CN103571516B - A kind of delayed coking method - Google Patents
A kind of delayed coking method Download PDFInfo
- Publication number
- CN103571516B CN103571516B CN201210271381.8A CN201210271381A CN103571516B CN 103571516 B CN103571516 B CN 103571516B CN 201210271381 A CN201210271381 A CN 201210271381A CN 103571516 B CN103571516 B CN 103571516B
- Authority
- CN
- China
- Prior art keywords
- carbonaceous particle
- weight
- oil
- dispersed
- delayed coking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of delayed coking method, comprise the steps: 1) first with wetting agent, carbonaceous particle is soaked, being dissolved or dispersed in by wetting carbonaceous particle is dispersed with in the dispersion agent of modified material, then dispersed with stirring agent 3 ~ 5 hours at normal temperature or 50 ~ 80 DEG C, leave standstill 18 ~ 24 hours, drying 2 ~ 4 hours at 120 ~ 150 DEG C, metallic element in modified material is deposited on carbonaceous particle, under nitrogen protection finally, in retort furnace, roasting 3 ~ 5 hours at 450 ~ 560 DEG C, obtains modification carbonaceous particle; 2) by step 1) in obtained modification carbonaceous even particulate dispersion in dispersed oil, obtain modification carbonaceous particle dispersion; 3) by step 2) in obtained modification carbonaceous particle dispersion add in stock oil, carry out pyrogenic reaction.Utilize method of the present invention can improve liquid product yield, reduce coke yield and reduce coke sulphur content.
Description
Technical field
The present invention relates to a kind of delayed coking method, relate in particular to a kind of delayed coking method adding 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, and due to its technology maturation, bottoms conversion is high, adaptability to raw material is strong, production cost is low, and is 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-sulfur, high bituminous matter crude oil with poor quality, the vacuum residuum of these crude oil is mainly processed by delay coking process, and the in poor quality degree of delayed coking raw material significantly improves, and brings 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.Receiving for improving liquid, reducing 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 for adopting in aligning device and adding solid or fluid additive, 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, under facing hydrogen state, coking raw material is heated to 454 ~ 593 DEG C, 427 ~ 649 DEG C 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, one or more rare earth organic acid salt or inorganics is added in heavy crude, pyrogenic reaction is carried out under 450 ~ 650 DEG C and certain pressure, 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. carbonous particle additive is on the impact of residual oil thermal response green coke. chemistry of fuel journal, 2006; 34 (1): 36-41.] have studied the impact of different carbonous particle additive on thermal response green coke under Kelamayi long residuum 420 DEG C of nitrogen atmospheres.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 delayed coking method of a kind of improvement disclosed in CN1676574 can reduce the sulphur content of product particularly coke, coking raw material together with optional coking recycle oil after the supercharging of radiation fresh feed pump, be the metal of VIII element, the catalyst exposure of metal oxide metal sulfide with hydrogen, active ingredient, enter after coking heater is heated to coking temperature, hydrogenated oil enters coke drum after throttling set step-down, the coke generated 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 DEG C, original nonconducting refinery coke is made into conductive material, again conduction refinery coke is placed in electric furnace be warmed to 1700 ~ 2300 DEG C make sulphur content and other impurity effusion, produce the refinery coke that sulfur-bearing is less than 0.1%.Chinese patent 20070121719.0 adds the object that any one sweetening agent be selected from zirconium white, cerium oxide and yttrium oxide carries out calcining to reach desulfurization in raw petroleum coke.
