CN1954051A - Delayed coking process for producing free-flowing coke using an overbased metal detergent additive - Google Patents

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. An overbased alkaline earth metal detergent 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

Use overbased metal detergent additive to produce the delayed coking method of free-pouring coke

Invention field

The present invention relates to the free-pouring basically coke of preparation, the delayed coking method of preferred shot coke.Arrive coking temperature at heating zone heating coking charge ratio such as vacuum resid, introduce the coking district then,, and form coke wherein at the overhead collection volatile matter.Before described charging is heated in described heating zone, before the coking district is introduced in described charging, or two places, overbasic alkaline-earth metal cleaning additive is added described charging.

The explanation of correlation technique

Delayed coking relates to thermolysis petroleum residue (Residual oil), to produce gas, the liquid stream of various boiling ranges, and coke.Carrying out the Residual oil delayed coking from heavy crude or heavy acid (high sulfur content) crude oil, mainly is as a kind of mode of handling these low value raw materials by the part Residual oil being converted into valuable liquid more or gas products.Although the coke that obtains is considered to the low value byproduct usually, depend on that its grade acts as a fuel (fuel grade coke), the electrode (anode grade coke) of aluminium in making etc., it also can have some value.

In delayed coking method, in fired heater or tube furnace, heat described charging apace.The charging of described heating is sent to coking tower then, and it remains on and takes place under the pyrogenic condition, usually under superatmospheric pressure is higher than 400 ℃ temperature.The resid feed of the heating in the coking tower also forms volatile constituent, and it is removed at cat head, and is sent to fractionator, stays coke.When described coking tower was full of coke, the charging of described heating forwarded another tower to, removed the hydrocarbon vapour of coking tower with steam.The described tower of water quenching is lower than 300  (149 ℃), draining afterwards to cool to then.When cooling and drain step are finished, remove described coke after opening tower and using high velocity water jets brill and/or cutting.

For example, usually use the spray nozzle that is positioned on the boring bar tool to get out hole by the coke bed center.Nozzle flatly is orientated at the parting tool head, cuts coke then from tower.Coke is removed the production time that step increases whole process significantly.Therefore, hope can be produced free-pouring coke in coking tower, does not need to remove with conventional coke the expense and the time of decorrelation.

Even coking tower cools off well as if fully, but the cooling fully of the zone of tower.This ＂ thermal tower that is sometimes referred to as " phenomenon, can be the result of the form families of the coke that exists in the tower, it can contain the solid that surpasses a type burnt product combination, i.e. needle coke, sponge coke and shot coke.Because the coke ratio of accumulative shot coke and other forms such as bulk shot coke or sponge coke are not compared and can more promptly be cooled off, thus wish in delayed coking unit, mainly to produce free-pouring basically shot coke, to avoid or to minimize thermal tower.

Summary of the invention

In one embodiment, provide delayed coking method, comprising:

(a) but in first heating zone heating fuel oil residuum be the temperature of pumping liquid still to being lower than coking temperature to Residual oil wherein;

(b) Residual oil of described heating is introduced second heating zone, wherein be heated coking temperature;

(c) Residual oil of described heating is introduced the coking district from described second heating zone,, and form coke product wherein in the overhead collection vapor product;

(d) will introduce described Residual oil for forming the effective at least a overbasic alkaline-earth metal detergent additive of free-pouring basically coke, wherein described containing metallic additive be introduced described Residual oil in the position at upstream, second heating zone, upstream, described coking district or two places.

In a kind of preferred embodiment, the coking district is in delayed coking drums, and the free-pouring basically shot coke product of formation.

In another embodiment, provide delayed coking method, comprising:

(a) under 70 ℃～370 ℃ temperature, make vacuum resid contact time enough, so that described reagent is dispensed into described charging equably with at least a overbased metal detergent additive of significant quantity;

(b) Residual oil of the described processing of heating is to the temperature of the described charging of effective coking;

(c) described heat treated Residual oil is fed to (the coking district under 103.42～551.58kPa) pressure reaches scorch time to form hot coke bed at 15～80psig; With

(d) water quenching is to the described hot coke bed of small part.

In another embodiment, form free-pouring basically shot coke product and remove from described coking district.Described coking district is delayed coking drums preferably.Can be introduced into described heating zone (pit kiln) in described charging and mix with described additive introducing and with described charging before, perhaps between described pit kiln and coking tower, be introduced into described charging.Described additive is introduced into described charging also in category of the present invention in position, two places.Can add identical additive respectively in each position, or can add different additives in each position.

