CN103571516A - Delayed coking method - Google Patents
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Abstract
The invention provides a delayed coking method. The delayed coking method comprises the following steps: 1) moistening carbon particles through a moistening agent; dissolving or dispersing the moistened carbon particles into a dispersing agent with modifying substances dispersed; agitating the dispersing agent for 3 to 5 hours under normal temperature or the temperature of 50 to 80 DEG C; standing for 18 to 24 hours; drying for 2 to 4 hours under 120 to 150 DEG C; depositing metal elements in the modifying substances onto the carbon particles; and roasting for 3 to 5 hours under 450 to 560 DEG C through a muffle with the nitrogen protection, thus obtaining the modified carbon particles; 2) uniformly dispersing the modified carbon particles obtained in the step 1) into dispersing oil to obtain a modified carbon particle dispersing substance; and 3) adding the modified carbon particle dispersing substance obtained in the step 2) into the raw oil, and coking. By adopting the delayed coking method, the yield of liquid products can be increased, the yield of coke can be decreased, and the content of sulphur in coke can be decreased.
Description
Technical field
The present invention relates to a kind of delayed coking method, relate in particular to a kind of delayed coking method that adds additive in delayed coking raw material.
Background technology
Hydrogenation and decarburization are two kinds of different approaches of residual oil weight-lightening, and delayed coking is as decarburization thermocracking process the most thoroughly, due to its technology maturation, bottoms conversion is high, adaptability to raw material is strong, production cost is low, and are widely used in residual oil deep processing.In recent years, along with oil supply day is becoming tight, high-quality and crude oil with poor quality price difference increase, domestic Petrochemical Enterprises is for increasing economic efficiency, a large amount of processing high-sulfurs, high bituminous matter crude oil with poor quality, the vacuum residuum of these crude oil is mainly to process by delay coking process, and the in poor quality degree of delayed coking raw material obviously improves, and has brought many problems.(1) liquid yield is low, and coke yield is high.(2) coke sulphur content is high, degradation.(3) furnace tubing coking is serious, affects long-term operation and the treatment capacity of device.For improving liquid, receive, reduce coke yield, refinery generally can take to reduce recycle ratio, reduces working pressure, improves service temperature, the technological measures such as distillate circulation.But also there is the method that adds solid or fluid additive in aligning device of adopting, as patent USP4,394,250 disclose a kind of delay coking process, add fluidized catalytic cracking catalyst powder or the hydrocracking catalyst powder of 0.1～3.0w% in coking raw material, preferred catalytic cracking catalyst powder, face under hydrogen state, coking raw material is heated to 454～593 ℃, 427～649 ℃ of reactions, to improve liquid yield, reduce coking yield.Patent USP5,407,560 disclose a kind of method of producing refinery coke and cracked oil from heavy crude, the rare earth organic acid salt or the inorganics that in heavy crude, add one or more, under 450～650 ℃ and certain pressure, carry out pyrogenic reaction, cracked oil yield improves, and coke yield reduces, and combustionproperty and the crushing performance of coke obviously improve.Wang Jiqian etc. [Wang Jiqian, Li Ming, Li Shufeng ，Li Chuan， fault state and. the impact of carbonous particle additive on residual oil thermal response green coke. chemistry of fuel journal, 2006; 34 (1): 36-41.] studied the impact of different carbonous particle additives on thermal response green coke under 420 ℃ of nitrogen atmospheres of Kelamayi long residuum.Experimental result shows, carbonaceous particle suppresses the thermal response green coke of residual oil to a certain extent in initial reaction stage, but there is promoter action in the later stage.The disclosed a kind of improved delayed coking method of CN1676574 can reduce the particularly sulphur content of coke of product, coking raw material with together with optional coking recycle oil after the supercharging of radiation fresh feed pump, be that the metal of VIII family element, the catalyzer of metal oxide metallic sulfide contact with hydrogen, active ingredient, entering coking heater is heated to after coking temperature, hydrogenated oil enters coke drum after throttling set step-down, the coke generating is stayed in coke drum, and coking oil gas is isolated to cooking gas, coker gasoline, coker gas oil, wax tailings.But reduce the method for the more employing aftertreatments of refinery coke sulphur content, as patent CN98114600 discloses a kind of method of high temperature desulfurizing, first refinery coke is heated to 600～1200 ℃, original nonconducting refinery coke is made into conductive material, again conduction refinery coke is placed in to electric furnace and is warmed to 1700～2300 ℃ sulphur content and other impurity are overflowed, produce the refinery coke that sulfur-bearing is less than 0.1%.20070121719.0 of Chinese patents add any one sweetening agent being selected from zirconium white, cerium oxide and yttrium oxide to calcine to reach the object of desulfurization in raw petroleum coke.
