CN100457856C - Delayed coking method for promoting light oil yield - Google Patents
Delayed coking method for promoting light oil yield Download PDFInfo
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- CN100457856C CN100457856C CNB2004100507915A CN200410050791A CN100457856C CN 100457856 C CN100457856 C CN 100457856C CN B2004100507915 A CNB2004100507915 A CN B2004100507915A CN 200410050791 A CN200410050791 A CN 200410050791A CN 100457856 C CN100457856 C CN 100457856C
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Abstract
The invention discloses a delay coking technique, which comprises: in common process, adding optimum-seeked coke-inhibitor and some lower carbon number hydrocarbons in bottom of coking tower. Compared with prior art, this invention increases light oil yield, reduces coke yield, needs low cost, and fis to different coking techniques.
Description
Technical field
The invention belongs to a kind of heavy oil delay coking process, specifically, is to improve a kind of method that the light-end products yield reduces the coke product yield in the delayed coking operation process.
Background technology
Delayed coking has been used for many years in petroleum refining industry as one of heavy oil upgrading means.This technology is to be raw material with heavy, poor residuum, enters coking tower after the process furnace heating, and thermolysis generates the liquid product and the coke product of gas products, different boiling in coking tower.
The raw material of refinery's delayed coking unit processing at present is more and more heavy, and some inferior raw material is under the cyclical operation condition, and coke yield is up to 30wt%-40wt%, and liquid product is quite few.Because delayed coking unit is subjected to the restriction of coke yield, is never well developed.
In order to improve the delayed coking yield of light oil, reduce the coke product yield, the investigator proposes many improving one's methods both at home and abroad.Domestic in recent years have many about the improved patent in delayed coking flow process aspect, external also have some about the patent that in stock oil, adds the thinner aspect as US4455219, the patent that adds free radical inhibitors in stock oil is as US4784744, US5006223, US4378288.The method of introducing in these patents all has some improved actions to improving delayed coking process liquid yield reduction coke yield aspect.Proposed in the residuum coking process as US4784744, added methyl free radicals.Free radical can under 500 ℃, produce free radical by passing through the MgO beds less than C4 gas (mixture), and the unsaturated hydrocarbons in order to saturated cracking reaction produces stops coking, thereby reduces the generation of coke.This procedure more complicated.
U.S. Pat 5407560 has been introduced a kind of rare earth metal organic compound (mostly being lipid acid) that adds in stock oil, improve the combustionproperty of coke, increases a kind of method of liquid yield simultaneously.Rare earth metal used in this method mainly contains: lanthanum, cerium, neodymium, praseodymium or the like.These rare earth metals join in the stock oil with the form of organic compound, and add-on is 5-5000ppm (in an element), claim and improve liquid yield 0.5%-8.0%.The used rare earth metal cost of this patented method height, it is little to improve the liquid yield amplitude.
U.S. Pat 4756819 has been introduced a kind of process that adds metal-salt in stock oil.Metal is: Mo, V, Cr, W, Fe, Co, Ni.Metallic compound is added in the stock oil with the forms such as solid suspension of organo-metallic sulfide.Add-on preferably adds 0.05～5% organosulfur simultaneously for to count 100～2500ppm with metallic element, 400 ℃-500 ℃ of temperature of reaction, operates under the condition of pressure: 1bar-100bars (with hydrogen or nitrogen or water vapor).It is higher that this method adds amount of metal, and the main and processes such as viscosity breaking under hydrogen exists are because metal is a hydrogenation sites, little for the thermally splitting effect.CN1448490A discloses a kind of coke inhibitor, can be used for various refining of petroleum and petrochemical process, comprising coking.But owing to be broad-spectrum coke inhibitor, component is comparatively complicated, is not optimized component and content at coking, contains oxime and sulfocompound, hydrogen receptor etc. as this coke inhibitor, show that through a large amount of experiments these materials are used the not outstanding Jiaozhuo that presses down of coking.And this patent does not more relate to and how to cooperate to reach the better burnt effect that presses down with other operational condition.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of raising light oil products yield, reduce coking yield, the coking delay process that running cost is low.
