CN103805271B - A kind of working method of ethylene cracker by-product - Google Patents
A kind of working method of ethylene cracker by-product Download PDFInfo
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Abstract
The invention discloses a kind of working method of ethylene cracker by-product.Ethylene bottom oil is fractionated into lighting end and last running by the method, last running mixes with conventional coking raw material, delayed coking obtains coker gasoline, coker gas oil, wax tailings, and the coker gasoline of gained and cracking of ethylene C 5 fraction are successively through pre-hydrofining, hydrofining; Coker gas oil and wax tailings mix with lighting end, and through hydrotreatment, gained hydrotreatment products, together with hydrotreated product, is isolated to C 5 fraction, gasoline fraction and diesel oil distillate.The inventive method is for the high feature of aromatic hydrocarbons, colloid, carbon residue and asphalt content in ethylene bottom oil, ethylene bottom oil is divided into lighting end and last running, select different working methods, not only increase utilization ratio and the added value of ethylene bottom oil, improve the yield of gasoline and diesel oil, improve the quality product of light-weight fuel oil, make the smooth operation of device long period, but also supply raw materials for ethylene cracker, add ethylene yield.
Description
Technical field
The present invention relates to a kind of method of producing clean fuel oil, specifically a kind ofly process the delayed coking of ethylene cracker by-product C5 and ethylene bottom oil and the combined technical method of hydrogenation.
Background technology
Current world petroleum resource is day by day deficient, 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, the refinery's by product not yet made full use of is converted into clean fuel oil and has realistic meaning.
Cracking of ethylene C 5 fraction is the by product coming from ethylene unit, usually 14% ~ 20%(of ethylene yield is accounted for 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%, is generally separated through depentanizer before Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline and obtains.C 5 fraction can take hot dimerization method, solvent extraction process, azeotropic distn etc. to isolate cyclopentadiene, isoprene and m-pentadiene (see " printing during 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 used as device or domestic fuel, or selec-tive hydrogenation makes gasoline or gasoline blending component, or separation and Extraction diolefine, or for the production of C5 resin, or be used 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 DEG C, and final boiling point > 600 DEG C, is generally 600 ~ 700 DEG C, belongs to last running scope.The mixture of the ethylene bottom oil mainly above condensed-nuclei aromatics of dicyclo, aromaticity content reaches more than 90%, and density (20 DEG C) is greater than 1.0 g/cm
3, the foreign matter content such as sulphur and nitrogen is low, substantially not metal impurities.
In order to increase economic efficiency, multiple method of comprehensive utilization developed by each refinery, such as extracts naphthalene and series product thereof, light constituent (<300 DEG C) synthesizing petroleum resin, tar heavy oil produce carbon fibre asphalt and gac etc. is produced in carbon fiber, >540 DEG C last running.Still have some intermediate oils not to be fully used in aforesaid method, overall economic efficiency needs to be further improved.
The report carrying out delayed coking about vacuum residuum blending ethylene tar has: CN101608132A, " Responds Surface Methodology optimizes the delayed coking research of blending ethylene pyrolysis fuel oil " is (see " refining of petroleum and chemical industry " the 8th phase P5-P8 in 2009, " delayed coking unit mixes the research of refining grand celebration pyrolysis fuel oil " (see " refining of petroleum and chemical industry " the 12nd phase P20-P22 in 2007), " blending ethylene cracking masout is on the impact of delayed coking " (see " petrochemical technology and application " the 1st phase P44-P49 in 2010) and " Coking Test of Vacuum Residue with Ethylene Heavy Tar " are (see " Maoming College's journal " the 1st phase P7-P9 in 2008 etc., these researchs are all complete for ethylene bottom oil cut and vacuum residuum are mixed to refine as delayed coking raw material, the yield of liquid yield and light Fuel oil production can be made so 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, ethene and vapour, ethylene cracker by-product that diesel oil fuel output is high working method.
Ethylene bottom oil of the present invention produces the method for light-weight fuel oil, comprising:
Ethylene bottom oil is fractionated into lighting end and last running, last running mixes with conventional coking raw material, and delayed coking obtains coker gasoline, coker gas oil, wax tailings; The coker gasoline of gained mixes rear first behind pre-hydrofining reaction district 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 directly coming from ethylene cracker, also can be through the cut after dialkene removal process, also can be above-mentioned mixture.
In the inventive method, the part of gasoline cut hydrofining reaction district that arrives capable of circulation is as hydrofining reactor raw material, and another part gasoline fraction and whole diesel oil distillates are as product caterpillar.The C 5 fraction of gained returns ethylene cracker as raw material.