In above-mentioned many patented methods, or to improving delayed coking liquid yield, reducing coke yield, or all obtained certain effect to reducing refinery coke sulphur content, but also come with some shortcomings.(1) need to face hydrogen, and catalytic cracking catalyst powder or metal oxide or sulfide is gathered in refinery coke, increases the ash content of refinery coke, reduce Petroleum Coke; (2) improving liquid yield, reduction coke yield and coke sulphur content can not realize simultaneously; (3) refinery coke aftertreatment reduces sulphur content, and high-temperature calcination not only needs to expend higher energy, and need to adopt expensive high temperature material, and desulphurization cost is very high.
Summary of the invention
The problems referred to above that exist in order to solve prior art, the invention provides a kind of delayed coking method, utilize the method can improve liquid product yield, reduce coke yield and reduce coke sulphur content.
Provided by the invention kind of delayed coking method comprises the steps:
1) preparation of modification carbonaceous particle: first with wetting agent, carbonaceous particle is wetting, wetting carbonaceous particle is dissolved or is dispersed in the dispersion agent that is dispersed with modified material, then dispersed with stirring agent 3～5 hours at normal temperature or 50～80 ℃, standing 18～24 hours, at 120～150 ℃, be dried 2～4 hours, the metallic element in modified material be deposited on carbonaceous particle, finally under nitrogen protection, in retort furnace, roasting 3～5 hours at 450～560 ℃, obtains modification carbonaceous particle;
2) the modification carbonaceous uniform particles making the preparation of modification carbonaceous particle dispersion: by step 1) is dispersed in dispersed oil, obtains modification carbonaceous particle dispersion;
3) the modification carbonaceous particle dispersion making pyrogenic reaction: by step 2) adds in stock oil, stirs, and carries out pyrogenic reaction, reaction pressure 0.1～0.2Mpa, 420～550 ℃ of temperature of reaction, preferably 450～530 ℃.
Described wetting agent is one or more the mixture in Xylo-Mucine (CMC), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), gum arabic, Styrene And Chloroalkyl Acrylates, methylene sodium dinaphthalenesulfonate (NF), sodium dibutyl naphthalene sulfonate and ammoniacal liquor.
Described carbonaceous particle is graphite, carbon black or gac, preferred graphite or carbon black, and carbonaceous particle is of a size of 30～100 μ m, preferably 40～80 μ m.
Described modified material is oxide compound or the salt compounds of lanthanum (La), cerium (Ce), neodymium (Nd), praseodymium (Pr) or vanadium (V), the salt compounds of lanthanum (La), cerium (Ce), neodymium (Nd) or praseodymium (Pr) is inorganic acid salt or organic acid salt, inorganic acid salt is muriate, carbonate, vitriol, nitrate or phosphoric acid salt, organic acid salt is one or more the mixture in naphthenate, acetate, Citrate trianion, tartrate, oleate, dodecylbenzene sulfonate and tosilate, and the salt compounds of vanadium (V) is vanadic acid ammonium salt; Lanthanum (La), cerium (Ce), neodymium (Nd), praseodymium (Pr) or the content of vanadium (V) in modification carbonaceous particle are 0.5 % by weight～8.0 % by weight, and preferred 1.5 % by weight～7.0 % by weight, in carbonaceous particle gross weight before modification; The oxide compound of modified material preferred cerium or lanthanum or salt compounds.
