.
Background technology
World petroleum resource is day by day deficient at present, and price is day by day raised, on the other hand, along with the raising of people's living standard, day by day vigorous to clean motor transport fuel demand.This contradiction, makes refinery reduce discharging synergy and necessitates, and the refinery's by product not yet making full use of is converted into clean fuel oil and has realistic meaning.
Cracking of ethylene C 5 fraction is the by product that comes from ethylene unit, conventionally account for 14% ~ 20%(of ethylene yield according to cracking stock and cracking severity fluctuation), C 5 fraction composition is mainly the alkene of C4 ~ C6, diolefine is about 35% ~ 50%, monoolefine is about 14% ~ 20%, generally before Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline, separates and obtains through depentanizer.C 5 fraction can take hot dimerization method, solvent extraction process, azeotropic distn etc. to isolate cyclopentadiene, isoprene and m-pentadiene (see " printing when chemical industry " the 2nd phase P7-P10 in 1998: " deep processing of carbon 5, carbon 9 ").At present, cracking of ethylene by-product C5 is mainly as device or domestic fuel, or select hydrogenation to make vapour Water Oil Or Gas blend component, or separation and Extraction diolefine, or for the production of C5 resin, or as ethylene cracking material (see " Tianjin chemical industry " the 5th phase P36-P37 in 2002: " industrial application of cracked C 5 fraction ").
Come from the ethylene bottom oil of ethylene cracker, main as heavy fuel oil (HFO) or carbon black raw material sale at present, added value is lower.Ethylene bottom oil be ethylene cracking material at steam cracking process Raw and product pyrocondensation product, its initial boiling point is at 170 ~ 260 ℃, 600 ℃ of final boiling point >, are generally 600～700 ℃, belong to last running scope.Ethylene bottom oil is mainly the mixture of the above condensed-nuclei aromatics of dicyclo, and aromaticity content reaches more than 90%, and density (20 ℃) is greater than 1.0 g/cm
3, the foreign matter contents such as sulphur and nitrogen are low, substantially metal impurities not.
In order to increase economic efficiency, each refinery is developed multiple method of comprehensive utilization, and such as extracting, naphthalene and series product thereof, light constituent (<300 ℃) synthesizing petroleum resin, tar heavy oil are produced carbon fibre asphalt and carbon fiber, gac etc. is produced in >540 ℃ last running.In aforesaid method, still have some intermediate oils not to be fully used, overall economic efficiency needs to be further improved.
The report that carries out delayed coking about vacuum residuum blending ethylene tar has: CN101608132A, " response surface analysis method is optimized the delayed coking research of blending ethylene pyrolysis fuel oil " (sees " refining of petroleum and chemical industry " the 8th phase P5-P8 in 2009, " delayed coking unit is mixed the research of refining grand celebration pyrolysis fuel oil " (seeing " refining of petroleum and chemical industry " the 12nd phase P20-P22 in 2007), " impact of blending ethylene cracking masout on delayed coking " (seeing " petrochemical technology and application " the 1st phase P44-P49 in 2010) and " Coking Test of Vacuum Residue with Ethylene Heavy Tar " (are shown in " Maoming College's journal " the 1st phase P7-P9 in 2008 etc., these researchs are all that full ethylene bottom oil cut and vacuum residuum are mixed to refining as delayed coking raw material, can make like this yield of liquid yield and light Fuel oil production lower, and its gained liquid product---coker gasoline, the quality of diesel oil and wax oil is still poor, also need further processing treatment.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides that a kind of ethylene bottom oil utilization ratio is high, the working method of ethene and vapour, ethylene cracker by-product that diesel oil fuel output is high.
Ethylene bottom oil of the present invention is produced the method for light-weight fuel oil, comprising:
Ethylene bottom oil is fractionated into lighting end and last running, and last running mixes with conventional coking raw material, and delayed coking obtains coker gasoline, coker gas oil, wax tailings; First behind pre-hydrofining reaction district after the coker gasoline of gained mixes with cracking of ethylene C 5 fraction, products therefrom is again through hydrofining reaction district; Coker gas oil and wax tailings mix with ethylene bottom oil lighting end, and through hydrotreatment, gained hydrotreatment products, together with hydrotreated product, is isolated to C 5 fraction, gasoline fraction and diesel oil distillate.
In the inventive method, cracking of ethylene C 5 fraction can be the by product that directly comes from ethylene cracker, can be also through dialkene removal cut after treatment, can be also above-mentioned mixture.
In the inventive method, part gasoline fraction capable of circulation to hydrofining reaction district as hydrofining reactor raw material, another part gasoline fraction and whole diesel oil distillate are as product caterpillar.The C 5 fraction of gained returns to ethylene cracker as raw material.
In the inventive method, the cut point of ethylene bottom oil lighting end and last running is 400～520 ℃, is preferably 460～520 ℃.