In above-mentioned many patented methods, or to raising delayed coking liquid yield, reduction coke yield, or certain effect is all achieved to reduction 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 are gathered in refinery coke, increase the ash content of refinery coke, reduce Petroleum Coke; (2) improve 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 needs to adopt expensive high temperature material, and desulphurization cost is very high.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the invention provides a kind of delayed coking method, utilizing 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 soaked, being dissolved or dispersed in by wetting carbonaceous particle is dispersed with in the dispersion agent of modified material, then dispersed with stirring agent 3 ~ 5 hours at normal temperature or 50 ~ 80 DEG C, leave standstill 18 ~ 24 hours, at 120 ~ 150 DEG C, drying 2 ~ 4 hours, is deposited on carbonaceous particle by the metallic element in modified material, under nitrogen protection finally, in retort furnace, roasting 3 ~ 5 hours at 450 ~ 560 DEG C, obtains modification carbonaceous particle;
2) preparation of modification carbonaceous particle dispersion: by step 1) in obtained modification carbonaceous even particulate dispersion in dispersed oil, obtain modification carbonaceous particle dispersion;
3) pyrogenic reaction: by step 2) in obtained modification carbonaceous particle dispersion add in stock oil, stir, carry out pyrogenic reaction, reaction pressure 0.1 ~ 0.2Mpa, temperature of reaction 420 ~ 550 DEG C, preferably 450 ~ 530 DEG C.
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 μm, preferably 40 ~ 80 μm.
Described modified material is lanthanum (La), cerium (Ce), neodymium (Nd), the oxide compound of praseodymium (Pr) or vanadium (V) or salt compounds, lanthanum (La), cerium (Ce), the salt compounds of 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 naphthenate, acetate, Citrate trianion, tartrate, oleate, one or more mixture in dodecylbenzene sulfonate and tosilate, 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, preferably 1.5 % by weight ~ 7.0 % by weight, with carbonaceous particle total weight before modified, 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 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, and 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 DEG C of reaction conditionss, modification carbonaceous particle is by suppressing the coalescence of coking precursor, providing cracking hydrocarbon chain carrier, improve the cracking reaction degree of depth, thus improving the quality of coking liquid yield, reduction coke yield, the sulphur content reduced in refinery coke, 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, reduces investment cost and the process cost of device.
Embodiment
Delayed coking method of the present invention is illustrated further below by way of specific embodiment.
Embodiment 1 ~ 12 is the preparation example of modification carbonaceous particle of the present invention, and embodiment 13 ~ 27 is the effect example of the inventive method.
Embodiment 1
In beaker 1, take carbon black and 1.0g Xylo-Mucine that 50g granularity is 60 μm, mix; Account for 1.0% of carbon black weight before modified by neodymium content to calculate; neodymium nitrate and 100g distilled water that 1.40g neodymium content is 36% is taken in beaker 2; stirring makes it fully dissolve; then the carbon black in beaker 1 and Xylo-Mucine mixture are joined in beaker 2 under agitation in batches, add rear continuation stirring 3 hours, leave standstill 20 hours; drying 3 hours at 120 DEG C; last under nitrogen protection, in retort furnace, roasting 3 hours at 550 DEG C, obtains neodymium modified carbon black particle.
Embodiment 2
In beaker 1, take graphite and 1.0g polyvinylpyrrolidone that 50g granularity is 60 μm, mix; Account for 3.5% of graphite weight before modified by lanthanum content to calculate, lanthanum nitrate and 100g distilled water that 4.86g lanthanum content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and polyvinylpyrrolidone mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 1.5% of graphite weight before modified by praseodymium content to calculate, praseodymium chloride and 100g distilled water that 2.08g praseodymium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and polyvinyl alcohol mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 4.5% of graphite weight before modified by cerium content to calculate, Cerium II Chloride and 100g distilled water that 6.25g cerium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and gum arabic mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 2.0% of carbon black weight before modified by praseodymium content to calculate, praseodymium chloride and 100g distilled water that 2.78g praseodymium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the carbon black in beaker 1 and styrene-propene acid mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 4.0% of carbon black weight before modified by cerium content to calculate, cerous nitrate and 100g distilled water that 5.56g cerium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the carbon black in beaker 1 and methylene sodium dinaphthalenesulfonate mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 2.5% of graphite weight before modified by neodymium content to calculate, Neodymium trichloride and 100g distilled water that 3.47g neodymium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and sodium dibutyl naphthalene sulfonate mixture are joined in beaker 2 under agitation in batches, repeat the step in embodiment 1, obtain neodymium modified graphite particle.