Described dispersion agent is water, alcohols or hydro carbons, as methyl alcohol, ethanol, benzene,toluene,xylene, octane-iso or No. 200 solvent oils.
Described dispersed oil is for mixing heavy arene, catalytic cracking recycle oil, fluid catalytic cracking decant oil, catalytically cracked oil, wax tailings or hydrocracking tail oil.
Described stock oil is mainly vacuum residuum, long residuum, high viscous crude, visbreaking residue or heavy fuel oil (HFO) or its mixing raw material.
Described modification carbonaceous particle accounts for 0.3 % by weight～3.5 % by weight of stock oil gross weight, preferably 0.5 % by weight～3.0 % by weight.
Compared with prior art, tool of the present invention has the following advantages:
1) delayed coking method of the present invention adds the carbonaceous particle of modification in coking raw material oil, under 420～550 ℃ of reaction conditionss, modification carbonaceous particle by suppress coking precursor coalescence, cracking hydrocarbon chain carrier is provided, improve the cracking reaction degree of depth, thereby improve coking liquid yield, reduce coke yield, reduce the sulphur content in refinery coke, the quality of raising refinery coke, carbonaceous particle is gathered in the use properties that can not affect refinery coke in refinery coke.
2) method of the present invention, owing to not needing to face hydrogen, has reduced investment cost and the process cost of device.
Embodiment
By specific embodiment, further illustrate delayed coking method of the present invention below.
Embodiment 1～12 is the preparation example of modification carbonaceous particle of the present invention, the effect example that embodiment 13～27 is the inventive method.
Embodiment 1
In beaker 1, take carbon black and 1.0g Xylo-Mucine that 50g granularity is 60 μ m, mix; By neodymium content, accounting for 1.0% of carbon black weight before modification calculates; in beaker 2, take neodymium nitrate and 100g distilled water that 1.40g neodymium content is 36%; stirring is fully dissolved it; then the carbon black in beaker 1 and Xylo-Mucine mixture are joined in beaker 2 under stirring state in batches, add rear continuation and stir 3 hours, standing 20 hours; at 120 ℃, be dried 3 hours; finally under nitrogen protection, in retort furnace, roasting 3 hours at 550 ℃, obtains neodymium modified carbon black particle.
Embodiment 2
In beaker 1, take graphite and 1.0g polyvinylpyrrolidone that 50g granularity is 60 μ m, mix; By lanthanum content, accounting for 3.5% of graphite weight before modification calculates, in beaker 2, take lanthanum nitrate and 100g distilled water that 4.86g lanthanum content is 36%, stirring is fully dissolved it, then the graphite in beaker 1 and polyvinylpyrrolidone mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain lanthanum modified graphite particle.
Embodiment 3
In beaker 1, take graphite and 1.0g polyvinyl alcohol that 50g granularity is 60 μ m, mix; By praseodymium content, accounting for 1.5% of graphite weight before modification calculates, in beaker 2, take praseodymium chloride and 100g distilled water that 2.08g praseodymium content is 36%, stirring is fully dissolved it, then the graphite in beaker 1 and polyvinyl alcohol mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain praseodymium modified graphite particle.
Embodiment 4
In beaker 1, take graphite and 1.0g gum arabic that 50g granularity is 60 μ m, mix; By cerium content, accounting for 4.5% of graphite weight before modification calculates, in beaker 2, take 6.25g cerium content and be 36% Cerium II Chloride and 100g distilled water, stirring is fully dissolved it, then the graphite in beaker 1 and gum arabic mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain cerium modified graphite granule.