Term ＂ the mixings ＂ that uses contacts ＂ with ＂ and represents broad sense, when promptly additive is present in described charging, sometimes at described additive, described charging or physics and/or the chemical transformation in the described additive of generation and/or the charging among both.In other words, the present invention is not limited to after described contact and/or mixing or in its process, the situation of chemistry and/or physical change is not carried out in additive and/or charging.The additive of ＂ significant quantity ＂ is for causing in the coking district the preferably amount of additive during free-pouring shot coke basically of formation shot coke when contact with charging.Significant quantity is generally 100～100,000ppm (based on the gross weight of metal in described additive and the charging), but depend on the kind of additive and its chemical species and physical form.Without wishing to be held to any theory or model, it is believed that the significant quantity of the additive types that obtains better dispersive physics and chemical species in charging is lacked than the significant quantity of more difficult dispersive additive types.This is to be partially soluble in organism why, and the additive that more preferably is dissolved in the resid feed is most preferred reason.

Described additive homodisperse is gone into the heterogeneous zone that helps avoiding forming coke morphology in the resid feed.That is to say that the coke of not wishing the position that has in the coking tower is basic gravity flow, and other regional coke do not flow automatically substantially.The dispersion of additive realizes by many methods, preferably by in desired location the additive effluent being introduced described feed stream.Described additive can enter described resid feed adding by dissolving described additive, or by reduced the viscosity of described Residual oil before sneaking into described additive, for example by heat, adds addings such as solvent.Can use the dispersion of high energy mixing or static mixer supplementary additive, particularly in described feed stream, have those additives of relative low solubility.Preferably, the whole or all basically coke that form in the described method are free-pouring basically coke, more preferably free-pouring basically shot coke.Also preferred at least a portion is during coke forms or the volatile matter that exists in coking tower afterwards is separated and from technology, draw in the cat head of preferred coking tower.

The accompanying drawing summary

Fig. 1 is the light micrograph of the coke that shows that the resid feed (heavy Canadian Residual oil) by the preparation sponge coke that does not comprise additive forms.Described figure shows 10～15 microns flow region size (typical sponge coke), the mosaic pattern that 3～10 microns medium/coarse is rough (typical shot coke).

Fig. 2 shows the effect of use on coke morphology of calcium.Described figure also is a light micrograph, but shows by containing the coke that the Heavy Canadian Resid of 500ppm (0.05wt.%) with the calcium of the over-based detergent form of calcium sulphonate forms.Described figure only shows the mosaic pattern that 1～8 micron medium/coarse is rough.

Fig. 3 shows the effect of use on coke morphology of calcium.Described figure also is a light micrograph, but shows by containing the coke that the Heavy Canadian Resid of 500ppm (0.05wt.%) with the calcium of calcium salicylate over-based detergent form forms.Described figure only shows the mosaic pattern that 1～9 micron medium/coarse is rough.

Whole Photomicrographs use cross polarization light, 170 * 136 microns in the visual field among these figure.

Detailed description of the invention

Oil vacuum residue (＂ Residual oil ＂) charging is suitable for delayed coking. These petroleum residues are removed from crude oil material under vacuum often and are obtained after the distillate, it is characterized in that comprising the component of large molecular size and macromolecule, usually contain:

(a) suppress hydrotreatment/hydrocracking and so that the pitch of catalysqt deactivation and other aromatic structure of HMW more; (b) be present in natively metal impurities in the crude oil or that produced by the processing before the described crude oil, described pollutant is often so that hydrotreatment/hydrogenation cracking catalyst inactivation and affect catalyst regeneration; (c) during the burning of described fuel oil residue, produce the SO of harmful amount₂、SO ₃And NO_xSulphur and the nitrogen compound of relative high-load. The nitrogen compound that is present in described Residual oil also is easy to make the catalytic cracking catalyst inactivation.

In one embodiment, resid feed includes, but are not limited to, the normal pressure of the normal pressure of crude oil and vacuum distillation or heavy oil and the residue of vacuum distillation, visbreaking Residual oil, coal liquid, shale oil, the tar of depitching unit or the combination of these materials. Also can use normal pressure and the heavy asphalt vacuum topping. Usually, these chargings are high boiling hydrocarbon materials, have 538 ℃ or higher initial boiling point of nominal, and api gravity is 20 ° or less, and Conradson Carbon Residue content is 0～40wt%.

