CN101314722B - Process for preparing olefin hydrocarbon and light aromatic hydrocarbon with poor oil in high limit - Google Patents
Process for preparing olefin hydrocarbon and light aromatic hydrocarbon with poor oil in high limit Download PDFInfo
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- CN101314722B CN101314722B CN2008101345723A CN200810134572A CN101314722B CN 101314722 B CN101314722 B CN 101314722B CN 2008101345723 A CN2008101345723 A CN 2008101345723A CN 200810134572 A CN200810134572 A CN 200810134572A CN 101314722 B CN101314722 B CN 101314722B
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Abstract
The invention provides a process for maximizing the production of alkenes and light arenes from poor-quality oil, wherein the poor-quality oil is fed into a delayed coking device, and the mixture of the produced coker gasoline, coker diesel and coker gatch is used as the feeding material form the main riser of a double-riser catalytic cracking device; and the catalytic gasoline containing C4 component or even partial diesel is used as the feeding material for the auxiliary riser.
Description
Technical field
The invention belongs to the catalytic cracking process technical field in the refining of petroleum; Relate in particular to a kind of inferior oil material through delayed coking; Coking generates the raw material of oil as the double lift pipe catalytic cracking device, the complete processing of production fluid liquefied oil gas (mainly being to be producing more propylene), benzene, toluene, xylol as much as possible.
Background technology
The world is increasing to the demand of oil, and the catalyzed cracking processing inferior raw material is the problem that must face.With regard to China because the crude supply quantity not sufficient, the CCU of some refinerys with the fuel heavy oil of import as catalytically cracked material, for example Muscovite M100 fuel heavy oil.The hydrogen richness of fuel heavy oil is very low, and metal contents such as Ni, V, Fe, Na are high, and condensed-nuclei aromatics content is high, S, N content height, and density is big, and carbon residue is high, is difficult to cracking.During with catalytic cracking process processing poor quality oil, since the difficult cracking of poor quality oil, a large amount of externally extracting oils of having to, and the amount of getting rid of is up to 10-15% outward; The total recovery of liquid product (liquefied gas, gasoline, diesel oil) is about 75%; The aromaticity content of catalytic diesel oil about 70%, proportion 0.9-0.92, cetane value about 20, oxidation stability and light stability are very poor, through conventional unifining, the light stability problem can solve, but proportion can not fall, cetane value improves hardly; For the micro-activity of keeping equilibrium catalyst about 60, catalyzer ton oil unit consumption is between 2.5-3.5kg.Because the catalytic diesel oil quality is too poor, concoct out the commercial Dissel oil of National standard with straight-run diesel oil, its difficulty is very big; It is non-remunerative on benefit that part is sold as nonstandard oil.Catalytic cracking is as long as process inferior raw material, and above-mentioned drawback all can occur, and only raw materials quality is better, can alleviate to some extent.
Process the refinery of above-mentioned inferior oil material and built delayed coking unit for the great majority of extricating oneself from a plight.The raw material of CCU is the mixture of above-mentioned poor quality oil and wax tailings, though above-mentioned drawback take a favorable turn, does not deal with problems at all; For solution catalytic cracking diesel oil, coker gasoline, coker gas oil can not certainly will will be built hydro-refining unit again as the problem of tank oil sale.At present, oil price is more and more expensive, and fuel type refinery produces liquefied gas, gasoline, diesel oil by routine even will lose money, and particularly goes up hydro-refining unit again, makes technical process very long, and is fortunately more severe.Most medium and small refinery has all adopted the patent of FDFCC technology, has set up the double lift pipe catalytic cracking device.Therefore, how utilizing delayed coking unit, double lift pipe catalytic cracking device, avoid the underproof problem of product, can not go up hydro-refining unit, shorten the technical process of poor quality oil processing, is the Technology that the refinery pleasure is seen.
Summary of the invention
The present invention provides the processing process of a kind of poor quality oil through the voluminous as far as possible LPG liquefied petroleum gas of catalytic cracking (mainly being to be producing more propylene), benzene, toluene, xylol.