In the inventive method, the blending ratio of ethylene bottom oil last running and conventional coking raw material is 1:1 ~ 9.
Described conventional coking raw material can be weight, the residual oil raw material of initial boiling point >350 ℃, generally can be selected from one or more in heavy deasphalted oil, catalytically cracked oil, viscous crude and the topped crude of long residuum, vacuum residuum, visbroken resids, deasphalting unit, certainly also can be selected from other as: one or more in liquefied coal coil, shale wet goods, are preferably vacuum residuum.Described delayed coking can adopt conventional operational condition, is generally: 480～530 ℃ of temperature of reaction, and reaction pressure 0.05 MPa～0.80MPa, is preferably in 0.10MPa～0.20MPa; Residence time 5min～50min, best 10 min～30min; Circulation weight ratio is 0.01～1.0, preferably 0.2～0.6.
In the inventive method, the add-on of cracking of ethylene C 5 fraction and coker gasoline weight ratio are 5 ~ 12:1.
In the inventive method, amount and coker gasoline weight ratio that gasoline fraction is recycled to hydrofining reaction district are 1 ~ 3:1.
The unifining process of described coker gasoline and cracking of ethylene C 5 fraction can adopt conventional method to carry out, and preferred process is as follows: coker gasoline and the pre-hydrofining reaction of cracking of ethylene C 5 fraction warp district, then pass through hydrofining reaction district.In the inventive method, Hydrogenation of Coker Gasoline pre-refining reaction zone and hydrofining reaction district preferably adopt one-stage serial technique, and two reaction zones are in different reactors.Wherein pre-hydrofining reaction district preferred operations condition is: hydrogen dividing potential drop be 3.0 ~ 8.0MPa, hydrogen to oil volume ratio while being 500:1 ~ 800:1, liquid volume space velocity be 2.0 ~ 6.0h
-1, temperature of reaction is 130 ~ 180 ℃; Hydrofining reaction district preferred operations condition is: volume space velocity 1.0 ~ 1.6h when 100 ~ 250 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0 ~ 3.0MPa, hydrogen to oil volume ratio 300:1 ~ 700:1 and liquid
-1.
Described coker gas oil, wax tailings mix with ethylene bottom oil lighting end, and the mixing raw material of gained carries out hydrotreatment, passes through successively hydrofining reaction district and hydrocracking reaction district.Wherein, the hydrofining reaction district of mixing raw material hydrotreatment and hydrocracking reaction district adopt one-stage serial technique, and two reaction zones are in same reactor, or respectively in different reactors.Wherein, mixing raw material hydrofining reaction district preferred operations condition is: volume space velocity 0.4 ~ 0.8h when 350 ~ 380 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 16.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid
-1.Hydrocracking reaction district preferred operations condition is: volume space velocity 0.4 ~ 0.8h when 380 ~ 400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.0 ~ 16.0MPa, hydrogen to oil volume ratio are 1300:1 ~ 1500:1 and liquid
-1.
In the inventive method, mixing raw material elder generation and the isocrackate heat exchange of coker gas oil and wax tailings and ethylene bottom oil lighting end, then the mode heating up through raw materials furnace and heating reaches the temperature in requirement in hydrofining reaction district.
In the inventive method, the Hydrobon catalyst that coker gasoline and the pre-hydrofining reaction of cracking of ethylene C 5 fraction adopt preferably uses the Hydrobon catalyst with high pore volume and high-specific surface area, this catalyzer is take group VIB and/or group VIII metal as active metal component, take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; Catalyzer preferred property is: pore volume 0.35 ~ 0.70ml/g, specific surface area is 280 ~ 400m
2/ g, take oxide compound hydrogenation active metals weight content as 5% ~ 20%, is preferably 8% ~ 16% in catalyzer.Applicable in the art commodity Hydrobon catalyst is as FHRS-1 catalyzer of Fushun Petrochemical Research Institute's development and production etc.
In the inventive method, the Hydrobon catalyst that the hydrofining reaction district of coker gasoline and cracking of ethylene C 5 fraction hydrofining reaction district and mixing raw material is used is conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, generally take group VIB and/or group VIII metal as active ingredient, take the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus as carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Take the weight of catalyzer as benchmark, group VIB metal content is counted 10wt% ~ 35wt% with oxide compound, and group VIII metal content is counted 3wt% ~ 15wt% with oxide compound, and its character is as follows: specific surface area is 100 ~ 350m
2/ g, pore volume is 0.15 ~ 0.60ml/g.Main catalyzer have China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develop 3936,3996, FF-16, FF-26 etc.In the inventive method; in the hydrofining reaction district of mixture; before Hydrobon catalyst, preferably load hydrogenation protecting catalyst; described hydrogenation protecting catalyst can adopt residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst, and hydrogenation protecting agent used accounts for 10% ~ 50% of Hydrobon catalyst volume.In the inventive method, hydrogenation protecting catalyst is take group VIB and/or group VIII metal as active metal component, and take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; Take the weight of catalyzer as benchmark, active metallic content is counted 0.5wt% ~ 18wt% with oxide compound.For example: FZC-103, the FZC-200 catalyzer of Fushun Petrochemical Research Institute's research and development.
