CN103102979A - Method for producing light fuel oil from ethylene tar - Google Patents

Abstract

The invention discloses a method for producing light fuel oil from ethylene tar. The method is as below: fractionating ethylene tar into a light fraction and a heavy fraction; mixing the heavy fraction with a conventional coking raw material, and subjecting the mixture to delayed coking to obtain coker gasoline, coker diesel and coker gas oil; mixing the coker gasoline and the coker diesel with the light fraction of the ethylene tar, and subjecting the mixture to a hydrofining reaction; distilling the product to obtain a gasoline fraction I and a fraction heavier than the gasoline; subjecting the fraction heavier than the gasoline to a hydrogenation treatment to obtain light fuel oil, and distilling to obtain a gasoline fraction II and a diesel product; and mixing the gasoline fraction I and the gasoline fraction II to obtain a final gasoline product. The method provided by the invention utilizes the characteristics of high contents of ethylene tar aromatic hydrocarbons, colloid, carbon residue and glial and asphaltene of ethylene tar to fractionate the ethylene tar into the light fraction and the heavy fraction; different processing methods are employed to improve the added value of ethylene tar, increase yield of gasoline and diesel, improve product quality of light fuel oil and realize long-period stable operation of devices.

Description

A kind of ethylene bottom oil is produced the method for light-weight fuel oil

Technical field

The present invention relates to a kind of ethylene bottom oil and produce the method for light-weight fuel oil, the specifically combined technical method of a kind of delayed coking of blending ethylene tar and hydrogenation.

Background technology

The scarcity day by day of world petroleum resource and price thereof day by day raised makes the refinery reduce discharging synergy and necessitates, and ethylene bottom oil is sold mainly as heavy fuel oil (HFO) or carbon black raw material at present, and 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 ℃, final boiling point＞600 ℃ are generally 600～700 ℃, belong to the 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, such as extract naphthalene and series product thereof, light constituent (＜300 ℃) synthesizing petroleum resin, tar heavy oil produce carbon fibre asphalt and carbon fiber, 540 ℃ of last running produce gac etc.Still have some intermediate oils not to be fully used in aforesaid method, overall economic efficiency needs to be further improved.

The disclosed method of CN1970688A is that ethylene bottom oil is cut out boiling point less than the lighting end of 260～280 ℃, remove unsaturated hydro carbons in this lighting end with hydrorefined method again, and then therefrom extract naphthalene and methylnaphthalene product, a small amount of solvent oil product of by-product simultaneously.The method has only been utilized proportion lighting end seldom in the ethylene bottom oil, and the ethylene bottom oil cut of still having an appointment more than 80% is not effectively addressed; Simultaneously its hydrofining condition that provides can't be processed boiling point higher than the ethylene bottom oil cut of 280 ℃.

the report that relevant vacuum residuum blending ethylene tar carries out delayed coking has: CN101608132A, " the 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 seen " Maoming College's journal " the 1st phase P7-P9 in 2008 etc., these researchs are all that the full cut of ethylene bottom oil and vacuum residuum are mixed refining as the 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 relatively poor, also need further processing treatment.

Summary of the invention

In order to overcome deficiency of the prior art, the invention provides a kind of method that ethylene bottom oil utilization ratio is high, the petrol and diesel oil fuel output is high, the measured ethylene bottom oil of matter is produced light-weight fuel oil.

ethylene bottom oil provided by the invention is produced the method for light-weight fuel oil, comprise: ethylene bottom oil is fractionated into lighting end and last running, last running mixes with conventional coking raw material, delayed coking obtains coker gasoline and coker gas oil, coker gasoline and coker gas oil and ethylene bottom oil lighting end are mixed to get mixing raw material, through hydrofining reaction, the hydrofining of gained generates the cut that oil is isolated to gasoline fraction I and overweights gasoline, the cut that overweights gasoline carries out hydrotreatment, namely successively through hydrofining reaction district and hydrocracking reaction district, the gained hydrocracking generates oil and is isolated to gasoline fraction II and diesel product, gasoline fraction II and gasoline fraction I are mixed to get gasoline products.