Embodiment 8
In beaker 1, take 50g granularity is the graphite of 60 μm and each 0.5g polyvinylpyrrolidone and ammoniacal liquor, mixes; Account for 4.5% of graphite weight before modified by lanthanum content to calculate, Lanthanum trichloride and 100g distilled water that 6.25g lanthanum content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1, polyvinylpyrrolidone and ammonia water mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 4.5% of graphite weight before modified by content of vanadium to calculate, ammonium meta-vanadate and 100g distilled water that 5.00g content of vanadium is 40% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and Xylo-Mucine mixture are joined in beaker 2 under agitation in batches, repeat the step in embodiment 1, obtain vanadium modified graphite particle.
Embodiment 10
In beaker 1, take 50g granularity is the carbon black of 60 μm and each 0.5g Styrene And Chloroalkyl Acrylates and gum arabic, mixes; Account for 6.5% of carbon black weight before modified by lanthanum content to calculate, lanthanum nitrate and 100g distilled water that 8.61g lanthanum content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the carbon black in beaker 1, Styrene And Chloroalkyl Acrylates and gum arabic mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 6.5% of graphite weight before modified by cerium content to calculate, cerous nitrate and 100g distilled water that 8.61g cerium content is 36% is taken in beaker 2, stirring makes it fully dissolve, then the graphite in beaker 1 and polyvinyl alcohol mixture are joined in beaker 2 under agitation 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 μm, mix; Account for 7.0% of carbon black weight before modified by content of vanadium to calculate, ammonium meta-vanadate and 100g distilled water that 8.75g content of vanadium is 40% is taken in beaker 2, stirring makes it fully dissolve, then the carbon black in beaker 1 and methylene dinaphthyl azochlorosulfonate acid sodium mixture are joined in beaker 2 under agitation 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 carried out on such as lower device, and this device is by high 210mm, the interior stainless steel reactor through 80mm, liquid header, gas trap and gas pressure piping composition.Raw materials used oil nature is as shown in table 1.During experiment, 20g stock oil is added in silica tube, add the modification carbonaceous particle be dispersed in dispersed oil in stock oil, stir, then silica tube is placed in stainless steel reactor, be filled with nitrogen by clean for the air displacement in stainless steel reactor, and make the pressure in stainless steel reactor maintain 0.1 ~ 0.2Mpa, stainless steel reactor is made to be warming up to 420 ~ 550 DEG C with the speed of 50 DEG C/min, react 8 hours at this temperature, collect gas and the liquid of reaction generation, the weight of silica tube PetroChina Company Limited. Jiao is weighed after the cooling of question response device, gaseous product gas chromatographic analysis is to determine its composition and calculated yield, product liquid is through weighing and calculated yield, sulphur content Infrared Carbon and Sulphur Determination instrument in refinery coke is analyzed, the amount of added dispersed oil catalytically cracked oil is deducted in liquid yield, the amount of added modification carbonaceous particle is deducted in refinery coke.The change adding sulphur content in front and back gas, liquid, coke yield and coke by comparing modification carbonaceous particle illustrates effect of the present invention.
Table 1 Vacuum Residue Properties
Embodiment 13
20g stock oil is joined in silica tube, puts it in stainless steel reactor, use N
2by clean for the air displacement in stainless steel reactor, and make the pressure in stainless steel reactor maintain 0.15Mpa, stainless steel reactor is made to be warming up to 495 DEG C with the speed of 50 DEG C/min, react 8 hours at this temperature, collect gas and the liquid of reaction generation, the weight of silica tube PetroChina Company Limited. Jiao is weighed after the cooling of question response device, gaseous product gas chromatographic analysis is to determine its composition and calculated yield, product liquid is through weighing and calculated yield, sulphur content Infrared Carbon and Sulphur Determination instrument in refinery coke is analyzed, and experimental result is in table 2.