Embodiment 5
In beaker 1, take carbon black and 1.0g Styrene And Chloroalkyl Acrylates that 50g granularity is 60 μ m, mix; By praseodymium content, accounting for 2.0% of carbon black weight before modification calculates, in beaker 2, take praseodymium chloride and 100g distilled water that 2.78g praseodymium content is 36%, stirring is fully dissolved it, then the carbon black in beaker 1 and styrene-propene acid mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain praseodymium modified carbon black particle.
Embodiment 6
In beaker 1, take carbon black and 1.0g methylene sodium dinaphthalenesulfonate that 50g granularity is 60 μ m, mix; By cerium content, accounting for 4.0% of carbon black weight before modification calculates, in beaker 2, take 5.56g cerium content and be 36% cerous nitrate and 100g distilled water, stirring is fully dissolved it, then the carbon black in beaker 1 and methylene sodium dinaphthalenesulfonate mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain cerium modified carbon black pellet.
Embodiment 7
In beaker 1, take graphite and 1.0g sodium dibutyl naphthalene sulfonate that 50g granularity is 60 μ m, mix; By neodymium content, accounting for 2.5% of graphite weight before modification calculates, in beaker 2, take Neodymium trichloride and 100g distilled water that 3.47g neodymium content is 36%, stirring is fully dissolved it, then the graphite in beaker 1 and sodium dibutyl naphthalene sulfonate mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain neodymium modified graphite particle.
Embodiment 8
In beaker 1, taking 50g granularity is graphite and each 0.5g polyvinylpyrrolidone and ammoniacal liquor of 60 μ m, mixes; By lanthanum content, accounting for 4.5% of graphite weight before modification calculates, in beaker 2, take Lanthanum trichloride and 100g distilled water that 6.25g lanthanum content is 36%, stirring is fully dissolved it, then the graphite in beaker 1, polyvinylpyrrolidone and ammonia water mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain lanthanum modified graphite particle.
Embodiment 9
In beaker 1, take graphite and 1.0g Xylo-Mucine that 50g granularity is 60 μ m, mix; By content of vanadium, accounting for 4.5% of graphite weight before modification calculates, in beaker 2, take 5.00g content of vanadium and be 40% ammonium meta-vanadate and 100g distilled water, stirring is fully dissolved it, then the graphite in beaker 1 and Xylo-Mucine mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain vanadium modified graphite particle.
Embodiment 10
In beaker 1, taking 50g granularity is carbon black and each 0.5g Styrene And Chloroalkyl Acrylates and gum arabic of 60 μ m, mixes; By lanthanum content, accounting for 6.5% of carbon black weight before modification calculates, in beaker 2, take lanthanum nitrate and 100g distilled water that 8.61g lanthanum content is 36%, stirring is fully dissolved it, then the carbon black in beaker 1, Styrene And Chloroalkyl Acrylates and gum arabic mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain lanthanum modified carbon black particle.
Embodiment 11
In beaker 1, take graphite and 1.0g polyvinyl alcohol that 50g granularity is 60 μ m, mix; By cerium content, accounting for 6.5% of graphite weight before modification calculates, in beaker 2, take 8.61g cerium content and be 36% cerous nitrate and 100g distilled water, stirring is fully dissolved it, then the graphite in beaker 1 and polyvinyl alcohol mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain cerium modified graphite granule.
Embodiment 12
In beaker 1, take carbon black and 1.0g methylene dinaphthyl sodium sulfonate that 50g granularity is 60 μ m, mix; By content of vanadium, accounting for 7.0% of carbon black weight before modification calculates, in beaker 2, take 8.75g content of vanadium and be 40% ammonium meta-vanadate and 100g distilled water, stirring is fully dissolved it, then the carbon black in beaker 1 and methylene dinaphthyl azochlorosulfonate acid sodium mixture are joined in beaker 2 under stirring state in batches, repeat the step in embodiment 1, obtain vanadium modified carbon black particle.
Be the implementation result example of the inventive method below.