The technical scheme that the present invention adopts is following:
A kind of complete processing of poor quality oil is characterized in that poor quality oil is introduced into delayed coking unit and takes off charcoal, demetalization, and the coking that constitutes with coker gasoline, coker gas oil and wax tailings generates the charging of oil as double lift pipe catalytic cracking master riser tube; Catalytic gasoline, comprise that the charging of carbon four components as subsidiary riser, cracking under severe condition, said severe condition are that the head temperature of subsidiary riser is controlled at 580-620 ℃, catalystoil ratio is 20-30; The gasoline that is obtained by the subsidiary riser outlet goes out aromatic hydrocarbons with the selective solvent extracting, and then isolates benzene, toluene and xylol; Raffinate oil and return subsidiary riser as cracked charge; Increasing production of liquid gas significantly.It is characterized in that the part catalytic diesel oil is also as the charging of subsidiary riser.Wherein selective solvent is diethylene glycol ether, triethylene glycol ether, methyl-sulphoxide, tetramethylene sulfone or dipropylene glycol.It is characterized in that described poor quality oil comprises fuel heavy oil, is difficult to the fcc raw material or the vacuum residuum of cracked naphthene base crude oil and middle base oil.
In particular; A kind of complete processing of poor quality oil; It is characterized in that poor quality oil is introduced into delayed coking unit and takes off charcoal, demetalization, the coking that constitutes with coker gasoline, coker gas oil and wax tailings generates the charging of oil as double lift pipe catalytic cracking master riser tube; Catalytic gasoline comprises the charging of carbon four components as subsidiary riser, cracking under severe condition, increasing production of liquid gas significantly.
Conventional processing condition are adopted in said delayed coking
The part catalytic diesel oil also can be used as the charging of subsidiary riser, and its amount depends on practical situation.
Wherein in the product of delayed coking, the productive rate of coke and coking gas roughly accounts for 25% of inlet amount gross weight, and the productive rate that coking generates oil (actual is the mixture of coker gasoline, coker gas oil and wax tailings) accounts for about 75%.
The head temperature of subsidiary riser is controlled at 580-620 ℃, and catalystoil ratio is 20-30.
The aromaticity content of the gasoline that CCU produces is up to 60-70wt%.The gasoline that available selective solvent extracting CCU produces obtains benzene, toluene, xylol, raffinates oil also can return subsidiary riser and carry out catalytic cracking.Its result, the economic benefit of CCU improves greatly.Wherein selective solvent is preferably diethylene glycol ether, triethylene glycol ether, methyl-sulphoxide, tetramethylene sulfone or dipropylene glycol.
The top exit of main riser tube links to each other with different settling vessels respectively with the subsidiary riser top exit.According to the difference of processing requirement, the product of two riser tubes can a shared separation column fractionation or by the fractionation respectively of different separation columns.Dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, coke are the reaction product of main riser tube; Main riser tube is carried out recycle stock, the full freshening of slurry oil.Dry gas, liquefied gas, high aromaticity content gasoline, coke are the reaction product of subsidiary riser.Liquefied gas obtains propane, propylene and carbon four components through gas fractionation.
Adopt this technical process catalytic diesel oil productive rate to descend greatly, and quality compares to the direct catalytic cracking of poor quality oil and increase, the refinery can be in harmonious proportion out commercial Dissel oil with straight-run diesel oil; The catalytic cracking charging is that delayed coking generates oil, and poor quality oil has passed through decarburization, demetalization, need not externally extracting oil; Refinery need not be set up hydro-refining unit again, promptly adopts the shortest work flow to realize poor quality oil processing, obtains high value added product, improves the economic benefit of processing poor quality oil.
Description of drawings
Fig. 1 is the principle synoptic diagram of this technology.
Embodiment
In conjunction with accompanying drawing the present invention is described further.