The common delayed coking of resid feed is processed. Usually, in delayed coking, residue cut such as petroleum residue raw material are pumped into heater under the pressure of 50-550psig (344.74-3792.12kPa), wherein it is heated to 480 ℃-520 ℃. Then the import via the tower bottom is discharged into it in coking district, normally the insulation coking tower of vertical direction. Pressure in the tower is usually relatively low, such as 15～80psig (103.42～551.58kPa), to remove volatile matter from cat head. The typical operating temperature of described tower is 410 ℃～475 ℃. During time in coking tower (＂ scorch time ＂), the feed heat cracking of described heat discharges the volatile matter that mainly is comprised of hydrocarbon products, and it rises by described charge of coke continuously, and in overhead collection. Described volatile products are sent to the distillation of coking fractionator and reclaim cooking gas, gasoline, light gas oil, and heavy gas oil. In one embodiment, the heavy coker gas oil of part that is present in the described product stream that is introduced into described coking fractionator can be hunted down, be used for circulating and mixing with described fresh feed (coking feed component), thereby form the charging of coking heater or coke oven. Except volatile products, delayed coking also forms the burnt product of solid.

Common three kinds of dissimilar solid delayed coking products have different value, outward appearance and performance, i.e. needle coke, sponge coke and shot coke. Needle coke is first water in described three kinds of variants. Needle coke in case further heat treatment has higher electric conductivity (with low thermal coefficient of expansion), is used for electric arc steelmaking. It has relatively low sulphur and tenor, and is usually made by the coking raw material of better quality, and this coking raw material comprises more aromatic raw material, the slurry attitude oil and decantation oil and the thermal cracking tar that are for example obtained by catalytic cracking unit. Usually, it does not form by the delayed coking of resid feed.

Sponge coke, a kind of than the low quality coke, often be formed at purifier. Produce these low-quality coke with the low quality purifier coking raw material with a large amount of pitches, hetero atom and metal. If sulphur and tenor are enough low, sponge coke can be used for the manufacturing of aluminium industry electrode. If sulphur and tenor are too high, described coke can be used as fuel. Title ＂ sponge coke ＂ is from the spongioid outward appearance of its porous. Use the common production sponge coke of delayed coking method of the routine of the preferred vacuum resid charging of the present invention, it obtains as the cohesion piece, and it needs a large amount of technique of removing, and comprises boring and the water spray technology. As discussed, circulation timei, this made described method complicated significantly owing to increasing.

Shot coke is considered to the coke of minimum quality. Term ＂ shot coke ＂ is similar to BB size [1/16 inch～3/8 inch (.16 centimetre～95 centimetres) ball from its shape. Shot coke as the coke of described other types, has the tendency of the bulk of being condensed into, and particularly with the mixture of sponge coke, diameter is greater than one foot sometimes. This can cause purifier equipment and process problem. Shot coke is usually by the high resin of minimum quality-asphalitine feed preparation, and becomes good high-sulfur combustor source, especially for the production of cement kiln and steel. Also have another kind of coke, it is considered to ＂ transition coke ＂, refers to have the coke of the form between sponge coke and the shot coke or by the coke of shot coke in conjunction with the compositions of mixtures of sponge coke. For example, be mainly the coke of spongy physics outward appearance, show with discrete shape and begin to form little ball but have evidence.

Have been found that free-pouring shot coke can be produced by processing resid feed with one or more overbasic alkaline-earth metal detergent additives of the present invention basically. Described additive is those of production that improve shot coke during delayed coking. Namely impel described additive to be scattered under the temperature of described charge raw material in effective temperature, with one or more additive treating resid feed. These temperature are generally 70 ℃～500 ℃, and preferred 150 ℃～370 ℃, more preferably 185 ℃～350 ℃.