In the inventive method, described hydrocracking reaction district filling hydrocracking catalyst, be preferably in hydrocracking catalyst upstream filling removal of ccr by hydrotreating catalyzer, wherein mixing raw material hydrofining reaction district Hydrobon catalyst used accounts for 70% ~ 100% of hydrocracking catalyst admission space, and the admission space of removal of ccr by hydrotreating catalyzer accounts for 10% ~ 40% of hydrocracking catalyst admission space.The hydrocracking catalyst adopting can adopt one or more conventional hydrocracking catalysts, and generally, take group VIB and/or group VIII metal as active metal component, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The carrier of this catalyzer is two or more in aluminum oxide, silicon-containing alumina and molecular sieve, preferably adopts the hydrocracking catalyst containing molecular sieve and amorphous aluminum silicide.That the present invention recommends is composed as follows (take the weight of catalyzer as benchmark): the content of Y molecular sieve or beta-molecular sieve is as 10% ~ 40%, the content of amorphous aluminum silicide is 20% ~ 60%, group vib hydrogenation active metals is take the content of oxide compound as 15% ~ 40%, group VIII hydrogenation active metals is take the content of oxide compound as 1% ~ 10%, and surplus is little porous aluminum oxide; The character of hydrocracking catalyst is as follows: specific surface area is 180 ~ 300m
2/ g, pore volume is 0.25 ~ 0.45ml/g.FC-14, ZHC-02, the hydrocracking catalysts such as 3974 developed such as Fushun Petrochemical Research Institute.
In the inventive method, described removal of ccr by hydrotreating catalyzer is take group VIB metal and group VIII metal as hydrogenation activity component, as two or three in W, Mo, Ni and Co, is preferably W, Mo and Ni, this catalyzer preferably contains auxiliary agent Si and Ti, take aluminum oxide as carrier.Take the weight of catalyzer as benchmark, WO
3content be 16% ~ 23%, MoO
3content be 6% ~ 13%, NiO content is 3% ~ 8%, silicone content is with SiO
2count 4% ~ 12%, be preferably 5% ~ 9%, titanium oxide content is 0.5% ~ 4%, is preferably 1% ~ 2%, and surplus is aluminum oxide.The character of this catalyzer is as follows: pore volume is 0.30 ~ 0.55cm
3/ g, specific surface area is 120 ~ 300m
2/ g, average pore diameter is 5 ~ 10nm, is preferably 5 ~ 8nm.
Tool of the present invention has the following advantages:
1, the inventive method is low and coking vapour for current ethylene bottom oil utilization ratio, the ropy problem of diesel product, be lighting end and last running by ethylene bottom oil fractionation, adopt different working methods according to the compositing characteristic of two cuts, last running is mixed refining and is obtained liquid product to first delayed coking in conventional coking raw material, wherein coker gas oil and wax tailings mix with ethylene bottom oil lighting end, carry out hydrotreatment, products therefrom and coker gasoline, cracking of ethylene C 5 fraction mixing raw material is through pre-hydrofining, the hydrotreated product of hydrofining gained together, obtain gasoline and the diesel oil of quality improvement through fractionation, improve so on the one hand the utilization ratio of ethylene bottom oil, the raw material sources of producing light-weight fuel oil are expanded, solve on the other hand coking vapour, the ropy problem of diesel product, effectively alleviated because the existence of alkene in hydrogenating materials causes device short problem running period simultaneously.
2, the inventive method is mixed ethylene bottom oil last running to refine the raw material as delayed coking in conventional coking raw material, the raw material sources of coker are expanded so on the one hand, ethylene bottom oil lighting end mixes with coker gas oil, wax tailings on the other hand, be converted into clean vapour, diesel oil blending component completely through hydrotreatment, by refinery's by-product---the light-weight fuel oil being converted into ethylene bottom oil maximum, two aspects are all favourable to improving refinery's economic benefit.
3, the inventive method is mixed the wax tailings of coking gained as hydrotreated feed with coker gas oil and ethylene bottom oil lighting end, can reduce to a certain extent the naphthalene series substance concentration in coker gas oil and ethylene bottom oil lighting end, alleviate the concentrated heat release problem of hydrogenation unit, favourable to reducing facility investment and assurance device smooth operation.On the other hand, the wax tailings ethylene bottom oil lighting end relatively high with final boiling point as hydrotreated feed, increased the treatment capacity of hydrotreater together with coker gas oil, improved the transformation efficiency of vapour, diesel product.