Implementation result example is to carry out on as lower device, and this device is by high 210mm, the interior stainless steel reactor through 80mm, liquid header, and gas trap and gas pressure piping form.Raw materials used oil nature is as shown in table 1.During experiment, 20g stock oil is added in silica tube, in stock oil, add the modification carbonaceous particle being dispersed in dispersed oil, stir, then silica tube is placed in stainless steel reactor, be filled with nitrogen the air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.1～0.2Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 420～550 ℃, at this temperature, react 8 hours, collect gas and liquid that reaction generates, cooling rear weighing silica tube Jiao's of PetroChina Company Limited. of question response device weight, gaseous product forms and calculated yield to determine it with gas chromatographic analysis, product liquid is through weighing and calculated yield, sulphur content in refinery coke is analyzed with Infrared Carbon and Sulphur Determination instrument, in liquid yield, deduct the amount of added dispersed oil catalytically cracked oil, in refinery coke, deduct the amount of added modification carbonaceous particle.By comparing modification carbonaceous particle, add the variation of sulphur content in front and back gas, liquid, coke yield and coke that effect of the present invention is described.
Table 1 Vacuum Residue Properties
Embodiment 13
20g stock oil is joined in silica tube, put it in stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, at this temperature, react 8 hours, collect gas and liquid that reaction generates, cooling rear weighing silica tube Jiao's of PetroChina Company Limited. of question response device weight, gaseous product forms and calculated yield to determine it with gas chromatographic analysis, product liquid is through weighing and calculated yield, sulphur content in refinery coke is analyzed with Infrared Carbon and Sulphur Determination instrument, and experimental result is in Table 2.
Embodiment 14
20g stock oil is joined in silica tube, and add therein the graphite granule being dispersed in catalytically cracked oil, the add-on of graphite granule is 1.5% of stock oil weight, stirs, and silica tube is put into stainless steel reactor, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, at this temperature, react 8 hours, collect gas and liquid that reaction generates, cooling rear weighing silica tube Jiao's of PetroChina Company Limited. of question response device weight, gaseous product forms and calculated yield to determine it with gas chromatographic analysis, product liquid is through weighing and calculated yield, in liquid yield, deduct the amount of added catalytically cracked oil, in refinery coke, deduct the amount of added graphite granule.Sulphur content in refinery coke is analyzed with Infrared Carbon and Sulphur Determination instrument, and experimental result is in Table 2.
Embodiment 15
20g stock oil is joined in silica tube, and adding therein the neodymium modified carbon black particle of being prepared by embodiment 1 being dispersed in catalytically cracked oil, the add-on of neodymium modified carbon black particle is 3.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 480 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 16
20g stock oil is joined in silica tube, and adding therein the lanthanum modified graphite particle of being prepared by embodiment 2 being dispersed in catalytic cracking recycle oil, the add-on of lanthanum modified graphite particle is 1.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 440 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 17
20g stock oil is joined in silica tube, and adding therein the praseodymium modified graphite particle of being prepared by embodiment 3 being dispersed in fluid catalytic cracking decant oil, the add-on of praseodymium modified graphite particle is 3.0% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 480 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 18
20g stock oil is joined in silica tube, and adding therein the cerium modified graphite granule of being prepared by embodiment 4 being dispersed in catalytically cracked oil, the add-on of cerium modified graphite granule is 1.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 465 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 19
20g stock oil is joined in silica tube, and adding therein the praseodymium modified carbon black particle of being prepared by embodiment 5 being dispersed in wax tailings, the add-on of praseodymium modified carbon black particle is 2.0% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 20
20g stock oil is joined in silica tube, and adding therein the cerium modified graphite granule of being prepared by embodiment 4 being dispersed in hydrogenation tail oil, the add-on of cerium modified graphite granule is 1.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 21
20g stock oil is joined in silica tube, and adding therein the cerium modified carbon black pellet of being prepared by embodiment 6 being dispersed in catalytically cracked oil, the add-on of cerium modified carbon black pellet is 2.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 22