Poor quality oil gets into the delayed coking unit cracking; Obtain coking gas, coker gasoline, coker gas oil, wax tailings and coke; The oily main riser tube of being made up of coker gasoline, coker gas oil and wax tailings that gets into the double lift pipe catalytic cracking device of coking generation carries out cracking reaction, and the catalytic gasoline of cracking gained gets into subsidiary riser and carries out catalytic cracking; The charging of subsidiary riser can comprise carbon four components in the liquefied gas, even can comprise the catalytic diesel oil that part obtains through main riser cracking.Catalytic gasoline produces a large amount of liquefied gas (being mainly producing more propylene) through the further cracking of subsidiary riser.It is dry gas, liquefied gas, gasoline, diesel oil and coke that coking generates the oily the finished product that obtain through the cracking of double lift pipe catalytic cracking device.If the high aromaticity content gasoline to obtaining through the subsidiary riser cracking carries out the selective solvent extracting, extract benzene, toluene, xylol out, raffinate oil and return the subsidiary riser cracking, will there be gasoline in the so final product.
Embodiment
With specific embodiment and Comparative Examples the present invention is further described below.
Percentage ratio among following Comparative Examples and the embodiment is weight percentage except that specifying.
The heavy oil catalytically cracking equipment that Comparative Examples 1 Shandong Province petrochemical industry group company one cover annual working ability is 250,000 tons directly uses Muscovite M100 fuel heavy oil to be charging.The physico-chemical property of M100 is seen table 1.The Flex-Tec catalyzer that catalyst system therefor is produced for Engelhard company, the physico-chemical property of its industrial poiser is seen table 2, and the processing condition of catalytic cracking are seen table 3, and the product distributed data and the product property data of catalytic cracking are seen table 4.
The physico-chemical property of table 1M100 fuel heavy oil
The character of table 2Flex-Tec equilibrium catalyst
Table 3 catalytic cracking process condition
Product distribution (%) and the product property data of table 4 catalytic cracking
Embodiment 1 Shandong Province petrochemical industry group has set up the delayed coking unit of 1,000,000 tons of cover annual working abilities, the double lift pipe catalytic cracking device that a cover annual working ability is 600,000 tons.Adopt the charging of the raw material of Comparative Examples 1 CCU as delayed coking unit, adopt conventional delay coking process condition, material balance is a coking gas 4%, coke 21%, and coking generates oil 75%.Coking is given birth to olefiant physico-chemical property and is seen table 5.Coking generates the charging of oil as double lift pipe catalytic cracking device master riser tube, and the catalytic gasoline that obtains is as the charging of subsidiary riser, under the given processing condition of table 3, carries out cracking.The Flex-Tec catalyzer that used catalyzer is produced for Engelhard company, the physico-chemical property of catalyzer poiser is seen table 2.The processing condition that this double lift pipe catalytic cracking device adopts are seen table 3, and the product distributed data and the product property data of catalytic cracking are seen table 4.