Contain the cleaning agent of overbasic alkali and alkaline earth metal ions as additive of the present invention. The example of these cleaning agents is the oil-soluble basic salt (or its mixture) that maybe can be scattered in oil with alkaline-earth metal of following one or more acidic materials: (1) sulfonic acid, (2) carboxylic acid, (3) salicylic acid, (4) alkyl phenol, (5) sulfenyl phenolate, (6) organic phosphoric acid is characterized by at least one direct C—P bond. These organic phosphoric acids comprise by processing those of olefin polymer (for example polyisobutene of molecular weight 1000) preparation with bonderite such as phosphorus trichloride, phosphorus heptasulfide, phosphoric sulfide, tri-chlorination p and s, white phosphorus and halogenation sulphur or D2EHDTPA chlorine. These acid salt of normal use are those of calcium and magnesium. Be used for the preferred TBN at least 50 of salt of these embodiments, preferably be higher than 100, most preferably be higher than 200 basic salt. In this connection, TBN determines according to ASTM D-2896-88.

Term ＂ basic salt ＂ is used for representing that the stoichiometry of wherein metal existence is greater than the slaine of organic acid. The normally used method for preparing described basic salt relates to, under 50 ℃ of temperature, heating has the sour mineral oil solution of the excessive metal nertralizer of stoichiometry, the metal nertralizer that described stoichiometry is excessive, such as metal oxide, hydroxide, carbonate, bicarbonate or sulfide, and filter the piece that obtains. Using ＂ promoter ＂ in the neutralization procedure is known with the auxiliary in a large number introducing of excessive metal equally. Example as the compound of promoter comprises aldehydes matter, such as phenol, and naphthols, alkyl phenol, benzenethiol, sulfenyl phenolate, and the condensation product of formaldehyde and aldehydes matter; Pure such as methyl alcohol, 2-propyl alcohol, octanol, Cellosolve alcohol, carbitol, ethylene glycol, octadecanol, and cyclohexyl alcohol; Amine is such as aniline, phenylenediamine, phenthazine, PBNA, and dodecyl amine. Prepare described basic salt especially effective method comprise alkaline-earth metal nertralizer and at least a pure promoter of mixed acid and excessive alkalescence, and at high temperature such as 60 ℃～200 ℃ described mixtures of lower carbonating.

The example of the suitable cleaning agent that contains alkaline-earth metal includes but not limited to that salt these material alkalescence or overbasic is such as calcium phenoxide, phenol magnesium, sulfuration calcium phenoxide, and sulfuration phenol magnesium, wherein each aryl has one or more fat bases to give the hydrocarbon dissolubility; Sulfoacid calcium, and sulfonic acid magnesium, wherein each sulfonic acid partly is connected to virtue nuclear, and it contains again one or more aliphatic substituting groups usually to give the hydrocarbon dissolubility; Calcium salicylate and magnesium salicylate, wherein said aromatic portion are usually replaced to give the hydrocarbon dissolubility by one or more aliphatic substituting groups and have 10～2,000 carbon atom; Calcium salt and the magnesium salts of the alkene of hydrolysis sulphur phosphatization, or have the alcohol of hydrolysis sulphur phosphatization of 10～2,000 carbon atom and/or calcium salt and the magnesium salts of the phenolic compound that aliphatic series replaces; Calcium salt and the magnesium salts of the ring grease carboxylic acid that aliphatic carboxylic acid and aliphatic series replace; With many other similar oil-soluble organic acid alkali salts. Can use the alkalescence of two or more different alkaline-earth metal or the mixture of high alkalinity salt. Similarly, also can use two or more different acid or the alkalescence of two or more dissimilar acid or mixtures (for example one or more calcium phenoxides and one or more sulfoacid calcium) of high alkalinity salt.

As everyone knows, overbased metal detergent is considered to contain the inorganic base of high alkalinity amount usually, may be with the form of a differential prose style free from parallelism or colloidal suspension. Therefore the oil-soluble ＂ of term ＂ and the oil dispersible ＂ of ＂ are applied to these metallic cleaning agents, to comprise the metal that wherein has inorganic base, its not necessarily with the strict definition of described term fully or oil-soluble truly, as long as show when these cleaning agents are sneaked into base oil with as they identical modes when fully being dissolved in oil fully.

In general, the basic organic acid salt that sometimes is called quite simply alkali metal containing or alkaline-earth metal at cleaning agent various alkalescence mentioned above or overbasic.