4, in the inventive method, condensed-nuclei aromatics content in wax tailings, coker gas oil and ethylene bottom oil lighting end mixture is higher, if without further hydrotreatment, its quality product is by very poor, especially cetane value is on the low side, and after employing the inventive method, the cetane value of gained diesel oil distillate is improved significantly, quality product is improved.
5, the inventive method adopts coker gasoline, cracking of ethylene C 5 fraction to mix, as pre-hydrofining reaction raw material, adopt part gasoline fraction product to loop back the method for hydrofining reactor entrance simultaneously, can effectively reduce diene and concentration of olefin in cracking of ethylene C 5 fraction, significantly reduce device temperature rise, move favourable to reduction temperature of reaction, assurance device safety and steady.
6, the inventive method by cracking of ethylene C 5 fraction, coker gasoline together after hydrofining, obtain C 5 fraction, clean gasoline and diesel product with together with the generation oil of hydrotreatment gained through fractionation, C 5 fraction returns to ethylene unit as cracking stock, can improve ethene, the about 10wt% ~ 15wt% of propone output, so, take full advantage of C 5 fraction, increased again ethene, propone output, to improve utilization ratio of device, increase economic benefit favourable.
7, the inventive method by the coker gasoline of coking gained together with cracking of ethylene C 5 fraction after hydrofining, obtain clean gasoline and diesel product with together with the generation oil of hydrotreatment gained through fractionation, improve so on the one hand the quality product of gasoline fraction, share on the other hand a separation column, favourable to economy system investment and reduction energy consumption.
8, in the inventive method, ethylene bottom oil lighting end, coker gas oil and wax tailings cut mixing raw material are in the time of hydrotreatment, pass through successively hydrogenation protecting agent, hydrofining agent, removal of ccr by hydrotreating catalyzer and hydrocracking agent, can hold back resin and asphalt a small amount of in raw material or make it be converted into micromolecular compound, protect host, extended the running period of device; Meanwhile, such grating mode also can make condensed-nuclei aromatics saturated by ring hydrogenation, is conducive to further cracking, useful to improving yield of light oil.
9, the present invention, for the lower ethylene bottom oil of added value provides a kind of working method that improves its economy, under the present situation of crude supply growing tension, reduces discharging synergy to refinery useful.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method.
Embodiment
In conjunction with Fig. 1, the invention will be further described.Ethylene bottom oil 1 obtains lighting end 3 and last running 4 through separation column 2, last running 4 and conventional coking raw material 5 mix, coker gasoline 7, coker gas oil 8 and wax tailings 9 that delayed coker 6 obtains, coker gas oil 8 and wax tailings 9 are mixed to get mixing raw material 10 with ethylene bottom oil lighting end 3, enter hydrotreating reactor 11, obtain generating oil 12 through hydrofining reaction district and hydrocracking reaction district, coker gasoline 7 and cracking of ethylene C 5 fraction 20 mix, through pre-hydrofining reactor 13, products therefrom mixes with the final gasoline fraction product 18 of part, enter after hydrofining reactor 14, obtain hydrofining and generate oil 15, generate oil 15 and obtain final C 5 fraction 17 through stripping tower and separation column 16 together with generating oil 12, gasoline fraction 18 and diesel oil distillate 19, wherein a part of gasoline fraction 18 mixes and carries out hydrofining reaction with pre-hydrotreated product before looping back gasoline hydrofinishing reactor, part gasoline fraction 18 is as gasoline products caterpillar, C 5 fraction 17 returns to ethylene unit and carries out scission reaction as Ethylene Unit Feedstocks.
The following examples will be further described present method, but be not limited in this.In the present invention, wt% is massfraction.
Embodiment of the present invention hydrocracking catalyst used is prepared as follows:
1, contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and Y zeolite: A1, A2.
(1) hydrocracking catalyst A1:
By amorphous aluminum silicide (specific surface area 520m2/g, SiO
235wt%, pore volume 1.2ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 9, lattice constant 2.432, specific surface 650m2/g, infrared acidity 0.45mmol/g), after mixing, add (added by the little porous aluminum oxide of pore volume 0.42ml/g prepared by rare nitric acid peptization) tackiness agent roll agglomerating after, put into after banded extruder extruded moulding, be dried 10 hours at 110 ℃, 500 ℃ of activation make carrier for 4 hours, then steep immersion by Mo-Ni total immersion and steep, then be dried 12 hours at 110 ℃, and 500 ℃ activate 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 48wt%, Y molecular sieve 15wt%, aluminum oxide 12wt%, nickel oxide 5wt%, molybdenum oxide 20wt%.Specific surface area of catalyst 220m
2/ g, pore volume 0.35ml/g.