Delay coke processing method of the present invention is as follows: under the delayed coking operation condition, with coking raw material with after coke inhibitor mixes, enter coking tower through heating and carry out cracking reaction, simultaneously sneak into a certain amount of lower carbon number hydrocarbons in the coking tower bottom, as C1～C4 hydro carbons, add-on generally accounts for 0.5%～10% of raw material weight, and preferred 2%～6%.Reacted liquid product enters separation column to be separated, and the sedimentation of coke that reaction generates after coke is full of, stops charging in coking tower at the bottom of tower.The concentration that coke inhibitor is added in the coking raw material is 50～2000 μ g/g, is preferably 100～1000 μ g/g.
Coke inhibitor is the composition of main fatty acid esters, phenol and Organophosphorous compounds, and its weight ratio is 1: 0.1～10: 0.1～10, be preferably 1: 0.5～3: 0.5～and 3.
Fatty acid ester can be the ester class that the oxy-compound of the lipid acid of C1～C20 and C1～C20 forms, better suited fatty acid ester is: ethyl acetate, propyl acetate, butylacetate, octyl acetate, pentyl acetate, phenylacetate, naphthyl acetate, methyl aceto acetate, ethylene glycol dilaurate, ethylene glycol oleic acid ester, Diethylene Glycol monooctadecyl acid ester, Diethylene Glycol SUNSOFT Q-182S, methyl tetradecanoate, dioctyl succinate, maleficent acid diethyl ester, this dish, tween etc., also can use two or more mixing wherein.
Aldehydes matter can contain the phenols of 1～3 phenyl ring.Better suited phenolic compound is: naphthols, phenol derivmives blend biology, 2,5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, Eugenol, thymol, to benzylphenol, 4-isobutyl--2-(α-Jia Bianji) phenol etc., also can be two or more mixture wherein.
Better suited Organophosphorous compounds are: triphenylphosphine, triphenylphosphine oxide, triphenylphosphate, triethyl phosphate, tripropyl phosphoric acid ester, triisooctyl phosphate, tricresyl phosphate naphthol ester, methyl acid phosphate diisoamyl ester, di-iso-octylmethylphosphonate, di-iso-amyl butylphosphonate, phosphenylic acid diisobutyl ester, mono phosphoric acid ester-2-(ethyl hexyl) ester etc., and also can be with wherein two or more mixes use.
Certainly, in coke inhibitor, can also add the organism that dissolves each other with it, as oil such as various petroleum fractionss, solvents.Coke inhibitor can directly add in the coking raw material, also can adopt the emulsion form to add, the preferred latter.
In the delay coking process of the present invention, add a small amount of coke inhibitor, add a certain amount of lower carbon number hydrocarbons simultaneously, both synergies can play the good burnt effect that presses down, and compare with only using coke inhibitor, and the coke yield in the coking obviously descends.The inventive method has been selected coke inhibitor component and content preferably at coking, makes it to cooperate with working method of optimizing and processing condition, has reached best reaction effect.The inventive method not only can be used for general weight, coking of residues is handled, and can also handle raw materials such as catalytically cracked oil inferior, shale oil, oil-sand, improves the economic benefit that these raw materials are handled.Coke inhibitor add-on of the present invention is few, and cost is low, presses down burnt effective.When coke inhibitor adopts the emulsion form to add raw material, has more outstanding effect to reducing coke yield and improving light oil yield.
Embodiment
Characteristics of the present invention are in conventional delay coking process process, and coke inhibitor is joined in the coking raw material, enter coking tower by process furnace and carry out cracking reaction; Simultaneously in reactor, charge into lower carbon number hydrocarbons in the coking tower bottom.Reacted product generally can be separated into C with it after entering and separating in the separation column
4Following cut (this cut can all or part ofly be got back to reactor lower part and recycle), C
5-180 ℃ of gasoline fractions, 180 ℃ of-350 ℃ of diesel oil distillates, 350 ℃ of-450 ℃ of wax oil cuts and tail oil more than 450 ℃.The sedimentation of coke that reaction generates in coking tower after coke is full of, can stop charging in coking tower at the bottom of tower, switch to another coking tower and carry out same operation (but each coking tower operate continuously 36 hours-48 hours).In addition, can be as the case may be, tail oil at the bottom of the isolated tower in the separation system is partly or entirely looped back the device front portion to be handled with fresh coking raw material again, can certainly adopt at the bottom of the tower not cyclic process of tail oil, one-pass scheme, generally can select part round-robin mode to operate, its recycle ratio is generally 0.01-1.0, preferably 0.15-0.45.