Accurate condition with the described resid feed of described additive treating depends on charging and additive. That is to say, depend on the charging for the treatment of coking and composition and the performance of employed additive with the condition of described additive treating charging. Can determine routinely these conditions. For example, laboratory scale reactor such as Microcarbon Residue Test Unit (MCRTU) in, with containing the special charging of additive, test several times and subsequently coking with different time and temperature. Then by utilizing coke optics and/or that the polarized light microscope analysis obtains as illustrating among the present invention. Preferred coke morphology (namely produce basically free-pouring coke) is to have average-size 0.5～10 μ m, and the coke microstructure of the discrete film micro area of preferred 1～5 μ m has point image at Fig. 1, the described mosaic that shows in 2 and 3. Expression does not have the coke microstructure of free-pouring shot coke to be shown in Fig. 1, and the coke microstructure of demonstration is by basically non-discrete, or up to 60 μ m or large scale more, the substantially large flow region of common 10～60 μ m forms.

Auxiliary agent is handled in conventional coking, comprises defoamer, can be used for method of the present invention.Though produce shot coke by ordinary method, it agglomerates to such degree usually so that still need the water spray technology to be removed.

In one embodiment of the present invention, described resid feed is at first with the additive treating of impelling free-pouring basically coke to form.By keeping coking tower at relatively low pressure, most of volatile matter that generates can be in overhead collection, and this prevents to form intermediate phase and undesirable cohesion.Recycle ratio (＂ CFR ＂) is the volume ratio of furnace charge (fresh feed adds turning oil) with the fresh feed of continuous delayed coking operation.Delayed coking operation is used the circulation of 5vol.%～25vol.% (CFRs1.05～1.25) usually.Being 0 circulation in some cases, in special the application, circulate sometimes up to 200%.Low CFRs helps the formation of free-pouring shot coke, does not preferably use circulation.

Without wishing to be held to any concrete theory or model, the additive or the additive agent mixture that use are considered to work by one or more following approach: a) when the metal that is present in described charging is converted into the metallic sulfide of the catalyzer that dehydrogenation and shot coke form, as dehydrogenation and linking agent; B) the containing metal material is added the reagent of described charging, the formation of its influence or guiding shot coke, or be converted into shot coke and form for example material of metallic sulfide of catalyzer; C) by microcosmic crystal grain of forming around it as shot coke as the particle that influence shot coke formation, as the Lewis acid of cracking and crosslinking catalyst etc.Additive also can change or cause the viscosity of the soft solid materials of reactive component, makes that the shearing force in pit kiln, transfer line and the coking tower is rolled into little ball with soft solid materials.Though can use different additives and additive agent mixture, can use similar method that additive is contacted with charging.

Usually, in a continuous manner additive is introduced described coking.If desired, additive can be dissolved in suitable transfering fluid or make slurry, it typically is the solvent compatible with Residual oil, and wherein said additive is essentially soluble.In described charging, to realize the speed of the additive concentration of needs, described fluid mixture or stock pump are sent into described coking then.The introducing point of additive can, for example at described stove charging pump outlet, or near the outlet of described coking transfer line.A pair of mixing vessel can be arranged, and it is operated in the mode of additive being introduced continuously coking.

Can be according to the speed of the property adjustments additive introducing for the treatment of the coking residue charging.Can need still less additive at the charge ratio of the stagnation point (threshold) that produces shot coke away from those of stagnation point.

For the additive that is difficult to dissolve or be dispersed in resid feed, described additive is transferred to mixing/pulp container, and mixes with the slurry medium compatible with charging.The unrestricted example of suitable slurry medium comprises coking heavy gas oil, water etc.Provide energy to disperse described additive can for described container, for example pass through mixing tank.

For can more easily dissolving or be dispersed in the additive of resid feed, described additive is transferred to described mixing vessel and mixes with the fluid transmission medium compatible with charging.The unrestricted example of suitable fluid transmission medium comprises hot Residual oil (150 ℃～300 ℃ temperature), coking heavy gas oil, light cycle, heavy reformate and its mixture.Also can use Cat slurry attitude oil (CSO) simultaneously, although under some conditions, it may suppress the ability of the loose shot coke of described Additive Production.Energy is provided for described container, for example, is used to disperse described additive to enter described fluid transmission medium by mixing tank.

Will be better appreciated by the present invention with reference to following illustrative non-limiting example.