Olefiant physico-chemical property is given birth in table 5 coking
| Project | Data |
| Density kg/m 3 | 877.4 |
| Sulphur % | 1.15 |
| Nitrogen μ g/g | 1485 |
| Boiling range ℃ | |
| IBP | 131.7 |
| 10％ | 237.1 |
| 20％ | 264.5 |
| 30％ | 286.8 |
| 40％ | 308.7 |
| 50％ | 329.9 |
| 60％ | 347.4 |
| 70％ | 364.2 |
| 80％ | 380.5 |
| 90％ | 396.7 |
| 96％ | 410.3 |
| 97％ | 414.1 |
| 98％ | 418.3 |
| 99％ | 427.2 |
| FBP | 442.3 |
Annotate: this coking generates oil and contains coker gasoline 7% approximately, coker gas oil 55%, wax tailings 38%
Carry out catalytic cracking owing to adopt coking to generate oil, the drawback of the direct catalytic cracking of above-mentioned poor quality oil no longer occurs.With regard to processing M100 fuel heavy oil, advance delayed coking unit, coke and coking gas productive rate roughly 25%, externally extracting oil 13% but direct catalytic cracking is had to.In the present embodiment, subsidiary riser is charging with the catalytic gasoline only, so listed liquefied gas and the yield of propylene are not too high in the table 4.The sulfolane unit of subsidiary riser outlet gasoline is not also gone up by this refinery, can't in industry, obtain benzene, toluene, xylol.But analytical data shows the aromaticity content of subsidiary riser outlet gasoline at 60-70%, is again the ten minutes proven technique with the selective solvent extracting aromatic hydrocarbons of tetramethylene sulfone.Therefore, the work flow that adopts this patent to propose, the refinery not only obtains the liquefied gas (mainly being to be producing more propylene) of high yield, and can also produce benzene, toluene, xylol, is ten minutes reliable technique route.Tetramethylene sulfone is extracted benzene, toluene, xylol out, raffinates oil also can return subsidiary riser and do charging.Be increasing production of liquid gas (mainly being to be producing more propylene) significantly, can be the charging of the carbon in the liquefied gas four as subsidiary riser, even can also use of the charging of part catalytic diesel oil as subsidiary riser.Adopt this patent, refinery processing poor quality oil will be a main products with liquefied gas, propylene, benzene, toluene, xylol, and its economic benefit is self-evident.
Claims (4)
1. the complete processing of a poor quality oil is characterized in that poor quality oil is introduced into delayed coking unit and takes off charcoal, demetalization, and the coking that constitutes with coker gasoline, coker gas oil and wax tailings generates the charging of oil as double lift pipe catalytic cracking master riser tube; Catalytic gasoline, comprise that the charging of carbon four components as subsidiary riser, cracking under severe condition, said severe condition are that the head temperature of subsidiary riser is controlled at 580-620 ℃, catalystoil ratio is 20-30; The gasoline that is obtained by the subsidiary riser outlet goes out aromatic hydrocarbons with the selective solvent extracting, and then isolates benzene, toluene and xylol; Raffinate oil and return subsidiary riser as cracked charge; Increasing production of liquid gas significantly.
2. the complete processing of poor quality oil according to claim 1 is characterized in that the part catalytic diesel oil is also as the charging of subsidiary riser.
3. the complete processing of poor quality oil according to claim 1, wherein selective solvent is diethylene glycol ether, triethylene glycol ether, methyl-sulphoxide, tetramethylene sulfone or dipropylene glycol.
4. the complete processing of poor quality oil according to claim 1 is characterized in that described poor quality oil comprises fuel heavy oil, is difficult to the fcc raw material or the vacuum residuum of cracked naphthene base crude oil and middle base oil.
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| CN102250641B (en) * | 2010-05-17 | 2014-08-20 | 宁波科元塑胶有限公司 | Method and apparatus for preparing ethylene and propylene with maximized yield |
| CN111057569A (en) * | 2020-01-02 | 2020-04-24 | 青岛惠城环保科技股份有限公司 | Waste plastic recycling method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710031A (en) * | 2005-07-01 | 2005-12-21 | 袁培林 | Method for producing propene by catalytic modification of gasoline while reducing olefin |
| CN1912065A (en) * | 2005-08-09 | 2007-02-14 | 中国石油化工股份有限公司 | Catalytic conversion method for preducing more propylene |
| CN1923971A (en) * | 2005-08-31 | 2007-03-07 | 中国石油化工股份有限公司 | Catalytic conversion method capable of increasing propylene yield |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710031A (en) * | 2005-07-01 | 2005-12-21 | 袁培林 | Method for producing propene by catalytic modification of gasoline while reducing olefin |
| CN1912065A (en) * | 2005-08-09 | 2007-02-14 | 中国石油化工股份有限公司 | Catalytic conversion method for preducing more propylene |
| CN1923971A (en) * | 2005-08-31 | 2007-03-07 | 中国石油化工股份有限公司 | Catalytic conversion method capable of increasing propylene yield |
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