Coking operation condition of the present invention is: coking raw material is heated to 450 ℃-530 ℃, and the temperature of reaction in the coking tower is generally at 465 ℃-525 ℃, and working pressure is 0.01MPa-1.5MPa etc., can require concrete definite according to feedstock property and product index.The lower carbon number hydrocarbons that charges in the reactor can be the lower carbon number hydrocarbons in other source, also can be the lower carbon number hydrocarbons that obtains in this technology.
Coking raw material is the heavy oil or the residual oil raw material of initial boiling point＞350 ℃, generally can be selected from residual oil, visbroken resids, the heavy deasphalted oil of deasphalting unit, catalytically cracked oil, viscous crude, the topped crude of atmospheric and vacuum distillation unit, also can be selected from other certainly as coal processing, shale, oil-sand etc.Technical solution of the present invention goes in various types of coking process.
Specify embodiment of the present invention and effect by the following examples.All experiments are all identical with stock oils, raw materials furnace and heating temperature out, reaction pressure, recycle ratio among the embodiment, are intended to the influence to pyrogenic reaction of comparison coke inhibitor add-on and lower carbon number hydrocarbons add-on.
Test raw materials used oil nature and see Table 1.The raw materials furnace and heating temperature out is 500 ℃, and working pressure is 0.17MPa, recycle ratio 0.0 (w/w).The C1 that lower carbon number hydrocarbons obtains for the coking fractionating system～C4 hydro carbons.The coking tower coke stops charging after amassing and expiring, and adustion 2 hours is removed volatile matter.The coke inhibitor composition sees Table 2.Coke inhibitor add-on and experiment condition and test-results see Table 3.
Table 1 raw material oil properties
| Project | Stock oil |
| Density, (20 ℃), Kg/m 3 | 984.2 |
| Carbon residue, wt% | 15.7 |
| Sulphur content, wt% | 1.04 |
| The H/C atomic ratio | 1.53 |
| Initial boiling point, ℃ | 385 |
| 50％，℃ | 460 |
| 95％，℃ | 556 |
Table 2 coke inhibitor is formed
| Numbering | R1 | R2 | R3 | R4 | R5 |
| Fatty acid ester | Ethyl acetate, octyl acetate (weight ratio 1: 2) | Ethylene glycol dilaurate | Dioctyl succinate | The maleficent acid diethyl ester | The ethylene glycol oleic acid ester |
| Phenol | To benzylphenol | Eugenol | Thymol | 2, the 5-di-tert-butylphenol | To benzylphenol, naphthols (weight ratio 2: 1) |
| Organophosphorous compounds | Triphenylphosphate | Triisooctyl phosphate | Triphenylphosphine, tripropyl phosphoric acid ester (weight ratio 1: 1) | Mono phosphoric acid ester-2-(ethyl hexyl) ester | Triethyl phosphate |
| Weight ratio | 1∶4∶0.5 | 1∶0.5∶0.3 | 1∶0.8∶5 | 1∶8∶4 | 1∶5.5∶2.5 |
| Other (not measuring during use) | / | / | The atmosphere 3rd side cut distillate accounts for 20% of gross weight | / | Be made into the emulsion of moisture 60 weight %, the anhydrous sorbitol stearate that adds 5 weight % is an emulsifying agent |
Table 3 coke inhibitor add-on and product distribute
Annotate: product distribution C in the table 2
1～C
4Data are to remove the lower carbon number hydrocarbons amount that charges into the coking tower bottom.Light oil yield improves and reduces with coke yield is the numerical value of comparing with Comparative Examples 1.From the table data as can be seen, coke inhibitor that the inventive method is selected for use and lower carbon number hydrocarbons have good coordinative role, have outstanding result of use during acting in conjunction.