In the inventive method, the cut point of ethylene bottom oil lighting end and last running is 400 ~ 520 DEG C, is preferably 460 ~ 520 DEG C.
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 DEG C, generally can be selected from long residuum, vacuum residuum, visbroken resids, the heavy deasphalted oil of deasphalting unit, catalytically cracked oil, viscous crude and topped crude one or more, 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, and be generally: temperature of reaction 480 ~ 530 DEG C, reaction pressure 0.05 MPa ~ 0.80MPa, preferably at 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, gasoline fraction is recycled to the amount in hydrofining reaction district and coker gasoline weight ratio is 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 cracking of ethylene C 5 fraction through pre-hydrofining reaction district, then 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: when hydrogen dividing potential drop is 3.0 ~ 8.0MPa, hydrogen to oil volume ratio is 500:1 ~ 800:1, liquid, volume space velocity is 2.0 ~ 6.0h
-1, temperature of reaction is 130 ~ 180 DEG C; Hydrofining reaction district preferred operations condition is: temperature of reaction 100 ~ 250 DEG C, hydrogen dividing potential drop 1.0 ~ 3.0MPa, hydrogen to oil volume ratio 300:1 ~ 700:1 and liquid time volume space velocity 1.0 ~ 1.6h
-1.
Described coker gas oil, wax tailings mix with ethylene bottom oil lighting end, and the mixing raw material of gained carries out hydrotreatment, namely successively through hydrofining reaction district and hydrocracking reaction district.Wherein, hydrofining reaction district and the hydrocracking reaction district of mixing raw material hydrotreatment adopt one-stage serial technique, two reaction zones in same reactor, or respectively in different reactors.Wherein, mixing raw material hydrofining reaction district preferred operations condition is: temperature of reaction 350 ~ 380 DEG C, hydrogen dividing potential drop 13.0 ~ 16.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid time volume space velocity 0.4 ~ 0.8h
-1.Hydrocracking reaction district preferred operations condition is: temperature of reaction 380 ~ 400 DEG C, hydrogen dividing potential drop 14.0 ~ 16.0MPa, hydrogen to oil volume ratio be 1300:1 ~ 1500:1 and liquid time volume space velocity 0.4 ~ 0.8h
-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 inlet temperature requirements in hydrofining reaction district is reached through the mode that raw materials furnace and heating heats up.
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 for active metal component with group VIB and/or group VIII metal, with aluminum oxide or silicon-containing alumina for 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, and specific surface area is 280 ~ 400m
2/ g, in catalyzer with oxide basis hydrogenation active metals weight content for 5% ~ 20%, be preferably 8% ~ 16%.The commodity Hydrobon catalyst be applicable in the art is as the FHRS-1 catalyzer etc. of Fushun Petrochemical Research Institute's development and production.
In the inventive method, the Hydrobon catalyst that 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 uses is routine or pretreating catalyst by hydrocracking, generally with group VIB and/or group VIII metal for active ingredient, with the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus for carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 10wt% ~ 35wt%, and group VIII metal content take oxide basis as 3wt% ~ 15wt%, 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 to develop 3936,3996, FF-16, FF-26 etc.In the inventive method; in the hydrofining reaction district of mixture; preferably hydrogenation protecting catalyst was loaded before Hydrobon 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 with group VIB and/or group VIII metal for active metal component, and with aluminum oxide or silicon-containing alumina for carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; With the weight of catalyzer for benchmark, active metallic content take oxide basis as 0.5wt% ~ 18wt%.Such as: FZC-103, FZC-200 catalyzer of Fushun Petrochemical Research Institute's research and development.
In the inventive method, described hydrocracking reaction district filling hydrocracking catalyst, preferably at hydrocracking catalyst loaded upstream removal of ccr by hydrotreating catalyzer, the Hydrobon catalyst that wherein mixing raw material hydrofining reaction district is 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 adopted can adopt one or more conventional hydrocracking catalysts, generally with group VIB and/or group VIII metal for 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.The present invention recommends (with the weight of catalyzer for benchmark) composed as follows: 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 with the content of oxide basis for 15% ~ 40%, group VIII hydrogenation active metals is with the content of oxide basis for 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 that such as Fushun Petrochemical Research Institute develops, the hydrocracking catalysts such as 3974.
In the inventive method, described removal of ccr by hydrotreating catalyzer is with group VIB metal and group VIII metal for hydrogenation active component, as two or three in W, Mo, Ni and Co, is preferably W, Mo and Ni, this catalyzer containing auxiliary agent Si and Ti, take preferably aluminum oxide as carrier.With the weight of catalyzer for benchmark, WO
3content be 16% ~ 23%, MoO
3content be the content of 6% ~ 13%, NiO be 3% ~ 8%, silicone content is with SiO
2count 4% ~ 12%, be preferably 5% ~ 9%, titanium oxide content is 0.5% ~ 4%, and be preferably 1% ~ 2%, 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, different working methods is adopted according to the compositing characteristic of two cuts, last running is mixed refining first delayed coking in conventional coking raw material and is obtained liquid product, 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, gasoline and the diesel oil of quality improvement is obtained through fractionation, such one side improves the utilization ratio of ethylene bottom oil, the raw material sources producing light-weight fuel oil are expanded, on the other hand solve coking vapour, the ropy problem of diesel product, effectively alleviate the problem causing due to the existence of alkene in hydrogenating materials device running period short simultaneously.
2, ethylene bottom oil last running is mixed refining in conventional coking raw material as the raw material of delayed coking by the inventive method, such one side expands the raw material sources of coker, ethylene bottom oil lighting end mixes with coker gas oil, wax tailings on the other hand, clean vapour, diesel oil blending component is converted into completely through hydrotreatment, by refinery's by-product---the light-weight fuel oil be converted into ethylene bottom oil maximum, two aspects are all favourable to raising refinery economic benefit.
3, the wax tailings of coking gained mixes as hydrotreated feed with coker gas oil and ethylene bottom oil lighting end by the inventive method, the naphthalene series substance concentration in coker gas oil and ethylene bottom oil lighting end can be reduced to a certain extent, alleviate the concentrated heat release problem of hydrogenation unit, to minimizing facility investment and assurance device smooth operation favourable.On the other hand, the relatively high ethylene bottom oil lighting end of wax tailings and final boiling point as hydrotreated feed, increases the treatment capacity of hydrotreater, improves the transformation efficiency of vapour, diesel product together with coker gas oil.
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 adopting the inventive method, the cetane value of gained diesel oil distillate is improved significantly, quality product is improved.
5, the inventive method adopts the mixing of coker gasoline, cracking of ethylene C 5 fraction, as pre-hydrofining reaction raw material, adopt part of gasoline cut product to loop back the method for hydrofining reactor entrance simultaneously, effectively can reduce the diene in cracking of ethylene C 5 fraction and concentration of olefin, significantly reduce device temperature rise, run 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, C 5 fraction, clean gasoline and diesel product is obtained through fractionation together with the generation oil of hydrotreatment gained, C 5 fraction returns ethylene unit as cracking stock, can ethene be improved, propone output is about 10wt% ~ 15wt%, so namely, take full advantage of C 5 fraction, turn increase ethene, propone output, to raising 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, clean gasoline and diesel product is obtained through fractionation together with the generation oil of hydrotreatment gained, such one side improves the quality product of gasoline fraction, on the other hand share a separation column, to economy system investment with to reduce energy consumption favourable.
8, in the inventive method, ethylene bottom oil lighting end, coker gas oil and wax tailings cut mixing raw material are when hydrotreatment, successively through hydrogenation protecting agent, hydrofining agent, removal of ccr by hydrotreating catalyzer and hydrocracking agent, resin and asphalt a small amount of in raw material can be retained or make it be converted into micromolecular compound, protect host, extend the running period of device; Meanwhile, such grating mode also can make condensed-nuclei aromatics by ring hydrotreated lube base oil, is conducive to further cracking, useful to raising yield of light oil.
9, the present invention is that the ethylene bottom oil that added value is lower provides a kind of working method improving its economy, under the present situation of crude supply growing tension, reduces discharging synergy useful to refinery.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method.
Embodiment
The invention will be further described for composition graphs 1.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, the coker gasoline 7 that delayed coker 6 obtains, coker gas oil 8 and wax tailings 9, 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 through hydrofining reaction district and hydrocracking reaction district generating oil 12, 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, after entering 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 generation oil 12, gasoline fraction 18 and diesel oil distillate 19, mix with pre-hydrotreated product before wherein a part of gasoline fraction 18 loops back gasoline hydrofinishing reactor and carry out hydrofining reaction, part gasoline fraction 18 is as gasoline products caterpillar, C 5 fraction 17 returns 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, containing 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), add after mixing (added by the little porous aluminum oxide of pore volume 0.42ml/g prepared by dust technology peptization) tackiness agent roll agglomerating after, after putting into banded extruder extruded moulding, 110 DEG C of dryings 10 hours, 500 DEG C of activation, 4 hours obtained carriers, then be total to impregnation fluid with Mo-Ni, then 110 DEG C of dryings 12 hours, and 500 DEG C 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), the tackiness agent adding (preparation being added dust technology peptization by the little porous aluminum oxide of pore volume 0.42ml/g) after mixing roll agglomerating after, after putting into banded extruder extruded moulding, 110 DEG C of dryings 10 hours, after 500 DEG C of activation, 4 hours obtained carriers, again with W-Ni impregnation fluid altogether, then 110 DEG C of dryings 12 hours, and 500 DEG C activate 3 hours.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, containing 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 by little porous aluminum oxide (the specific surface area 240m of the dilute nitric acid solution peptization of concentration 3.3wt%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute obtains the drying 12 hours at 110 DEG C of shaping bar, 500 DEG C activate 4 hours obtained activated carriers after.The carrier of above-mentioned preparation is flooded again with W-Ni co-impregnated solution, then 110 DEG C of dryings 8 hours, and 500 DEG C 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 used catalyst preparing is 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 at 108 DEG C dry 4 hours, roasting 4 hours at 550 DEG C.With the impregnated activated metal of ordinary method, molybdenum, tungsten and nickel, then at 120 DEG C dry 2 hours, at 550 DEG C, roasting 3 hours, namely made catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
The composition of table 1 removal of ccr by hydrotreating catalyzer and character
| Catalyzer | HDC-1 |
| Composition, %(massfraction) | |
| WO 3 | 22 |
| MoO 3 | 11 |
| NiO | 5 |
| SiO 2 | 9 |
| TiO 2 | 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 with 420 DEG C and 480 DEG C for cut point, light, last running is obtained respectively after distillation, character lists in table 2, Vacuum Residue Properties lists in table 3, cracking of ethylene C 5 fraction character lists 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, gained gasoline and diesel oil distillate is in table 5.Coker gasoline and cracking of ethylene C 5 fraction pre-hydrofining technology condition 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; the one anti-hydrogenation protecting of filling from top to bottom agent FZC-103, Hydrobon catalyst 3936; two anti-from top to bottom filling removal of ccr by hydrotreating catalyzer and hydrocracking catalysts; 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, product slates and each narrow fraction product property is substantially constant or change is very little, illustrates that present method is improving vapour, while diesel product quality, also can solving device running period short problem.
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; the one anti-hydrogenation protecting of filling from top to bottom agent FZC-103, Hydrobon catalyst 3936; two anti-from top to bottom filling removal of ccr by hydrotreating catalyzer and hydrocracking catalysts; 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 is 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 ethylene C 5 fraction |
| Main composition | C4~C6 |
| Boiling range /℃ | 50~100 |
| Density (20 DEG C), 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, DEG C | 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 naphtha character | G1 | G2 | G3 | G4 |
| Boiling range, DEG C | 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, DEG C | 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 DEG C), 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, DEG C | 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 | Embodiment 2 | Embodiment 3 | 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, MPa | 7. 5 | 5. 5 | 3. 5 | 5. 5 |
| Temperature of reaction, DEG C | 135~140 | 160~165 | 170~175 | 160~165 |
| Volume space velocity during 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, DEG C | 150~155 | 170~175 | 190~195 | 170~175 |
| Volume space velocity during 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 | Embodiment 2 | Embodiment 3 | 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, DEG C | 370~375 | 375~380 | 360~365 | 360~365 |
| Two anti-temperature, DEG C | 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 table 8 embodiment and the final gained diesel oil distillate of comparative example and gasoline fraction
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Diesel oil distillate character | ||||
| Yield, wt%(is to ethylene bottom oil) | 63.4 | 62.7 | 64.1 | 53.4 |
| Density (20 DEG C), g/cm 3 | 0.8853 | 0.8870 | 0.8794 | 0.8801 |
| Sulphur content, μ g/g | 12 | 11 | 12 | 12 |
| Nitrogen content, μ g/g | 2 | 1 | 2 | 3 |
| Condensation point/DEG C | -51 | -51 | ＜-53 | ＜-53 |
| Cold filter clogging temperature/DEG C | -28 | -27 | -30 | -30 |
| Boiling range/DEG C | ||||
| 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, complete for ethylene bottom oil cut is mixed delayed coking gained gasoline, diesel oil and wax oil cut with vacuum residuum, this three cut all adopts the processing and treating method similar with 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 is minimum is 85.7%, higher than the former.In product property, the inventive method is also better than the former.
Claims (13)
1. ethylene bottom oil produces a method for light-weight fuel oil, comprising:
Ethylene bottom oil is fractionated into lighting end and last running, last running mixes with conventional coking raw material, and delayed coking obtains coker gasoline, coker gas oil, wax tailings; The coker gasoline of gained mixes rear first behind pre-hydrofining reaction district 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; Described ethylene bottom oil lighting end and the cut point of last running are 460 ~ 520 DEG C; Described ethylene bottom oil last running and the mixing quality ratio of conventional coking raw material are 1:1 ~ 9; The operational condition of described delayed coking is: temperature of reaction 480 ~ 530 DEG C, reaction pressure 0.05 MPa ~ 0.80MPa, residence time 5min ~ 50min, and circulation weight ratio is 0.01 ~ 1.0; Described coker gas oil, wax tailings mix with ethylene bottom oil lighting end, the mixing raw material of gained carries out hydrotreatment, namely successively through hydrofining reaction district and hydrocracking reaction district, wherein hydrofining reaction district and hydrocracking reaction district adopt one-stage serial technique; Described hydrofining reaction district operational condition is: temperature of reaction 350 ~ 380 DEG C, hydrogen dividing potential drop 13.0 ~ 16.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid time volume space velocity 0.4 ~ 0.8h
-1, hydrocracking reaction district operational condition is: temperature of reaction 380 ~ 400 DEG C, hydrogen dividing potential drop 14.0 ~ 16.0MPa, hydrogen to oil volume ratio be 1300:1 ~ 1500:1 and liquid time volume space velocity be 0.4 ~ 0.8h
-1.
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 directly coming from ethylene cracker, or be the cut after dialkene removal process, 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, gasoline fraction is recycled to the amount in hydrofining reaction district and coker gasoline weight ratio is 1 ~ 3:1.
5. in accordance with the method for claim 1, it is characterized in that the C 5 fraction of gained returns ethylene cracker as raw material.
6. 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 DEG C, be selected from one or more in long residuum, vacuum residuum, visbroken resids, the heavy deasphalted oil of deasphalting unit, catalytically cracked oil, viscous crude, topped crude, liquefied coal coil, shale oil.
7. 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, again through hydrofining reaction district, hydrofining reaction zone and hydrofining reaction district adopt one-stage serial technique, and wherein pre-hydrofining reaction district operational condition is: when hydrogen dividing potential drop is 3.0 ~ 8.0MPa, hydrogen to oil volume ratio is 500:1 ~ 800:1, liquid, volume space velocity is 2.0 ~ 6.0h
-1, temperature of reaction is 130 ~ 180 DEG C; Hydrofining reaction district operational condition is: temperature of reaction 100 ~ 250 DEG C, hydrogen dividing potential drop 1.0 ~ 3.0MPa, hydrogen to oil volume ratio 300:1 ~ 700:1 and liquid time volume space velocity 1.0 ~ 1.6h
-1.
8. in accordance with the method for claim 1, it is characterized in that mixing raw material elder generation and the isocrackate heat exchange of described coker gas oil and wax tailings and ethylene bottom oil lighting end, then reach the inlet temperature requirements in hydrofining reaction district through the mode that raw materials furnace and heating heats up.
9. in accordance with the method for claim 1; it is characterized in that in described hydrofining reaction district; hydrogenation protecting catalyst was loaded before Hydrobon 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.
10. in accordance with the method for claim 1, it is characterized in that described hydrocracking reaction district filling hydrocracking catalyst, hydrocracking catalyst adopts the hydrocracking catalyst containing molecular sieve and amorphous aluminum silicide.
11. in accordance with the method for claim 1, it is characterized in that described hydrocracking reaction district filling hydrocracking catalyst, with the weight of catalyzer for 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 with the content of oxide basis for 15% ~ 40%, and group VIII hydrogenation active metals is with the content of oxide basis for 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.
12. in accordance with the method for claim 10, it is characterized in that: at hydrocracking catalyst loaded upstream removal of ccr by hydrotreating catalyzer, the Hydrobon catalyst that wherein hydrofining reaction district is 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.
13. in accordance with the method for claim 12, it is characterized in that described removal of ccr by hydrotreating catalyzer, with the weight of catalyzer for benchmark, and WO
3content be 16% ~ 23%, MoO
3content be the content of 6% ~ 13%, NiO be 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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