Embodiment 14
Joined in silica tube by 20g stock oil, and add the graphite granule be dispersed in catalytically cracked oil wherein, 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
2by clean for the air displacement in stainless steel reactor, and make the pressure in stainless steel reactor maintain 0.15Mpa, stainless steel reactor is made to be warming up to 495 DEG C with the speed of 50 DEG C/min, react 8 hours at this temperature, collect gas and the liquid of reaction generation, the weight of silica tube PetroChina Company Limited. Jiao is weighed after the cooling of question response device, gaseous product gas chromatographic analysis is to determine its composition and calculated yield, product liquid is through weighing and calculated yield, deduct the amount of added catalytically cracked oil in liquid yield, in refinery coke, deduct the amount of added graphite granule.Sulphur content Infrared Carbon and Sulphur Determination instrument in refinery coke is analyzed, and experimental result is in table 2.
Embodiment 15
20g stock oil is joined in silica tube, and adding the neodymium modified carbon black particle prepared by embodiment 1 be dispersed in catalytically cracked oil wherein, 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, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, make stainless steel reactor be warming up to 480 DEG C with the speed of 50 DEG C/min, 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 the lanthanum modified graphite particle prepared by embodiment 2 be dispersed in catalytic cracking recycle oil wherein, the add-on of lanthanum modified graphite particle is 1.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 440 DEG C with the speed of 50 DEG C/min, 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 the praseodymium modified graphite particle prepared by embodiment 3 be dispersed in fluid catalytic cracking decant oil wherein, the add-on of praseodymium modified graphite particle is 3.0% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 480 DEG C with the speed of 50 DEG C/min, 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 the cerium modified graphite granule prepared by embodiment 4 be dispersed in catalytically cracked oil wherein, the add-on of cerium modified graphite granule is 1.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 465 DEG C with the speed of 50 DEG C/min, 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 the praseodymium modified carbon black particle prepared by embodiment 5 be dispersed in wax tailings wherein, 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, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, make stainless steel reactor be warming up to 495 DEG C with the speed of 50 DEG C/min, 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 the cerium modified graphite granule prepared by embodiment 4 be dispersed in hydrogenation tail oil wherein, the add-on of cerium modified graphite granule is 1.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 495 DEG C with the speed of 50 DEG C/min, 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 the cerium modified carbon black pellet prepared by embodiment 6 be dispersed in catalytically cracked oil wherein, 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, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, make stainless steel reactor be warming up to 495 DEG C with the speed of 50 DEG C/min, 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 the rubidium modified graphite particle prepared by embodiment 7 be dispersed in hydrogenation tail oil wherein, the add-on of rubidium modified graphite particle is 1.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 505 DEG C with the speed of 50 DEG C/min, 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 the lanthanum modified graphite particle prepared by embodiment 8 be dispersed in fluid catalytic cracking decant oil wherein, the add-on of lanthanum modified graphite particle is 1.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 525 DEG C with the speed of 50 DEG C/min, 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 the vanadium modified graphite particle prepared by embodiment 9 be dispersed in mixing heavy arene wherein, the add-on of vanadium modified graphite particle is 2.0% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 515 DEG C with the speed of 50 DEG C/min, 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 the lanthanum modified carbon black particle prepared by embodiment 10 be dispersed in catalytically cracked oil wherein, 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, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, make stainless steel reactor be warming up to 495 DEG C with the speed of 50 DEG C/min, 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 the cerium modified graphite granule prepared by embodiment 11 be dispersed in wax tailings wherein, the add-on of cerium modified graphite granule is 0.5% of stock oil weight, stirs, 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, make stainless steel reactor be warming up to 515 DEG C with the speed of 50 DEG C/min, 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 the vanadium modified carbon black particle prepared by embodiment 12 be dispersed in catalytically cracked oil wherein, 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, uses N
2air displacement in stainless steel reactor is clean, and make the pressure in stainless steel reactor maintain 0.15Mpa, make stainless steel reactor be warming up to 485 DEG C with the speed of 50 DEG C/min, 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 soaked, being dissolved or dispersed in by wetting carbonaceous particle is dispersed with in the dispersion agent of modified material, then dispersed with stirring agent 3 ~ 5 hours at normal temperature or 50 ~ 80 DEG C, leave standstill 18 ~ 24 hours, at 120 ~ 150 DEG C, drying 2 ~ 4 hours, is deposited on carbonaceous particle by the metallic element in modified material, under nitrogen protection finally, in retort furnace, roasting 3 ~ 5 hours at 450 ~ 560 DEG C, obtains modification carbonaceous particle;
2) preparation of modification carbonaceous particle dispersion: by step 1) in obtained modification carbonaceous even particulate dispersion in dispersed oil, obtain modification carbonaceous particle dispersion;
3) pyrogenic reaction: by step 2) in obtained modification carbonaceous particle dispersion add in stock oil, stir, carry out pyrogenic reaction, reaction pressure 0.1 ~ 0.2Mpa, temperature of reaction 420 ~ 550 DEG C;
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 μm;
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, with carbonaceous particle total weight before modified;
Described dispersion agent is water, alcohols or hydro carbons;
Described dispersed oil is 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 DEG C.