(2) hydrocracking catalyst A2:
By amorphous aluminum silicide (specific surface area 490m2/g, SiO
245wt%, pore volume 1.0ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 12, lattice constant 2.436, specific surface 680m2/g, infrared acidity 0.41mmol/g), after mixing, add the tackiness agent of (being added the preparation of rare nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g) roll agglomerating after, put into after banded extruder extruded moulding, 110 ℃ dry 10 hours, 500 ℃ of activation make after carrier for 4 hours, by W-Ni total immersion stain immersion stain, be then dried 12 hours at 110 ℃, and 500 ℃ activate 3 hours again.Catalyzer finally consists of: amorphous aluminum silicide 45wt%, Y molecular sieve 13wt%, aluminum oxide 12wt%, nickel oxide 6.5wt%, Tungsten oxide 99.999 22.5wt%.Specific surface area of catalyst 210m
2/ g, pore volume 0.31ml/g.
2, contain the preparation of the hydrocracking catalyst B1 of amorphous aluminum silicide and beta-molecular sieve.
Hydrocracking catalyst B1:
By beta-molecular sieve (SiO
2/ Al
2o
3mol ratio is 40, specific surface area 580m2/g, infrared acidity 0.21mmol/g), amorphous aluminum silicide (specific surface 450m2/g, SiO
255wt%, pore volume 0.9ml/g) mix, add little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization by concentration 3.3wt%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains is dried 12 hours at 110 ℃, and 500 ℃ of activation make after activated carrier for 4 hours.Flood again the carrier of above-mentioned preparation with W-Ni co-impregnated solution, then be dried 8 hours at 110 ℃, and 500 ℃ activate 3 hours.Catalyzer finally consists of: β zeolite 25wt%, amorphous aluminum silicide 25wt%, aluminum oxide 20wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Specific surface area of catalyst 235m
2/ g, pore volume 0.32ml/g.
Embodiment of the present invention removal of ccr by hydrotreating catalyzer used is prepared as follows:
Take 298g Si-Al
2o
3(butt 67w%, dioxide-containing silica is 19w%) powder, sesbania powder 5g, is mixed, and adds by 188g water, 43.0g containing 17wt%TiCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extruded moulding, this strip is dried 4 hours at 108 ℃, roasting 4 hours at 550 ℃.Flood active metal by ordinary method, molybdenum, tungsten and nickel are then dried 2 hours at 120 ℃, and at 550 ℃, roasting 3 hours, makes catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
Composition and the character of table 1 removal of ccr by hydrotreating catalyzer
| Catalyzer | HDC-1 |
| Composition, %(massfraction) | |
| WO 3 | 22 |
| |
11 |
| NiO | 5 |
| |
9 |
| |
2 |
| Al 2O 3 | Surplus |
| Character | |
| Specific surface area, m 2/g | 220 |
| Average pore diameter, nm | 6.8 |
Embodiment 1 ~ 3
Adopt Fig. 1 flow process.Ethylene bottom oil is divided into lighting end and last running through distillation, respectively take 420 ℃ and 480 ℃ as cut point, after distillation, obtain respectively light, last running, character is listed in table 2, Vacuum Residue Properties is listed in table 3, cracking of ethylene C 5 fraction character is listed in table 4, and the last running of gained ethylene bottom oil mixes with vacuum residuum, and the character of mixing raw material and delay coking process condition thereof, gained gasoline and diesel oil distillate is in table 5.Coker gasoline and the pre-hydrofining technology condition of cracking of ethylene C 5 fraction hydrofining technology condition are in table 6.In embodiment, coker gas oil and wax tailings mix with ethylene bottom oil lighting end, obtain light-weight fuel oil through hydrotreatment.Hydroprocessing technique condition is in table 7.In embodiment; hydrotreating reactor adopts two reactors in series modes; one instead loads hydrogenation protecting agent FZC-103, Hydrobon catalyst 3936 from top to bottom; two instead load removal of ccr by hydrotreating catalyzer and hydrocracking catalyst from top to bottom; in embodiment 1 and 3, the volume ratio of these four kinds of catalyzer is 12:38:10:40; in embodiment 2, the volume ratio of these four kinds of catalyzer is 15:35:12:38; product enters separation system together with coking gasoline hydrogenation refining product; obtain quality clean vapour, diesel oil blending component preferably, reaction result is in table 8.In addition, this device has carried out the service test of 5000 hours, and product distributes and each narrow fraction product property is substantially constant or it is very little to change, and illustrates that present method, also can solving device short problem running period in improving vapour, diesel product quality.
Comparative example 1
Ethylene bottom oil is without distillation, and full cut mixes with mass ratio 1:1 with vacuum residuum, and this mixture carries out the processing condition of delayed coking and product property in table 5.The pre-hydrofining technology condition of coker gasoline and hydrofining technology condition are in table 6, and coker gas oil and wax oil cut obtain light-weight fuel oil through hydrotreatment, and hydroprocessing technique condition is in table 7.Hydrotreating reactor adopts two reactors in series modes; one instead loads hydrogenation protecting agent FZC-103, Hydrobon catalyst 3936 from top to bottom; two instead load removal of ccr by hydrotreating catalyzer and hydrocracking catalyst from top to bottom; the volume ratio of these four kinds of catalyzer is 10:40:10:40, and reaction result is in table 8.