20g stock oil is joined in silica tube, and adding therein the rubidium modified graphite particle of being prepared by embodiment 7 being dispersed in hydrogenation tail oil, the add-on of rubidium modified graphite particle is 1.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 505 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 23
20g stock oil is joined in silica tube, and adding therein the lanthanum modified graphite particle of being prepared by embodiment 8 being dispersed in fluid catalytic cracking decant oil, the add-on of lanthanum modified graphite particle is 1.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 525 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 24
20g stock oil is joined in silica tube, and adding therein the vanadium modified graphite particle of being prepared by embodiment 9 being dispersed in mixing heavy arene, the add-on of vanadium modified graphite particle is 2.0% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 515 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 25
20g stock oil is joined in silica tube, and adding therein the lanthanum modified carbon black particle of being prepared by embodiment 10 being dispersed in catalytically cracked oil, the add-on of lanthanum modified carbon black particle is 0.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 495 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 26
20g stock oil is joined in silica tube, and adding therein the cerium modified graphite granule of being prepared by embodiment 11 being dispersed in wax tailings, the add-on of cerium modified graphite granule is 0.5% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 515 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Embodiment 27
20g stock oil is joined in silica tube, and adding therein the vanadium modified carbon black particle of being prepared by embodiment 12 being dispersed in catalytically cracked oil, the add-on of vanadium modified carbon black particle is 1.0% of stock oil weight, stirs, silica tube is put into stainless steel reactor, use N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, with the speed of 50 ℃/min, make stainless steel reactor be warming up to 485 ℃, all the other steps are with embodiment 14.Experimental result is in Table 2.
Table 2 experimental result
Claims (9)
1. a delayed coking method, is characterized in that comprising the steps:
1) preparation of modification carbonaceous particle: first with wetting agent, carbonaceous particle is wetting, wetting carbonaceous particle is dissolved or is dispersed in the dispersion agent that is dispersed with modified material, then dispersed with stirring agent 3～5 hours at normal temperature or 50～80 ℃, standing 18～24 hours, at 120～150 ℃, be dried 2～4 hours, the metallic element in modified material be deposited on carbonaceous particle, finally under nitrogen protection, in retort furnace, roasting 3～5 hours at 450～560 ℃, obtains modification carbonaceous particle;
2) the modification carbonaceous uniform particles making the preparation of modification carbonaceous particle dispersion: by step 1) is dispersed in dispersed oil, obtains modification carbonaceous particle dispersion;
3) the modification carbonaceous particle dispersion making pyrogenic reaction: by step 2) adds in stock oil, stirs, and carries out pyrogenic reaction, reaction pressure 0.1～0.2Mpa, 420～550 ℃ of temperature of reaction;
Described wetting agent is one or more the mixture in Xylo-Mucine, polyvinylpyrrolidone, polyvinyl alcohol, gum arabic, Styrene And Chloroalkyl Acrylates, methylene sodium dinaphthalenesulfonate, sodium dibutyl naphthalene sulfonate and ammoniacal liquor;
Described carbonaceous particle is graphite, carbon black or gac, and carbonaceous particle is of a size of 30～100 μ m;
Described modified material is oxide compound or the salt compounds of lanthanum, cerium, neodymium, praseodymium or vanadium, the salt compounds of lanthanum, cerium, neodymium or praseodymium is inorganic acid salt or organic acid salt, inorganic acid salt is muriate, carbonate, vitriol, nitrate or phosphoric acid salt, organic acid salt is one or more the mixture in naphthenate, acetate, Citrate trianion, tartrate, oleate, dodecylbenzene sulfonate and tosilate, and the salt compounds of vanadium is vanadic acid ammonium salt; Lanthanum, cerium, neodymium, praseodymium or the vanadium content in modification carbonaceous particle is 0.5 % by weight～8.0 % by weight, in carbonaceous particle gross weight before modification;
Described dispersion agent is water, alcohols or hydro carbons;
Described dispersed oil is for mixing heavy arene, catalytic cracking recycle oil, fluid catalytic cracking decant oil, catalytically cracked oil, wax tailings or hydrocracking tail oil;
Described stock oil is mainly vacuum residuum, long residuum, high viscous crude, visbreaking residue or heavy fuel oil (HFO) or its mixing raw material;
Described modification carbonaceous particle accounts for 0.3 % by weight～3.5 % by weight of stock oil gross weight.