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 μm.
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. the delayed coking method according to Claims 2 or 3, 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 content of lanthanum in modification carbonaceous particle are 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210271381.8A CN103571516B (en) | 2012-07-25 | 2012-07-25 | A kind of delayed coking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103571516A CN103571516A (en) | 2014-02-12 |
| CN103571516B true CN103571516B (en) | 2015-09-23 |
Family
ID=50044237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210271381.8A Active CN103571516B (en) | 2012-07-25 | 2012-07-25 | A kind of delayed coking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103571516B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-07-25 CN CN201210271381.8A patent/CN103571516B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103571516A (en) | 2014-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101927167B (en) | Compound coal tar hydrogenation catalyst and preparation method thereof | |
| CN107754818B (en) | A kind of hydrocracking catalyst for suspension bed and preparation method | |
| CN104946306B (en) | A kind of full fraction of coal tar floating bed hydrocracking and fixed bed hydrogenation modification combined method | |
| CN102453534B (en) | Method for producing gasoline and diesel oil through hydrogenation of coal tar | |
| CN104907078B (en) | A kind of hydrogenation catalyst and its preparation method and application | |
| WO2014117309A1 (en) | Liquid-phase hydrogenation reaction method for multi-stage hydrogen dissolution | |
| CN111644208B (en) | Preparation method and application of oil-soluble suspension bed hydrogenation catalyst | |
| CN103571516B (en) | A kind of delayed coking method | |
| CN101301616B (en) | Method for preparing and using coal-tar pitch hydrocracking oil production pretreatment catalyst | |
| CN111468097B (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN108579777B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN102041047A (en) | Heavy oil hydrogenation modifying method | |
| CN106883871A (en) | A kind of production method of needle-shape coke raw material | |
| CN1903434A (en) | Catalyst for modifying faulty gasoline, preparing method and application thereof | |
| CN105713647B (en) | A kind of utilization coal tar maximization prepares the method and device of carbolic oil and diesel oil | |
| CN102989486B (en) | Heavy-oil hydrogenation modifying catalyst and preparation method thereof and heavy oil hydrogenation modifying method | |
| CN102559260A (en) | Rear inferior gasoline fraction hydrotreating method for heating furnace | |
| CN106281449A (en) | A kind of coal tar produces light Fuel and the method and system of needle coke | |
| CN1123633C (en) | Hydrogenating process for reducing viscosity of heavy oil or residual oil | |
| CN102816598B (en) | Method for decreasing carbon deposits on carbon residue removing catalyst of residual oil hydrotreater | |
| CN102989495B (en) | A kind of heavy-oil hydrogenation modifying catalyst and preparation method thereof and heavy oil hydrogenation modifying method | |
| CN1244669C (en) | Activating additive for delayed coking and cracking heavy oil and preparing method thereof | |
| CN107841336B (en) | A kind of heavy oil floating bed hydrocracking method | |
| CN101993740A (en) | Method for producing diesel by hydrogenating anthrancene oil | |
| Sukandar et al. | Effect of Additional Polyethylene Glycol and Citric Acid on Characteristics of NiMo/g-Al2O3 Catalyst in Light Cycle Gas Oil Hydrodesulfurisation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |