CN1954046A - Delayed coking process for producing free-flowing coke using polymeric additives - Google Patents
Delayed coking process for producing free-flowing coke using polymeric additives Download PDFInfo
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Abstract
A delayed coking process for making substantially free-flowing coke, preferably shot coke. A coker feedstock, such as a vacuum residuum, is heated in a heating zone to coking temperatures then conducted to a coking zone wherein volatiles are collected overhead and coke is formed. A low molecular weight additive is added to the feedstock prior to it being heated in the heating zone, prior to its being conducted to the coking zone, or both.
Description
Invention field
The present invention relates to a kind of delayed coking method that is used to produce fundamental freedom mobile coke, preferred free flowing granule shape coke (shot coke).In the heating zone, coking furnace charging (as vacuum residuum) is heated to coking temperature, imports the coking district subsequently, wherein collect volatile matter and form coke at the top.Before in the heating zone, heating, before the importing coking district or before the two, the suitable polymer blend additive is added in the charging, to strengthen the formation of free-flowing coke.
Description of Related Art
Delayed coking comprises gas, liquid stream and the coke of thermolysis to generate various boiling ranges of petroleum residue (residual oil).By part residual oil being converted into more valuable liquid and gas products, postpone to use mainly as a kind of method that is used for these low value chargings of waste treatment from the residual oil in coking heavy and heavy acid (high-sulfur) crude oil.Though the coke that obtains is considered to the by product of low value usually, it can have some value, can be used as fuel (fuel grade coke), is used to generate the electrode (anode level coke) of aluminium etc. according to its quality.
In delay coking process, rapid heating charging in fired heater or tube furnace.Subsequently the charging of heating is led to and maintain in the coking drum that produces under the pyrogenic condition, typical temperature is higher than 400 ℃ and be higher than under the atmospheric pressure.The resid feed of the heating in the coking drum also forms volatile component, and volatile component removes and lead to separation column at the top, remaining coke.When the coking drum was full of coke, the charging of heating switched in another drum, and hydrocarbon vapour blows out from the coking drum with steam.Water quenching subsequently should be roused so that temperature is reduced less than 300 (149 ℃), drainage water afterwards.When cooling and drain step end, use the high speed water injection to bore and/or cut and open drum discharge coke afterwards.
Usually use and portal from the coke beds center drill from the high-pressure water jet that is positioned at the nozzle on the drill tools.The nozzle of the head horizontal alignment of parting tool cuts out coke from this drum subsequently.Coke excision step has increased the time of passing through and the cost of whole technology considerably.Therefore, expectation can be produced free-pouring coke in the coking drum, need not and common relevant expense and the time of coke excision.
Even the coking drum can be rendered as fully and be cooled, but the subregion of this drum can thoroughly not cooled off.This phenomenon also is known as " heat drum " sometimes, and this may be the result of combination who has the coke of variform in the drum, and it can contain more than one type solid coke product combination, just needle coke, sponge coke and particulate state coke.Because the particulate state coke of reuniting can be than the faster cooling of other form coke (as bigger particulate state coke mass or sponge coke), should be desirably in the delay coking stove to produce and be mainly fundamental freedom mobile coke, preferred particulates shape coke, to avoid or minimum heat-transmission drum.
Summary of the invention
In one embodiment, provide a kind of delayed coking method, it comprises:
(a) but in first heating zone, petroleum residual oil is heated to and is lower than coking temperature but residual oil is the temperature of pumping liquid under this temperature;
(b) residual oil with described heating imports in second heating zone that is heated coking temperature;
(c) residual oil with described heating imports the coking district from described second heating zone, wherein collects vapor product at the top and forms solid coking product; With
(d) introduce at least a effective polymeric additive of formation for fundamental freedom mobile coke in described residual oil, wherein in the upstream of second heating zone selects, between described second heating zone and the described coking district one selects or two places introduce described polymeric additive in the described residual oil.
In a preferred embodiment, the coking district is in delayed coker drum, and formation fundamental freedom mobile particulate state coke produced.