Claims (10)
1, a kind of delayed coking method that improves light oil yield, under the delayed coking operation condition, with coking raw material with after coke inhibitor mixes, enter coking tower through heating and carry out cracking reaction, sneak into lower carbon number hydrocarbons in the coking tower bottom simultaneously, add-on accounts for 0.5%～10% of raw material weight, reacted liquid product enters separation column to be separated, the sedimentation of coke that reaction generates after coke is full of, stops charging in coking tower at the bottom of tower; Wherein coke inhibitor is the composition of main fatty acid esters, phenol and Organophosphorous compounds, and its weight ratio is 1: 0.1～10: 0.1～10, and the concentration of coke inhibitor in coking raw material is 50～2000 μ g/g; Wherein: described lower carbon number hydrocarbons is C1～C4 hydro carbons; Described fatty acid ester is the ester class that the oxy-compound of the lipid acid of C1～C20 and C1～C20 forms; Described aldehydes matter is the phenols that contains 1～3 phenyl ring; Described Organophosphorous compounds are: triphenylphosphine, triphenylphosphine oxide, triphenylphosphate, triethyl phosphate, tripropyl phosphoric acid ester, triisooctyl phosphate, tricresyl phosphate naphthol ester, methyl acid phosphate diisoamyl ester, di-iso-octylmethylphosphonate, di-iso-amyl butylphosphonate, phosphenylic acid diisobutyl ester or mono phosphoric acid ester-2-(ethyl hexyl) ester, or two or more mixture wherein.
2, in accordance with the method for claim 1, it is characterized in that described lower carbon number hydrocarbons add-on accounts for 2%～6% of raw material weight.
3, in accordance with the method for claim 1, it is characterized in that the concentration of described coke inhibitor in coking raw material is 100～1000 μ g/g.
4, in accordance with the method for claim 1, the weight ratio that it is characterized in that fatty acid ester, phenol and Organophosphorous compounds in the described coke inhibitor is 1: 0.5～3: 0.5～3.
5, according to claim 1 or 4 described methods, it is characterized in that described fatty acid ester is: ethyl acetate, propyl acetate, butylacetate, octyl acetate, pentyl acetate, phenylacetate, naphthyl acetate, methyl aceto acetate, ethylene glycol dilaurate, ethylene glycol oleic acid ester, Diethylene Glycol monooctadecyl acid ester, Diethylene Glycol SUNSOFT Q-182S, methyl tetradecanoate, dioctyl succinate, maleficent acid diethyl ester, this dish or tween, or two or more mixture wherein.
6, according to claim 1 or 4 described methods, it is characterized in that described phenolic material pledge is: 2,5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, Eugenol, thymol, to benzylphenol or 4-isobutyl--2-(α-Jia Bianji) phenol, or two or more mixture wherein.
7, in accordance with the method for claim 1, it is characterized in that coke inhibitor directly adds in the coking raw material, or add in the coking raw material with the emulsion form.
8, according to claim 1 or 2 described methods, it is characterized in that the fractionating system of described lower carbon number hydrocarbons from coking.
9, in accordance with the method for claim 1, it is characterized in that described coking operation condition is: coking raw material is heated to 450 ℃～530 ℃, and the temperature of reaction in the coking tower is at 465 ℃～525 ℃, and working pressure is 0.01MPa～1.5MPa.
10, in accordance with the method for claim 1, it is characterized in that described coking raw material is the heavy oil or the residual oil raw material of initial boiling point＞350 ℃.
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| CNB2004100507915A CN100457856C (en) | 2004-10-29 | 2004-10-29 | Delayed coking method for promoting light oil yield |
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| CN100457856C true CN100457856C (en) | 2009-02-04 |
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| CN101597518B (en) * | 2009-06-25 | 2012-12-12 | 中国石油化工集团公司 | Improved delayed coking process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593568A (en) * | 1994-05-13 | 1997-01-14 | Nalco Chemical Company | Coker/visbreaker and ethylene furnace antifoulant |
| CN1448466A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Method for raising production efficiency of delayed coking liquid product |
| CN1448490A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Coking-suppressing antiscale and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593568A (en) * | 1994-05-13 | 1997-01-14 | Nalco Chemical Company | Coker/visbreaker and ethylene furnace antifoulant |
| CN1448466A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Method for raising production efficiency of delayed coking liquid product |
| CN1448490A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Coking-suppressing antiscale and application thereof |
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