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 initial boiling point〉weight, the residual oil raw material of 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 be adopted conventional operational condition, is generally: 480～530 ℃ of temperature of reaction, and reaction pressure 0.05MPa～0.80MPa is preferably in 0.10MPa～0.20MPa; Residence time 5min～50min, best 10 min～30min; The circulation weight ratio is 0.01～1.0, preferably 0.2～0.6.The coker gasoline of delayed coking gained and coker gas oil can not be isolated to the mixing oil of coker gasoline and coker gas oil, also can obtain respectively coker gasoline and coker gas oil, and then mix.

In the inventive method, after coker gasoline, coker gas oil and ethylene bottom oil lighting end mix, first generate oily heat exchange with hydrofining, then the mode that heats up through process furnace reaches the requirement of hydrofining reactor temperature in.The cut that overweights gasoline first generates oily heat exchange with hydrocracking, then reaches the temperature in requirement in hydrofining reaction district through the mode that raw materials furnace and heating heats up.

In the inventive method; load Hydrobon catalyst in the mixing raw material hydrofining reactor; the hydrogenation protecting agent is preferably loaded in upstream at Hydrobon catalyst, and wherein hydrogenation protecting agent and Hydrobon catalyst are seated in same reactor, perhaps is seated in respectively in two reactors.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% ~ 30% 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, the group vib metal is Mo and/or W, and the 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, mixing raw material hydrofining reaction condition is: volume space velocity 0.3 ~ 0.7h when 320 ~ 370 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 17.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid ^-1

In the inventive method, the hydrofining reaction district of hydrotreatment and hydrocracking reaction district's employing one-stage serial technique, two reaction zones are in same reactor, perhaps respectively in different reactors.Hydrofining reaction district's filling Hydrobon catalyst of hydrotreatment; Described hydrocracking reaction loads hydrocracking catalyst in the district, be preferably in the upstream filling removal of ccr by hydrotreating catalyzer of hydrocracking catalyst, wherein hydrotreatment Hydrobon catalyst used accounts for 60% ~ 100% of hydrocracking catalyst admission space, and the admission space of removal of ccr by hydrotreating catalyzer accounts for 5% ~ 40% of hydrocracking catalyst admission space.In the inventive method, the hydrofining reaction district preferred operations condition of hydrotreatment is: volume space velocity 0.3 ~ 0.7h when 360 ~ 390 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 17.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid ^-1Described hydrocracking reaction district preferred operations condition is: 380 ~ 400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.0 ~ 17.0MPa, volume space velocity 0.3 ~ 0.7h when hydrogen to oil volume ratio is 1300:1 ~ 1500:1 and liquid ^-1

In the inventive method, the Hydrobon catalyst that the hydrofining reaction district of the Hydrobon catalyst that the mixing raw material hydrofining reaction is used and hydrotreatment uses is Hydrobon catalyst or the pretreating catalyst by hydrocracking of routine, 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, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.Take the weight of catalyzer as benchmark, the group vib metal content is counted 10wt% ~ 35wt% with oxide compound, and the 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 are 0.15 ~ 0.60ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, FF-16, FF-26 etc.

In the inventive method, hydrocracking catalyst can adopt one or more conventional hydrocracking catalysts, generally take group vib and/or group VIII metal as active ingredient, the group vib metal is generally Mo and/or W, and the 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, the preferred hydrocracking catalyst that contains molecular sieve and amorphous aluminum silicide that adopts.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%, the group vib hydrogenation active metals is take the content of oxide compound as 15% ~ 40%, the 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 are 0.25 ~ 0.45ml/g.FC-14, the ZHC-02 that develops such as Fushun Petrochemical Research Institute, the hydrocracking catalysts such as 3974.

Described removal of ccr by hydrotreating catalyzer is take group vib metal and group VIII metal as the hydrogenation activity component, as two or three in W, Mo, Ni and Co, is preferably W, Mo and Ni, and 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 that the content of 6% ~ 13%, NiO 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.

The inventive method has following advantage:

1, the inventive method is mixed refining raw material as delayed coking in the conventional coking raw material with ethylene bottom oil last running, the raw material sources of delayed coking unit have been enlarged so on the one hand, ethylene bottom oil lighting end and coking vapour on the other hand, diesel oil mixes, first through hydrofining, the cut that overweights gasoline after separation is converted into the vapour of cleaning more fully through hydrotreatment, diesel oil blending component, with refinery's by-product---be converted into to the ethylene bottom oil maximum light-weight fuel oil of the huge market demand, while vapour, the diesel product quality be improved significantly, these are all favourable to improving refinery's economic benefit.

2, the inventive method is mixed coker gasoline and the coker gas oil of coking gained with the ethylene bottom oil lighting end, as hydrorefined raw material, can alleviate the ethylene bottom oil lighting end because of the difficult feed problem that viscosity causes greatly so on the one hand, effectively reduces energy consumption; Also reduced simultaneously the olefin(e) centent in coker gasoline and coker gas oil, and made carbon residue and also corresponding reduction of asphalt content in the ethylene bottom oil lighting end, this two aspect all is conducive to the device long-term operation.

3, the inventive method is mixed into hydrofining reactor with the coker gasoline of coking gained and coker gas oil and ethylene bottom oil lighting end, the employing lesser temps first removes sulphur, the nitrogen impurity in lighting end, gasoline fraction as the product caterpillar is cleaned, so also can save the energy.

4, the inventive method will be separated after distillation through the product after hydrofining, obtain the gasoline fraction I that sulphur content obviously reduces, this gasoline fraction I mixes with the gasoline fraction II of follow-up generation as final gasoline blend component product caterpillar, rather than proceed again hydrotreatment and react, can reduce like this yield of C1 ~ C4 component, favourable to improving yield of light oil.

5, the inventive method in hydrotreating reactor hydrocracking catalyst upstream grading loading Hydrobon catalyst, make the above aromatic hydrocarbons of dicyclo that in raw material, content is higher pursue ring filling, these the aromatic hydrocarbons of fractional saturation again under the hydrocracking catalyst effect, be converted into more the more satisfactory component of cleaning vapour, diesel oil---with the monocycle hydro carbons of side chain, and then can effectively improve yield of light oil, and improved quality product.

6, the inventive method grading loading the removal of ccr by hydrotreating catalyzer, the running period that not only is conducive to extension fixture, and the increase of removal of ccr by hydrotreating catalyzer, also improved the saturation exponent of aromatic hydrocarbons, the hydrocracking reaction that is conducive to next step, the yield of raising light-weight fuel oil.In addition, raw material can make exothermic heat of reaction even successively through Hydrobon catalyst, removal of ccr by hydrotreating catalyzer and hydrocracking catalyst, avoids the temperature rise of hydrocracking bed too high, and is favourable to the safety and steady operation of device.

7, the present invention provides a kind of working method that improves its economy for the lower ethylene bottom oil of added value; Under the present situation of crude supply growing tension, the refinery is reduced discharging synergy useful.

Description of drawings

Fig. 1 is the block diagram of the inventive method.

Embodiment

The invention will be further described in conjunction with Fig. 1.ethylene bottom oil 1 obtains lighting end 3 and last running 4 through separation column 2 fractionation, last running 4 and conventional coking raw material 5 mix, delayed coker 6 obtains coker gasoline 7, coker gas oil 8 and wax tailings 9, coker gasoline 7, after coker gas oil 8 and ethylene bottom oil lighting end 3 mix, obtain mixed hydrogenation and process raw material 10, mixed hydrogenation is processed raw material 10 after hydrofining reactor 11, gained hydrofining generates oil 12 and tells gasoline fraction I 14 and the cut 15 that overweights gasoline through stripping tower and distillation tower 13, the cut 15 that overweights gasoline advances hydrotreating reactor 16 and carries out the hydrotreatment reaction, gained generates oil 17, obtain gasoline fraction II 19 and diesel product 20 through stripping tower and separation column 18, gasoline fraction II 19 and gasoline fraction I 14 are mixed to get final gasoline products.The general raw material caterpillar as catalytic cracking or hydrocracking of wax tailings 9.

The described ethylene bottom oil of the inventive method is ethylene cracker by-product---Pyrolysis fuel oil PFO.