In another embodiment, provide a kind of delayed coking method, it comprises:
(a) be under 70 ℃～370 ℃ in temperature, vacuum residuum is contacted with at least a polymeric additive of significant quantity to be enough to this additive is distributed to time in the charging substantially equably;
(b) vacuum residuum with contact is heated to the significant temp of the described charging of coking;
(c) vacuum residuum of described heating being loaded into pressure is 15～80psig (the significant quantity time that hot coke beds is formed, this hot coke beds unrestricted flow of at least a portion; With
(d) this hot coke beds of water quenching at least a portion.
In another embodiment, polymeric additive is selected from the ethylenediamine tetraacetic alcohol alcoxylates of polyoxyethylene, polyoxypropylene, polyoxyethylene-polyoxypropylene multipolymer, Volpo S 10, the ethylenediamine tetraacetic alcohol alcoxylates of polyoxypropylene alcohol, ethylenediamine tetraacetic alcohol alcoxylates and its mixture of polyoxyethylene-polyoxypropylene alcohol.The polymeric additive molecular weight is preferably 1,000～30, and 000, more preferably 1,000～10,000.Multipolymer is preferably segmented copolymer.In Fig. 1 and 2 of the application, provided the illustrative example of this polymkeric substance.
In another embodiment, form fundamental freedom mobile particulate state coke produced, and from the coking district, shift out.The coking district is preferably delayed coker drum.Can be incorporated into heating zone (it is coking furnace) in charging and mix with the additive introducing and with charging before, perhaps can between coking furnace and coking drum, be introduced in the charging.Within the scope of the invention, be that additive is all introduced in the charging at two places also.Can add same additives or multiple additives in each position independently; Perhaps can add different additive or multiple additives in each position.
The term " combination " that uses is got its broad sense with " contact ", just in some cases, when having additive in the charging in additive, charging or the physics and/or the chemical transformation of additive and/or charging can take place in the two.In other words, the present invention is not restricted to additive wherein and/or charging after contact and/or combination or the situation of chemistry and/or physical change do not take place during it." significant quantity " of additive will be for causing forming the additive amount of free-pouring coke, preferred fundamental freedom mobile particulate state coke in the coking district when contacting with charging.The common scope of significant quantity is 100～100,000ppm (based on the charging gross weight).Certainly, consumption depends on employed special additive kind and its chemistry and physical aspect.For the additive materials of disperseing better physics and chemical species in being in charging, to compare with more being difficult to those additive materials of dispersive, significant quantity is littler usually.Therefore, most preferably be partially dissolved at least organism, more preferably be dissolved in additive in the resid feed.
Expectation is distributed to additive in the resid feed equably, with the heterogeneous body zone of avoiding coke morphology to form.That is, do not wish in coking drum, to have such position, in the basic unrestricted flow of this coke and coke not unrestricted flow substantially in other zone.Realize the dispersion of additive by the technology of any suitable, preferably the effluent of additive is introduced in the charging by position in expectation.Can add this additive in the resid feed by additive is dissolved in.The viscosity (for example by heating, interpolation solvent etc.) that reduced residual oil before sneaking into additive will promote that additive is dissolved in the resid feed.Can utilize high energy to mix or use static mixing equipment to participate in additive, especially in incoming flow, have a dispersion of the additive of relative low solubility.
Preferably, the whole or basic whole coke that form in the methods of the invention are fundamental freedom mobile coke, fundamental freedom mobile particulate state coke more preferably.Also preferably, during coke forms and afterwards, at least a portion is present in volatile matter in the coking drum from this method, separates and derive, preferably carry out at the bulging top of this coking.
Description of drawings
The application Fig. 1 does not wherein use additive for the light micrograph of the residual oil of demonstration the embodiment of the present application.
The application Fig. 2 has wherein used polyoxyethylene-polyoxypropylene (Pluronic) additive for the light micrograph of the residual oil of demonstration the embodiment of the present application.