Embodiment

Additive is added general step in the vacuum resid charging

Described resid feed is heated to 70-150 ℃ to reduce its viscosity.(1,000,000/weight, wppm), the mixing time enough is with dispersion and/or dissolve described additive (＂ jitter time ＂) to add described additive then at leisure.For breadboard test, preferably at first dissolve usually and/or disperse described additive in solvent, for example toluene, tetrahydrofuran (THF), or water, and under agitation it is mixed into the Residual oil of described heating, or is mixed into and adds some solvents to reduce the Residual oil of its viscosity.Can remove then and desolvate.In a refining unit, when additive is added into resid feed or with the resid feed blended time, described additive contacts with described Residual oil.As discussing, can sneak into described charging by the feeding part (comprising the feeding part that contains these materials natively) that will contain additive materials and realize contacting of described additive and described charging.For being dispensed into described vacuum resid charging with guaranteeing described additive maximum, can the described reaction mixture of soaking.

Use the additive of various resid feed to carry out following test.By the determined additive concentration of light micrograph, soaking time and the coke morphology that obtains are listed in the table below 1.As a comparison, use the Residual oil control sample that does not have additive.

Table 1

Resid feed	Additive (metal wppm)	The microtexture of MCR coke	Shown in coke type
Heavy Canadian	Do not have	The mosaic pattern (3-10 μ m) that zonule (10-15 μ m) and medium/coarse are rough	Transition
				Heavy Canadian	Calcium sulphonate OB sanitising agent (500)	Medium/coarse is rough Mosaic pattern (1-8 μ m)	Spherical
Heavy Canadian	Calcium salicylate OB sanitising agent (500)	Medium/coarse is rough Mosaic pattern (1-9 μ m)	Spherical

Claims (11)

1. delayed coking method comprises:

(a) but in first heating zone heating fuel oil residuum be the temperature of pumping liquid still to being lower than coking temperature to Residual oil wherein;

(b) Residual oil of described heating is introduced second heating zone, the Residual oil of wherein said heating is heated to coking temperature;

(c) Residual oil of described heating is introduced the coking district from described second heating zone,, and form coke product wherein in the overhead collection vapor product; With

(d) will introduce described Residual oil for forming the effective at least a overbased metal detergent additive of free-pouring basically coke, wherein in the upstream of described second heating zone, the upstream in described coking district or the position at two places, described overbased metal detergent additive is introduced described Residual oil.

2. delayed coking method comprises:

(a) under 70 ℃～370 ℃ temperature, make vacuum resid contact time enough, so that described reagent is dispensed into described charging equably with at least a overbasic alkaline-earth metal detergent additive of significant quantity;

(b) Residual oil of the described processing of heating is to the temperature of the described charging of effective coking;

(c) described heat treated Residual oil is fed to (the coking district under 103.42～551.58kPa) pressure reaches scorch time to form hot coke bed at 15～80psig; With

(d) water quenching is to the described hot coke bed of small part.

3. method as claimed in claim 1, wherein said resid feed are vacuum resid.

4. each method of claim as described above wherein dissolves in described charging to the described additive of small part.

5. each method of claim as described above, wherein said additive is one or more in calcium phenylate, phenol magnesium, sulfuration calcium phenylate and the sulfuration phenol magnesium, wherein each aryl has one or more fat bases to give the hydrocarbon solvability.

6. each method of claim as described above, wherein said additive is one or more in calcium sulphonate and the sulfonic acid magnesium, and wherein each sulfonic acid partly is connected to virtue nuclear, and it contains one or more aliphatic substituting groups again usually to give the hydrocarbon solvability.

7. each method of claim as described above, wherein said additive is one or more in calcium salicylate and the magnesium salicylate, wherein said aromatic portion is replaced by one or more aliphatic substituting groups, to give the hydrocarbon solvability.

8. each method of claim as described above, wherein said additive is selected from has 10～2, the alkene of the hydrolysis sulphur phosphatization of 000 carbon atom or have the alcohol of hydrolysis sulphur phosphatization of 10～2,000 carbon atom and/or the calcium salt and the magnesium salts of the phenolic compound that aliphatic series replaces.

9. each method of claim as described above, wherein said additive are the calcium salt of the ring grease carboxylic acid that replaces of aliphatic carboxylic acid and aliphatic series and in the magnesium salts one or more.

10. each method of claim as described above, wherein the coke of Sheng Chaning is essentially shot coke.

11. method as claimed in claim 1 wherein in the upstream of the upstream of described first heating zone, described second heating zone or the position at two places, is introduced described vacuum resid with described overbased metal detergent additive.

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