Table 2 ethylene bottom oil adopts that different cut point gained are light, last running character
| Cut point | 420℃ | 420℃ | 480℃ | 480℃ |
| Crude title | Lighting end | Last running | Lighting end | Last running |
| Numbering | L1 | H1 | L2 | H2 |
| S，μg/g | 398 | 458 | 402 | 466 |
| N，μg/g | 48 | 196 | 56 | 218 |
| CCR，wt% | 3.9 | 23.65 | 4.6 | 26.9 |
| Aromatic hydrocarbons, wt % | 50.1 | 38.1 | 46.6 | 33.2 |
| Colloid+bituminous matter, wt % | 46.9 | 61.7 | 51.4 | 65.1 |
| Metal content, μ g/g | ||||
| Ni | 0.06 | 0.1 | 0.07 | 0.1 |
| V | 0.01 | 0.01 | 0.01 | 0.01 |
Table 3 Vacuum Residue Properties
| Crude title | Vacuum residuum |
| S，wt% | 2.98 |
| N，mg/kg | 4913 |
| CCR，wt% | 17.12 |
| Aromatic hydrocarbons, wt % | 47.7 |
| Colloid+bituminous matter, wt % | 34.6 |
| Metal content, μ g/g | |
| Ni | 61.7 |
| V | 172.5 |
Table 4 cracking of ethylene C 5 fraction character
| Title | Cracking of |
| Chief component | C4~C6 |
| Boiling range /℃ | 50~100 |
| Density (20 ℃), g/cm 3 | 0.62 |
| Olefin(e) centent, wt % | 49.15 |
| Aromaticity content, wt % | 0.3 |
Table 5 delayed coking condition and product property
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Processing condition | ||||
| Temperature of reaction, ℃ | 505 | 500 | 495 | 500 |
| Reaction pressure, MPa | 0.15 | 0.17 | 0.12 | 0.17 |
| Circulation weight ratio | 0.5 | 0.4 | 0.5 | 0.4 |
| Ethylene bottom oil last running | H1 | H1 | H2 | - |
| Ethylene bottom oil last running: vacuum residuum (mass ratio) | 1：3 | 1：5 | 1：7 | The full cut of 1:1(: subtract slag) |
| Coker gasoline cut character | G1 | G2 | G3 | G4 |
| Boiling range, ℃ | 57~182 | 50~175 | 53~180 | 48~176 |
| Yield, wt%(is to mixing raw material) | 9.40 | 9.46 | 9.38 | 9.37 |
| Sulphur content, μ g/g | 2752 | 2603 | 2711 | 2688 |
| Research octane number (RON) | 76 | 75 | 77 | 78 |
| Fraction of coker gas oil character | D1 | D2 | D3 | D4 |
| Boiling range, ℃ | 175~365 | 173~363 | 178~366 | 174~361 |
| Yield, wt%(is to mixing raw material) | 41.71 | 46.44 | 40.58 | 42.53 |
| Density (20 ℃), g/cm 3 | 0.9668 | 0.9540 | 0.9697 | 0.9651 |
| Sulphur content, μ g/g | 5095 | 4951 | 5252 | 5013 |
| Cetane value | ＜-21.5 | ＜-21.5 | ＜-21.5 | ＜-21.5 |
| Wax tailings cut character | W1 | W2 | W3 | W4 |
| Boiling range, ℃ | 352~528 | 363~524 | 358~521 | 350~526 |
| Yield, wt%(is to mixing raw material) | 25. 45 | 25.15 | 25. 31 | 26.03 |
| Sulphur content, μ g/g | 16705 | 15301 | 15628 | 16800 |
Table 6 hydrofining/hydrofining technology condition
| Scheme | Embodiment 1 | |
|
Comparative example 1 |
| Raw material | G2+ C5 | G1+ C5 | G3+ C5 | G4 |
| C5: coker gasoline (mass ratio) | 6：1 | 8：1 | 10：1 | - |
| Hydrofining catalyzer | FHRS-1 | FHRS-1 | FHRS-1 | FHRS-1 |
| Processing condition | ||||
| Hydrogen dividing potential drop, |
7. 5 | 5. 5 | 3. 5 | 5. 5 |
| Temperature of reaction, ℃ | 135~140 | 160~165 | 170~175 | 160~165 |
| Volume space velocity when liquid, h -1 | 4.0 | 3.0 | 5.0 | 3.0 |
| Hydrogen to oil volume ratio | 600 | 800 | 700 | 800 |
| Hydrobon catalyst | FF-26 | FF-26 | FF-26 | FF-26 |
| Distillation tower gasoline: coker gasoline (mass ratio) | 2：1 | 2：1 | 3：1 | 2：1 |
| Processing condition | ||||
| Hydrogen dividing potential drop, MPa | 1.5 | 2.0 | 2.5 | 2.0 |
| Temperature of reaction, ℃ | 150~155 | 170~175 | 190~195 | 170~175 |
| Volume space velocity when liquid, h -1 | 1.5 | 1.1 | 1.3 | 1.1 |
| Hydrogen to oil volume ratio | 600 | 400 | 500 | 400 |
Table 7 hydroprocessing technique condition
| Scheme | Embodiment 1 | |
|
Comparative example 1 |
| Raw material | L1+ D2+W2 | L2+ D3+W3 | L1+D1+W1 | D4+W4 |
| Hydrogenation protecting agent | FZC-103 | FZC-103 | FZC-103 | FZC-103 |