The application Fig. 3 is the light micrograph of the residual oil of demonstration the embodiment of the present application, has wherein used ethylenediamine tetraacetate (Tetronic) additive of Volpo S 10.
It is 170 * 136 microns cross polarization light opticmicroscope that whole Photomicrographs among these figure have used viewing area.
Detailed Description Of The Invention
The charging that is applicable to delayed coking is oil decompression residue (" residual oil "). Such petroleum residue obtains usually under reduced pressure remove distillation from crude oil feeding after, and it is characterized in that being formed by the component of large molecular dimension and molecular weight, generally contain: (a) asphalitine and other HMW aromatic structure, it will suppress the speed of hydrotreatment and/or hydrocracking and cause catalysqt deactivation; (b) metal pollutant naturally occurring in the crude oil or that from the crude oil pre-treatment, obtain, this pollutant tends to make hydrotreatment and/or hydrocracking catalyst inactivation and affects catalyst regeneration; (c) sulphur and the nitrogen compound of relative high-load, it produces the SO of unfavorable amount when the burning petroleum residue2、SO
3, and NOx The nitrogen compound that exists in the residual oil also tends to make the catalytic cracking catalyst inactivation.
In one embodiment, resid feed is including but not limited to the tar in the residue in normal pressure or decompression distillation crude oil or normal pressure or the decompression distillation heavy oil, visbroken resids, coal slurry, shale oil, the depitching unit or the combination of these materials. Also can use normal pressure and decompression topping heavy asphalt. Usually, this charging is high boiling hydrocarbon material, and the bubble point that rises of demarcation is that about 538 ℃ or higher, api gravity are that 20 ° or less, Kang Laxun carbon residue content are 0～40wt%.
Usually resid feed is carried out delayed coking. Usually, in delayed coking, it is that (in the heater under 344.74～3792.12kPa), wherein be heated to temperature is 480 ℃～520 ℃ to 50～500psig that residue oil fraction (such as the petroleum residue charging) is pumped into pressure. Subsequently its entrance by the drum end is discharged into the coking district, is generally in the adiabatic coking drum of vertical orientation. Pressure is usually relatively low in the drum, as 15～80psig (103.42～551.58kPa), remove at the top can make volatile matter. The typical operation temperature of drum is 410 ℃～475 ℃. Hot feed is thermal cracking a period of time (" scorch time ") in the coking drum, discharges the volatile matter that mainly is comprised of hydrocarbon products, and it rises continuously by coke mass (bed) and at the top it is collected. Volatile products are delivered to distill in the coking fractionator and reclaim coking gas, naphtha, lightweight gas oil and heavy gas oil cut. In one embodiment, fraction can be present in heavy coker gas oil in the product stream of introducing in the coking fractionator collects and circulates, and with fresh feed (coker feed component) combination, form thus coker heater or coking furnace charging. Except volatile products, delayed coking also forms the solid coke product.
Three kinds of dissimilar solid delay coking device products are arranged usually, and they have different value, outward appearance and performance, namely needle coke, sponge coke and graininess coke. Needle coke is top-quality in the three types. Needle coke has high conductance (with low thermal coefficient of expansion) when further heat treatment, and is used for the production of electric arc steel. The content of its sulphur and metal is relatively low, and usually produces from some more high-quality coker feed, and this charging comprises more aromatic feed, such as the tar of the slurry in the cat cracker and decanted oil and thermal cracking. Usually, can not form this product by the delayed coking resid feed.
Sponge coke (a kind of more inferior coke) forms in refinery usually. Inferior refinery coker feed has a large amount of asphalitines, hetero atom and metal, and it generates this more inferior coke. If the content of sulphur and metal is enough low, sponge coke can be for the production of the electrode in the aluminium industry. If the content of sulphur and metal is too high, coke can be used as fuel so. Title " sponge coke " comes from the outward appearance of its porous spongy. The conventional delayed coking method of the preferred vacuum resid feed of use the present invention can generate the sponge coke of aggregation substance usually, and it need to comprise the strong process of removing of brill and water-jet technology. As discussed above, make the method very complex circulation timei owing to having increased.
The graininess coke is considered to the coke of lowest quality. Term " graininess coke " derives from its shape that is similar to BB size [about 1/16 inch to 3/8 inch (.16cm～.95cm)] ball. The graininess coke is the same with other type coke to tend to be gathered into relatively large (especially with the mixture of sponge coke in), and diameter is greater than 1 foot sometimes. Can cause like this problem of refinery's equipment and processing aspect. The graininess coke makes from the high resin asphalitine charging of lowest quality usually, and obtains especially for the good high-sulfur combustor of cement kiln and steel production former. Also have other coke, it is known as " transition coke (transition coke) ", and the expression form is between sponge coke and graininess coke or owing to the coke of compositions of mixtures of the graininess coke that combines sponge coke. For example, mainly have the physical appearance that is similar to sponge, but have little particulate ball to begin to form the coke of the sign of discrete shape.
According to the present invention, by processing resid feed with one or more polymeric additives, can make basic free flowing granule shape coke. This additive is those that enhancing graininess coke generates during delayed coking. Under effective temperature, namely will promote to process resid feed with one or more additives under the temperature that additive disperses in charging. This temperature is generally 70 ℃～500 ℃, is preferably 150 ℃～370 ℃, more preferably 185 ℃～350 ℃.
The non-limiting example of polymeric additive of the present invention comprises those that are selected from following material: ethylenediamine tetraacetic alcohol alcoxylates and its mixture of the ethylenediamine tetraacetic alcohol alcoxylates of polyoxyethylene, polyoxypropylene, Pluronic F68, polyoxyethylene alcohol, the ethylenediamine tetraacetic alcohol alcoxylates of polyoxypropylene alcohol, PULLRONIC F68 alcohol.
Use this polymeric additive with effective dose. That is, consumption is at least the amount of the free-flowing coke that obtains expected degree. This consumption is generally 300～500wppm, be preferably 300～3000wppm and 300～2000wppm more preferably, based on the weight of heavy oil feed.
Within the scope of the present invention, additive and the polymeric additive of the second type can be used in combination. The additive of this second type is can be with the metallic additive of liquid or solid form use, preferred liquid form. The non-limiting example of the metallic additive that can use in the invention process comprises metal hydroxides, naphthenate and/or carboxylate, metal acetylacetonates, lewis acid, metal sulfide, metal acetate, metal carbonate, metallic high surface area solids, the salt of inorganic oxide and oxide. The preferable alloy of hydroxide is alkali and alkaline earth metal ions, more preferably potassium and sodium. Preferred basic salt. If metallic additive and polymeric additive are used in combination, the total amount of two kinds of additives should not surpass for the given research on maximum utilized quantity of polymeric additive, namely is 5000wppm to the maximum.
Preferably the cut with 900 (482.22 ℃)～1040 (560 ℃) normal pressure boiling point (AEBP) material of equal value remains under the 10wt%, will promote the coke morphology that coke morphology is got back to less combination and less self-supporting like this.
The initial liquid spheres that causes forming the graininess coke that forms of the rapid draing/coking of phase (mesophase)/division forms in the middle of the liquid. Being on good terms in the middle of slowly dry scatter and on the spot coking in the middle of making initial liquid mutually, and causes forming the extended network of sponge coke. Medium dry speed is produced as the transition coke of the mixture of spongy and graininess coke, and wherein the graininess coke embeds in the sponge coke. When the sealer that forms embedded particles shape coke and superheated vapor owing to sponge coke cut/bore the coking drum of delayed coking, rear a kind of situation can cause coke outburst or " heat drum ". When the bit hits sealing, it relates to steam and graininess coke BB. Very expectation can be produced particulate or sponge coke with controlled manner, and avoids forming transition coke. Refinery can need not to bore and just cut out sponge coke or discharge the graininess coke. Add polymeric additive of the present invention coking is carried out under higher temperature, because its heat cross-linking that has slowed down between the middle phase layer reacts, allow quickly dry coke and formation graininess coke ball. Except higher temperature, can allow the volatility crackate to overflow at the lower operation of lower pressure (for example 15psi vis 45psi (103.42 vis 310.26kPa)) coking drum, and make they as liquid in the centre time of staying in mutually minimum. The polyethers additive disturb form mutually in the middle of the mink cell focus and crosslinked aspect also be effectively because they in the coking drum with the speed decomposition (usually 425 ℃ under) slower than coke rate of drying.
Accurate condition during with the additive treating resid feed depends on charging and additive. That is the condition during, with the additive treating charging depends on the charging for the treatment of coking and composition and the performance of additive therefor. Can determine these conditions according to routine. For example, can pass through coking in mini-reactor (such as Mirocarbon Residue Test Unit (MCRTU)), under different time and temperature, operate several times with the specific charging that contains additive. The coke that obtains is analyzed in subsequently utilization herein described optical crossover polarization microscope. Preferred coke morphology (namely, to generate the coke of basic free fluid) for average-size is 0.5～10 μ m, is preferably the coke micro-structural of the discrete film micro area of 1～5 μ m, be similar to a certain extent the mosaic described in the application Fig. 2 and 3 (mosaic). Shown the coke micro-structural that represents non-free flowing granule shape coke among the application Fig. 1, the coke micro-structural of demonstration mainly is comprised of non-discrete or larger basin, size up to 60 μ m or larger, be generally 10～60 μ m.
Also can use coking processing aid commonly used in the inventive method, comprise defoamer. When by conventional method production graininess coke, the graininess coke gathers usually still needs water-jet technology with its degree that shifts out.
In one embodiment of the invention, at first with promoting the polymeric additive of the present invention that forms substantially free-pouring coke to process resid feed. By keeping the coking drum under relatively low pressure, can collect at the top a large amount of volatile matters that form, the gathering of the graininess coke that obtains that has suppressed not expect. Combined feed is the volume ratio of the fresh feed of furnace charge (fresh feed+recycle oil) and continuous delayed coking operation than (" CFR "). Delayed coking operation adopts the circulation of 5 volume %～25 volume % (CFR is 1.05～1.25) usually. Sometimes be 0 circulation, sometimes in application-specific, circulate up to 200%. Should reduce CFR helping forming free flowing granule shape coke, and preferably not use circulation.
Usually, with continuous mode additive is imported in the coking process. If necessary, additive can be dissolved in the suitable transfering fluid or form therein slurry, this fluid is generally and additive compatible with residual oil and substantially dissolves in wherein solvent. With the speed that in charging, realizes desired additive concentration fluid mixture or slurry pump are delivered in the coking process subsequently. The introducing position of additive can be for example in the exit of stove charging charge pump or near the outlet of coker conveyer line. Can have a pair of mixer, this operates in the mode that additive is incorporated in the coking process continuously mixer.
Can regulate the introducing speed of additive according to the kind of resid feed in the coking furnace.Charging can be than needing less additive away from the charging in the ultimate value in the ultimate value of production particulate state coke.
For the additive that is difficult to be dissolved or dispersed in the resid feed, additive is transferred in mixing/slurry container, and mixed with the slurry medium compatible with charging.The non-limiting example of suitable slurry medium comprises coker heavy gas oil, water etc.Can for example in container, provide energy to disperse this additive by mixing tank.
For the additive that can be dissolved or dispersed in comparalive ease in the resid feed, additive is transferred in the mixing vessel, and mixed with the fluid transfer medium compatible with charging.The non-limiting example of suitable fluid transfer medium comprises warm sludge oil (temperature is 150 ℃～300 ℃), coker heavy gas oil, light cycle, heavy reformate and its mixture.Also can use catalysis slurry oil (cat slurry oil) (CSO), although it may suppressant additive generates the ability of discrete particle shape coke in some cases.Can for example in container, provide energy to disperse this additive by mixing tank.
The present invention may be better understood with reference to the following indefiniteness embodiment that provides for purposes of illustration.
Embodiment
Use is set forth the present invention from Tetronic and Pluronic polymkeric substance that BASF Corporation obtains.These polymkeric substance are the multipolymer of oxyethane and propylene oxide.The molecular-weight average of every kind of polymeric additive is 1500.
Polymeric additive shown in below using in the present embodiment.These polymkeric substance are the multipolymer and the commercially available acquisition of oxyethane and propylene oxide.Left side additive is the Tetronic multipolymer, and the right additive is the Pluronic copolymer additives, obtains from BASF Corporation.The molecular-weight average of every kind of polymeric additive is 1500.
2g Baton Rouge Refinery Vacuum Tower Bottoms is fed among the Microcarbon Reactor Test Unit (MCR).With residual oil be heated to 400 ℃ and remain on 400 ℃ following 2 hours, the gravimetric analysis residue.Add two kinds of above-mentioned polymeric additives of 3000wppm and operate residual oil once more.The polarized light optical microphotograph that carries out residue detects.Following table has shown this result.
Table
| Additive | Residual oil (g) | Additive, mg | Additive (wppm) | R.T. to 400 ℃ and kept 4 hours |
| Do not have | 4.52 | ----- | ----- | 27.38 |
| Pluronic F-108 | 4.20 | 12.80 | 3048 | 26.90 |
| Tetronic 1508 | 4.63 | 13.90 | 3002 | 27.39 |
The application Fig. 1,2 and 3 Photomicrograph have shown this microscopic analysis result, and it has confirmed the effect of polymeric additive of the present invention.Fig. 1 is for non-additive result and can observe the spheroid of many lights, and it shows and has a large amount of anisotropy coke.Fig. 2 represents use polyoxyethylene-polyoxypropylene (Pluronic) and the operation carried out, wherein observes with respect to Fig. 1 to have less relatively microballoon, shows the formation that has suppressed the anisotropy coke thus.The application Fig. 3 represents the ethylenediamine tetraacetic alcohol alcoxylates (Tetronic) of use polyoxyethylene-polyoxypropylene alcohol and the operation carried out, wherein observes to have isotropic phase, and it shows the formation that has suppressed the anisotropy coke substantially up hill and dale.Thus, polymeric additive of the present invention has suppressed the formation of anisotropy coke and has changed coke morphology.
Claims (10)
1, a kind of delayed coking method comprises:
(a) but in first heating zone, petroleum residual oil is heated to and is lower than coking temperature but residual oil is the temperature of pumping liquid under this temperature;
(b) residual oil with described heating imports in second heating zone that is heated coking temperature;
(c) residual oil with described heating imports the coking district from described second heating zone, wherein collects vapor product at the top and forms the coking product; With
(d) introduce at least a effective polymeric additive of formation for fundamental freedom mobile coke in described residual oil, wherein in the upstream of second heating zone selects, between described second heating zone and the described coking district one selects or two places introduce described polymeric additive in the described residual oil.
2, a kind of delayed coking method comprises:
(a) be under 70 ℃～370 ℃ in temperature, vacuum residuum is contacted with at least a polymeric additive of significant quantity to be enough to this reagent is evenly spread to time in the charging;
(b) residual oil is heated to the significant temp of the described charging of coking;
(c) vacuum residuum of described heating being loaded into pressure is 15～80psig (scorch time that hot coke beds is formed, this hot coke beds unrestricted flow of at least a portion; With
(d) this hot coke beds of water quenching at least a portion.
3, each method in the aforementioned claim, wherein resid feed is a vacuum residuum.
4, each method in the aforementioned claim, wherein this additive of at least a portion dissolves in charging.
5, each method in the aforementioned claim, wherein the significant quantity of additive is 300～5,000wppm.
6, each method in the aforementioned claim, wherein polymeric additive is selected from the ethylenediamine tetraacetic alcohol alcoxylates of polyoxyethylene, polyoxypropylene, polyoxyethylene-polyoxypropylene multipolymer, Volpo S 10, the ethylenediamine tetraacetic alcohol alcoxylates of polyoxypropylene alcohol, pure and mild its mixture of ethylenediamine tetraacetic alkoxylate of polyoxyethylene-polyoxypropylene alcohol.