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:

With 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 area 650m2/g, infrared acidity 0.45mmol/g), add after mixing (adding rare nitric acid peptization preparation by the little porous aluminum oxide of pore volume 0.42ml/g) tackiness agent roll agglomerating after, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, 500 ℃ of activation made carrier in 4 hours, then with Mo-Ni steeping fluid dipping altogether, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation 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:

With 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 area 680m2/g, infrared acidity 0.41mmol/g), add after mixing 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, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, after 500 ℃ of activation made carrier in 4 hours, again with W-Ni steeping fluid dipping altogether, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation 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, contain the preparation of the hydrocracking catalyst B1 of amorphous aluminum silicide and beta-molecular sieve

Hydrocracking catalyst B1:

With 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 area 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 are 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains drying 12 hours under 110 ℃, 500 ℃ activate 4 hours and make activated carrier after.Again with the carrier of the above-mentioned preparation of W-Ni co-impregnated solution dipping, then 110 ℃ of dryings 8 hours, and 500 ℃ of activation 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 are 19w%) powder, sesbania powder 5g mixes it, adds by 188g water, 43.0g and contains 17wt%TiCl ₃TiCl ₃The acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, the gained plastic, extruded moulding, this strip under 108 ℃ dry 4 hours was 550 ℃ of lower roastings 4 hours.Flood reactive metal with ordinary method, molybdenum, tungsten and nickel then under 120 ℃ dry 2 hours, 550 ℃ of lower roastings 3 hours, are namely made 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
		Form the %(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 take 420 ℃ and 480 ℃ as cut point, obtains respectively light, last running after distillation, character is listed in table 2, and Vacuum Residue Properties is listed in table 3.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 sees Table 4.Coker gasoline, coker gas oil and ethylene bottom oil lighting end mix; raw material as hydrofining reactor; this reactor loads hydrogenation protecting agent FZC-103, Hydrobon catalyst 3936 from top to bottom; the volume ratio of two kinds of catalyzer is 1:4, and the cut character that hydrofining reaction processing condition and gained overweight gasoline sees Table 5.In the present embodiment, take the cut that overweights gasoline as raw material, obtain light-weight fuel oil through hydrotreatment, the hydroprocessing technique condition sees Table 6.Hydrotreating reactor adopts two reactors in series modes, and an anti-filling Hydrobon catalyst 3936, two instead loads the removal of ccr by hydrotreating catalyzer from top to bottom HDC-1And hydrocracking catalyst, in embodiment 1 and 3, the volume ratio of these three kinds of catalyzer is 40:15:45, in embodiment 2, the volume ratio of these three kinds of catalyzer is 45:10:45, product separates through separation system, together with the gasoline fraction of gained after hydrofining, obtain quality be improved significantly cleaning vapour, diesel oil blending component product, reaction result sees Table 7.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 present method be described in raising vapour, diesel product quality, but solving device short problem running period also.

Comparative Examples 1

Ethylene bottom oil is without distillation, and full cut mixes with mass ratio 1:1 with vacuum residuum, and processing condition and product property that this mixture carries out delayed coking see Table 4.The hydrofining reaction processing condition of coker gasoline and coker gas oil mixture and overweight gasoline fraction character and see Table 5; the volume ratio that this hydrofining reactor loads hydrogenation protecting agent FZC-103,3936, two kinds of catalyzer of Hydrobon catalyst from top to bottom is 1:6.Overweight gasoline fraction and obtain light-weight fuel oil through hydrotreatment, the hydroprocessing technique condition sees Table 6.Hydrotreating reactor adopts two reactors in series modes, and an anti-filling Hydrobon catalyst 3936, two instead loads the removal of ccr by hydrotreating catalyzer from top to bottom HDC-1And hydrocracking catalyst, the volume ratio of these three kinds of catalyzer is 55:10:35, reaction result sees Table 7.

The different cut point gained of table 2 ethylene bottom oil employing 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 delayed coking condition and product property

Scheme	Embodiment 1	Embodiment 2	Embodiment 3	Comparative Examples 1
					Processing condition
Temperature of reaction, ℃	510	495	500	495
					Reaction pressure/MPa	0.10	0.17	0.15	0.17
Recycle ratio	0.4	0.5	0.4	0.5
					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, ℃	55~181	50~176	52~180	49~179
					Yield, wt%(is to mixing raw material)	9.45	9.32	9.39	9.35
Sulphur content, μ g/g	2742	2613	2719	2701
					Research octane number (RON)	74	78	76	78
Fraction of coker gas oil character	D1	D2	D3	D4
					Boiling range, ℃	173~458	174~463	178~461	179~452
Yield, wt%(is to mixing raw material)	56.75	51.47	50.50	52.10
					Density (20 ℃), g/cm 3	0.9768	0.9840	0.9887	0.9850
Sulphur content, μ g/g	5956	6115	6221	6134
					Cetane value	＜-21.5	＜-21.5	＜-21.5	＜-21.5
Wax tailings cut character	W1	W2	W3	W4
					Boiling range, ℃	458~528	463~524	461~521	450~526
Yield, wt%(is to mixing raw material)	15.52	15.41	15.16	16.10
					Sulphur content, μ g/g	17900	17400	16882	17607

Table 5 hydrofining technology condition and gained overweight the character of gasoline fraction

Scheme	Embodiment 1	Embodiment 2	Embodiment 3	Comparative Examples 1
					Raw material	G1+D1+L1	G2+D2+L1	G3+D3+L2	G4+D4
Processing condition
					Hydrogen dividing potential drop/MPa	16.0	15. 0	14. 0	12.0
Temperature of reaction/℃	330~335	340~345	350~355	340~345
					Volume space velocity/h during liquid -1	0.4	0.5	0.6	0.8
Hydrogen to oil volume ratio	1400	1300	1500	1300
					Overweight the character of gasoline fraction	HH1	HH2	HH3	HH4
Boiling range/℃
					IBP	172	170	168	174
EBP	458	451	486	453
					Density (20 ℃), g/cm 3	0.9901	0.9882	0.9879	0.9896
S，μg/g	990	984	950	950
					N，μg/g	163	154	160	166
Four components, wt%
					Aromatic hydrocarbons	68.5	70.28	69.54	68.90
Colloid	11.05	10.00	10.81	10.10
					Bituminous matter	0.65	0.57	0.62	0.56

Table 6 hydroprocessing technique condition

Scheme	Embodiment 1	Embodiment 2	Embodiment 3	Comparative Examples 1
					Raw material	HH1	HH2	HH3	HH4
Hydrobon catalyst	3936	3936	3936	3936
					The removal of ccr by hydrotreating catalyzer	HDC-1	HDC-1	HDC-1	HDC-1
Hydrocracking catalyst	A2	B2	A1	B2
					Processing condition
Hydrogen dividing potential drop/MPa	14.5	15.5	16.5	15.0
					One anti-temperature/℃	370~375	380~385	360~365	360~365
Two anti-temperature/℃	395~400	380~385	390~395	390~395
					One anti-/ two anti-air speed/h -1	0.5/0.5	0.4/0.4	0.6/0.6	1.0/1.0
Hydrogen to oil volume ratio	1500	1400	1300	1200

The character of the final gained diesel oil distillate of table 7 embodiment and Comparative Examples and gasoline fraction

Scheme	Embodiment 1	Embodiment 2	Embodiment 3	Comparative Examples 1
					Diesel oil distillate character
Yield, wt%(is to ethylene bottom oil)	53.2	50.7	54.1	40.6
					Density (20 ℃), g/cm 3	0.8678	0.8641	0.8720	0.8681
Sulphur content, μ g/g	9	8	8	9
					Nitrogen content, μ g/g	1	1	1	1
Condensation point/℃	-52	＜-53	＜-52	＜-53
					Cold filter clogging temperature/℃	-30	-28	-29	-30
Boiling range/℃
					50%	194	193	201	195
90%	270	270	278	278
					95%	304	301	308	305
Cetane value	36.5	37.0	36.7	34
					Gasoline fraction character
Yield, wt%(is to ethylene bottom oil)	25.9	26.0	25.9	20.7
					Research octane number (RON)	85	82	84	84
Sulphur content, μ g/g	7	6	4	6

Can be seen by table 7, the full cut of ethylene bottom oil is mixed delayed coking gained gasoline, diesel oil and wax oil with vacuum residuum, gasoline fraction and diesel oil distillate adopt and the similar processing and treating method of present method, and the gained yield of light oil is only 61.3%, and total liquid yield is 77.4%; Present method gained light-weight fuel oil yield minimum is 76.7%, and it is 85.9% that total liquid is received minimum, all higher than the former.Aspect product property, present method also is better than the former.

Claims (16)

1. an ethylene bottom oil is produced the method for light-weight fuel oil, comprise: ethylene bottom oil is fractionated into lighting end and last running, last running mixes with conventional coking raw material, delayed coking obtains coker gasoline and coker gas oil, coker gasoline and coker gas oil and ethylene bottom oil lighting end are mixed to get mixing raw material, through hydrofining reaction, the hydrofining of gained generates the cut that oil is isolated to gasoline fraction I and overweights gasoline, the cut that overweights gasoline carries out hydrotreatment, namely successively through hydrofining reaction district and hydrocracking reaction district, the gained hydrocracking generates oil and is isolated to gasoline fraction II and diesel product, gasoline fraction II and gasoline fraction I are mixed to get gasoline products.

2. the cut point that in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil lighting end and last running is 400～520 ℃.

3. the cut point that in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil lighting end and last running is 460～520 ℃.

4. the blending ratio that in accordance with the method for claim 1, it is characterized in that described ethylene bottom oil last running and conventional coking raw material is 1:1 ~ 9.

5. in accordance with the method for claim 1, it is characterized in that described conventional coking raw material is initial boiling point〉weight, the residual oil raw material of 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.

6. in accordance with the method for claim 1, it is characterized in that described conventional coking raw material is vacuum residuum.

7. in accordance with the method for claim 1, it is characterized in that the operational condition of described delayed coking, for: 480～530 ℃ of temperature of reaction, reaction pressure 0.05MPa～0.80MPa, residence time 5min～50min, the circulation weight ratio is 0.01～1.0.

8. in accordance with the method for claim 1, after it is characterized in that described coker gasoline, coker gas oil and ethylene bottom oil lighting end mix, first generate oily heat exchange with hydrofining, then the mode that heats up through process furnace reaches the requirement of hydrofining reactor temperature in.

9. in accordance with the method for claim 1, it is characterized in that, the cut that overweights gasoline first generates oily heat exchange with hydrocracking, then reaches the temperature in requirement in hydrofining reaction district through the mode that raw materials furnace and heating heats up.

10. in accordance with the method for claim 1; it is characterized in that; load Hydrobon catalyst in the mixing raw material hydrofining reactor, in the agent of the upstream of Hydrobon catalyst filling hydrogenation protecting, hydrogenation protecting agent used accounts for 10% ~ 30% of Hydrobon catalyst volume.

11. in accordance with the method for claim 1, it is characterized in that, mixing raw material hydrofining reaction condition is: volume space velocity 0.3 ~ 0.7h when 320 ~ 370 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 17.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid ^-1

12. in accordance with the method for claim 1, it is characterized in that hydrofining reaction district's filling Hydrobon catalyst of hydrotreatment; Described hydrocracking reaction loads hydrocracking catalyst in the district, at the upstream of hydrocracking catalyst filling removal of ccr by hydrotreating catalyzer, wherein hydrotreatment Hydrobon catalyst used accounts for 60% ~ 100% of hydrocracking catalyst admission space, and the admission space of removal of ccr by hydrotreating catalyzer accounts for 5% ~ 40% of hydrocracking catalyst admission space.

13. in accordance with the method for claim 1, it is characterized in that, the hydrofining reaction district operational condition of hydrotreatment is: volume space velocity 0.3 ~ 0.7h when 360 ~ 390 ℃ of temperature of reaction, hydrogen dividing potential drop 13.0 ~ 17.0MPa, hydrogen to oil volume ratio 1300:1 ~ 1500:1 and liquid ^-1Described hydrocracking reaction district operational condition is: 380 ~ 400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.0 ~ 17.0MPa, volume space velocity 0.3 ~ 0.7h when hydrogen to oil volume ratio is 1300:1 ~ 1500:1 and liquid ^-1

14. it is characterized in that in accordance with the method for claim 1, the hydrocracking catalyst of described hydrocracking reaction district's employing is the hydrocracking catalyst that contains molecular sieve and amorphous aluminum silicide.

15. according to the described method of claim 12 or 14, it is characterized in that described 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%, the group vib hydrogenation active metals is take the content of oxide compound as 15% ~ 40%, and the 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 are 0.25 ~ 0.45ml/g.

16. according to the described method of claim 12 or 15, it is characterized in that described removal of ccr by hydrotreating catalyzer, take the weight of catalyzer as benchmark, WO ₃Content be 16% ~ 23%, MoO ₃Content be that the content of 6% ~ 13%, NiO 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.

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