| Hydrobon catalyst | 3936 | 3936 | 3936 | 3936 |
| Removal of ccr by hydrotreating catalyzer | HDC-1 | HDC-1 | HDC-1 | HDC-1 |
| Hydrocracking catalyst | A1 | A2 | B2 | A1 |
| Processing condition | ||||
| Hydrogen dividing potential drop, MPa | 14.5 | 15.5 | 16.5 | 15.5 |
| One anti-temperature, ℃ | 370~375 | 375~380 | 360~365 | 360~365 |
| Two anti-temperature, ℃ | 395~400 | 380~385 | 390~395 | 380~385 |
| One anti-/ bis-anti-air speeds, h -1 | 0.5/0.5 | 0.4/0.4 | 0.6/0.6 | 0.8/0.8 |
| Hydrogen to oil volume ratio | 1500 | 1400 | 1300 | 1400 |
The character of the final gained diesel oil distillate of table 8 embodiment and comparative example and gasoline fraction
| Scheme | Embodiment 1 | |
|
Comparative example 1 |
| Diesel oil distillate character | ||||
| Yield, wt%(is to ethylene bottom oil) | 63.4 | 62.7 | 64.1 | 53.4 |
| Density (20 ℃), g/cm 3 | 0.8853 | 0.8870 | 0.8794 | 0.8801 |
| Sulphur content, μ g/ |
12 | 11 | 12 | 12 |
| Nitrogen content, μ g/ |
2 | 1 | 2 | 3 |
| Condensation point/℃ | -51 | -51 | ＜-53 | ＜-53 |
| Cold filter clogging temperature/℃ | -28 | -27 | -30 | -30 |
| Boiling range/℃ | ||||
| 50% | 204 | 208 | 194 | 195 |
| 90% | 270 | 271 | 265 | 270 |
| 95% | 305 | 308 | 300 | 303 |
| Cetane value | 38.0 | 38.6 | 37.2 | 35.1 |
| Gasoline fraction character | ||||
| Yield, wt%(is to ethylene bottom oil) | 23.4 | 23.0 | 24.1 | 24.0 |
| Research octane number (RON) | 86 | 86 | 87 | 86 |
| Sulphur content, μ g/g | 6 | 5 | 7 | 6 |
Can be seen by table 8, full ethylene bottom oil cut is mixed to delayed coking gained gasoline, diesel oil and wax oil cut with vacuum residuum, this three cut all adopts and the similar processing and treating method of the inventive method, and gained yield of light oil (being also total liquid) is 77.4%; The inventive method gained light-weight fuel oil yield minimum is 85.7%, higher than the former.Aspect product property, the inventive method is also better than the former.
Claims (19)
1. ethylene bottom oil is produced a method for light-weight fuel oil, comprising:
Ethylene bottom oil is fractionated into lighting end and last running, and last running mixes with conventional coking raw material, and delayed coking obtains coker gasoline, coker gas oil, wax tailings; First behind pre-hydrofining reaction district after the coker gasoline of gained mixes with cracking of ethylene C 5 fraction, products therefrom is again through hydrofining reaction district; Coker gas oil and wax tailings mix with ethylene bottom oil lighting end, and through hydrotreatment, gained hydrotreatment products, together with hydrotreated product, is isolated to C 5 fraction, gasoline fraction and diesel oil distillate.
2. in accordance with the method for claim 1, it is characterized in that described cracking of ethylene C 5 fraction is the by product that directly comes from ethylene cracker, or be process dialkene removal cut after treatment, or be above-mentioned mixture.
3. the add-on and the coker gasoline weight ratio that in accordance with the method for claim 1, it is characterized in that described cracking of ethylene C 5 fraction are 5 ~ 12:1.
4. in accordance with the method for claim 1, it is characterized in that described gasoline fraction is partly recirculated to hydrofining reaction district as hydrofining reactor raw material, amount and coker gasoline weight ratio that gasoline fraction is recycled to hydrofining reaction district are 1 ~ 3:1.
5. the C 5 fraction that in accordance with the method for claim 1, it is characterized in that gained returns to ethylene cracker as raw material.
6. in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil lighting end and the cut point of last running are 400～520 ℃.