7, each method in the aforementioned claim, wherein the polymeric additive molecular weight is 1,000～30,000.
8, each method in the aforementioned claim, wherein the coke that is generated is the particulate state coke substantially.
9, each method in the aforementioned claim, wherein also use second additive of significant quantity, wherein second additive is metallic additive, and it is selected from the salt of one or more metal ring alkyl salts, metal acetylacetonates, Lewis acid, metallic high surface area material, inorganic oxide and inorganic oxide.
10, each method in the aforementioned claim, wherein second additive is one or more in KOH, NaOH, carboxylate salt and the acetylacetonate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/846,034 US7303664B2 (en) | 2003-05-16 | 2004-05-14 | Delayed coking process for producing free-flowing coke using a metals-containing additive |
| USPCT/US2004/015319 | 2004-05-14 | ||
| US10/846,034 | 2004-05-14 | ||
| PCT/US2004/015319 WO2004104139A1 (en) | 2003-05-16 | 2004-05-14 | Delayed coking process for producing free-flowing shot coke |
| PCT/US2005/016714 WO2005113712A1 (en) | 2004-05-14 | 2005-05-12 | Delayed coking process for producing free-flowing coke using polymeric additives |
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| Publication Number | Publication Date |
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| CN1954046A true CN1954046A (en) | 2007-04-25 |
| CN1954046B CN1954046B (en) | 2011-08-10 |
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| CN 200580015512 Pending CN1954048A (en) | 2004-05-14 | 2005-05-12 | Delayed coking process for producing free-flowing coke using low molecular weight aromatic additives |
| CN2005800154051A Expired - Fee Related CN1954046B (en) | 2004-05-14 | 2005-05-12 | Delayed coking process for producing free-flowing coke using polymeric additives |
| CN 200580015561 Pending CN1954051A (en) | 2004-05-14 | 2005-05-12 | Delayed coking process for producing free-flowing coke using an overbased metal detergent additive |
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| CN103797089A (en) * | 2011-09-14 | 2014-05-14 | 西格里碳素欧洲公司 | Production of carbon fibre-reinforced coke |
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| US8496805B2 (en) * | 2009-07-10 | 2013-07-30 | Exxonmobil Research And Engineering Company | Delayed coking process |
| US9139781B2 (en) * | 2009-07-10 | 2015-09-22 | Exxonmobil Research And Engineering Company | Delayed coking process |
| CN110734779B (en) * | 2019-10-15 | 2021-03-05 | 湖南中科星城石墨有限公司 | Isotropic coke suitable for lithium ion battery cathode raw material and preparation method thereof |
| CN112779038B (en) * | 2021-01-19 | 2022-02-18 | 山西沁新能源集团股份有限公司 | Preparation method of special coke for ceramic fiber vertical melting furnace, special coke for ceramic fiber vertical melting furnace and application of special coke |
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| US4612109A (en) * | 1980-10-28 | 1986-09-16 | Nl Industries, Inc. | Method for controlling foaming in delayed coking processes |
| US5258115A (en) * | 1991-10-21 | 1993-11-02 | Mobil Oil Corporation | Delayed coking with refinery caustic |
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| CN103797089A (en) * | 2011-09-14 | 2014-05-14 | 西格里碳素欧洲公司 | Production of carbon fibre-reinforced coke |
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| CN1954046B (en) | 2011-08-10 |
| BRPI0511023B1 (en) | 2016-03-29 |
| CN1954051A (en) | 2007-04-25 |
| BRPI0511019A (en) | 2007-11-27 |
| BRPI0511045A (en) | 2007-11-27 |
| JP2008504375A (en) | 2008-02-14 |
| BRPI0511023A (en) | 2007-11-27 |
| JP2008504376A (en) | 2008-02-14 |
| JP2008502743A (en) | 2008-01-31 |
| CN1954048A (en) | 2007-04-25 |
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