2. delayed coking method according to claim 1, is characterized in that, described pyrogenic reaction temperature is 450～530 ℃.
3. delayed coking method according to claim 1, is characterized in that, described carbonaceous particle is graphite or carbon black, and carbonaceous particle is of a size of 40～80 μ m.
4. delayed coking method according to claim 1, is characterized in that, described modified material is oxide compound or the salt compounds of cerium or lanthanum.
5. delayed coking method according to claim 1, is characterized in that, described dispersion agent is methyl alcohol, ethanol, benzene,toluene,xylene, octane-iso or No. 200 solvent oils.
6. delayed coking method according to claim 1, is characterized in that, described lanthanum, cerium, neodymium, praseodymium or the vanadium content in modification carbonaceous particle is 1.5 % by weight～7.0 % by weight.
7. delayed coking method according to claim 1, is characterized in that, described modification carbonaceous particle accounts for 0.5 % by weight～3.0 % by weight of stock oil gross weight.
8. according to the delayed coking method described in claim 2 or 3, it is characterized in that, described modified material is oxide compound or the salt compounds of cerium or lanthanum.
9. delayed coking method according to claim 8, is characterized in that, described cerium or the lanthanum content in modification carbonaceous particle is 1.5 % by weight～7.0 % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210271381.8A CN103571516B (en) | 2012-07-25 | 2012-07-25 | A kind of delayed coking method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980743A (en) * | 2014-05-12 | 2014-08-13 | 梁洪奎 | Method for producing a chemically modified carbon black |
| CN111704924A (en) * | 2020-06-22 | 2020-09-25 | 山东京博石油化工有限公司 | Method for inhibiting coke yield increase in delayed coking |
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| CN1244669C (en) * | 2004-06-09 | 2006-03-08 | 沈阳工业大学 | Activating additive for delayed coking and cracking heavy oil and preparing method thereof |
| CN101113367A (en) * | 2007-07-19 | 2008-01-30 | 茂名学院 | Adding substance for reducing furnace tube deposition coking and improving liquid yield of delayed coker |
| CN102575171A (en) * | 2009-07-10 | 2012-07-11 | 埃克森美孚研究工程公司 | Delayed coking process |
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| CN1244669C (en) * | 2004-06-09 | 2006-03-08 | 沈阳工业大学 | Activating additive for delayed coking and cracking heavy oil and preparing method thereof |
| CN101113367A (en) * | 2007-07-19 | 2008-01-30 | 茂名学院 | Adding substance for reducing furnace tube deposition coking and improving liquid yield of delayed coker |
| CN101113367B (en) * | 2007-07-19 | 2010-11-10 | 茂名学院 | Adding substance for reducing furnace tube deposition coking and improving liquid yield of delayed coker |
| CN102575171A (en) * | 2009-07-10 | 2012-07-11 | 埃克森美孚研究工程公司 | Delayed coking process |
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| CN103980743A (en) * | 2014-05-12 | 2014-08-13 | 梁洪奎 | Method for producing a chemically modified carbon black |
| CN103980743B (en) * | 2014-05-12 | 2016-08-24 | 潍坊世纪阳光知识产权代理有限公司 | A kind of production method of chemical method modified carbon black |
| CN111704924A (en) * | 2020-06-22 | 2020-09-25 | 山东京博石油化工有限公司 | Method for inhibiting coke yield increase in delayed coking |
| CN111704924B (en) * | 2020-06-22 | 2021-11-16 | 山东京博石油化工有限公司 | Method for inhibiting coke yield increase in delayed coking |
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