7. in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil lighting end and the cut point of last running are 460～520 ℃.
8. in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil last running and the blending ratio of conventional coking raw material are 1:1 ~ 9.
9. in accordance with the method for claim 1, it is characterized in that described conventional coking raw material is weight, the residual oil raw material of initial boiling point >350 ℃, be selected from one or more in the heavy deasphalted oil, catalytically cracked oil, viscous crude, topped crude, liquefied coal coil, shale oil of long residuum, vacuum residuum, visbroken resids, deasphalting unit.
10. in accordance with the method for claim 1, it is characterized in that the operational condition of described delayed coking is: 480～530 ℃ of temperature of reaction, reaction pressure 0.05 MPa～0.80MPa, residence time 5min～50min, circulation weight ratio is 0.01～1.0.
11. in accordance with the method for claim 1, it is characterized in that described coker gasoline and cracking of ethylene C 5 fraction are through pre-hydrofining reaction district, pass through again hydrofining reaction district, hydrofining reaction zone and hydrofining reaction district adopt one-stage serial technique, and wherein pre-hydrofining reaction district operational condition is: hydrogen dividing potential drop be 3.0 ~ 8.0MPa, hydrogen to oil volume ratio while being 500:1 ~ 800:1, liquid volume space velocity be 2.0 ~ 6.0h
-1, temperature of reaction is 130 ~ 180 ℃; Hydrofining reaction district operational condition is: volume space velocity 1.0 ~ 1.6h when 100 ~ 250 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0 ~ 3.0MPa, hydrogen to oil volume ratio 300:1 ~ 700:1 and liquid
-1.
12. in accordance with the method for claim 1, it is characterized in that described coker gas oil, wax tailings mix with ethylene bottom oil lighting end, the mixing raw material of gained carries out hydrotreatment, pass through successively hydrofining reaction district and hydrocracking reaction district, wherein hydrofining reaction district and hydrocracking reaction district adopt one-stage serial technique.
13. in accordance with the method for claim 12, it is characterized in that described hydrofining reaction district operational condition is: volume space velocity 0.4 ~ 0.8h when 350 ~ 380 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 16.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid
-1, hydrocracking reaction district operational condition is: volume space velocity 0.4 ~ 0.8h when 380 ~ 400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.0 ~ 16.0MPa, hydrogen to oil volume ratio are 1300:1 ~ 1500:1 and liquid
-1.
14. in accordance with the method for claim 1, it is characterized in that the mixing raw material elder generation and isocrackate heat exchange of described coker gas oil and wax tailings and ethylene bottom oil lighting end, then the mode heating up through raw materials furnace and heating reaches the temperature in requirement in hydrofining reaction district.
15. in accordance with the method for claim 12; it is characterized in that in described hydrofining reaction district; before Hydrobon catalyst, load hydrogenation protecting catalyst; described hydrogenation protecting catalyst adopts residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst, and hydrogenation protecting agent used accounts for 10% ~ 50% of Hydrobon catalyst volume.
16. in accordance with the method for claim 12, it is characterized in that described hydrocracking reaction district filling hydrocracking catalyst, and hydrocracking catalyst adopts the hydrocracking catalyst containing molecular sieve and amorphous aluminum silicide.
17. in accordance with the method for claim 12, it is characterized in that described hydrocracking reaction district filling hydrocracking catalyst, take the weight of catalyzer as benchmark, the content of Y molecular sieve or beta-molecular sieve is 10% ~ 40%, the content of amorphous aluminum silicide is 20% ~ 60%, group vib hydrogenation active metals is take the content of oxide compound as 15% ~ 40%, and group VIII hydrogenation active metals is take the content of oxide compound as 1% ~ 10%, and surplus is little porous aluminum oxide; The character of hydrocracking catalyst is as follows: specific surface area is 180 ~ 300m
2/ g, pore volume is 0.25 ~ 0.45ml/g.
18. in accordance with the method for claim 16, it is characterized in that: at hydrocracking catalyst upstream filling removal of ccr by hydrotreating catalyzer, wherein hydrofining reaction district Hydrobon catalyst used accounts for 70% ~ 100% of hydrocracking catalyst admission space, and the admission space of removal of ccr by hydrotreating catalyzer accounts for 10% ~ 40% of hydrocracking catalyst admission space.
19. in accordance with the method for claim 18, it is characterized in that described removal of ccr by hydrotreating catalyzer, take the weight of catalyzer as benchmark, and WO
3content be 16% ~ 23%, MoO
3content be 6% ~ 13%, NiO content is 3% ~ 8%, silicone content is with SiO
2count 4% ~ 12%, titanium oxide content is 0.5% ~ 4%, and surplus is aluminum oxide; The character of this catalyzer is as follows: pore volume is 0.30 ~ 0.55cm
3/ g, specific surface area is 120 ~ 300m
2/ g, average pore diameter is 5 ~ 10nm.
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