CN109135818A - The preparation method and production equipment of slag oil desulfurization method and petroleum coke - Google Patents
The preparation method and production equipment of slag oil desulfurization method and petroleum coke Download PDFInfo
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- CN109135818A CN109135818A CN201811176272.1A CN201811176272A CN109135818A CN 109135818 A CN109135818 A CN 109135818A CN 201811176272 A CN201811176272 A CN 201811176272A CN 109135818 A CN109135818 A CN 109135818A
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- residual oil
- desulfurization
- petroleum coke
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The present invention provides a kind of slag oil desulfurization method and the preparation methods and production equipment of petroleum coke, it is related to petroleum coking technology field, the slag oil desulfurization method, comprising the following steps: S1) residual oil is provided as reaction raw materials, residual oil is mixed with pretreating agent, residual oil is pre-processed；Wherein, the pretreating agent includes metal base and/or metal carbonate；S2) preconditioned mixture obtained by step S1) is placed in electrostatic field after carrying out Electrostatic Absorption desulfurization process and completes the desulfurization of residual oil, obtain the residual oil of low sulfur content.Technology difficulty big, at high cost and poor desulfurization effect technical problem when can be alleviated in the prior art using the slag oil desulfurization method to petroleum coke progress desulfurization, desulfurization is carried out from raw material and reaches reduction desulfurization difficulty and improves desulfurization effect purpose.
Description
Technical field
The present invention relates to petroleum coking technology fields, more particularly, to a kind of slag oil desulfurization method and the preparation side of petroleum coke
Method and production equipment.
Background technique
Petroleum coke is that a kind of coke obtained is processed in the delayed coking of residual oil.Currently, the petroleum coke product in China portion big absolutely
Dividing is high sulfur petroleum coke (sulfur content is higher than 3%).The use of high sulfur petroleum coke not only results in the corrosion of equipment, makes the life of enterprise
It produces cost to increase, while environment can be caused seriously to pollute.With the attention of Environmental protection in recent years, environmental protection grade
Gradually upgrade, future will be increasing to the demand of the low sulfur petroleum coke of high-quality, therefore reduces the sulfur content in petroleum coke
It is imperative.
Currently, in order to obtain low sulfur petroleum coke, mainly using high-temperature calcination, wet chemical oxidation, dielectric gas desulfurization and
The methods of solvent extraction carries out desulfurization process to high sulfur petroleum coke.High-temperature calcination method is the hot conditions by petroleum coke at 1600 DEG C
Under calcined, desulfurization degree is more than 50%, but energy consumption is larger.Wet chemical oxidation method is will using the method for chemical reagent oxidation
Organic sulfur conversion not soluble in water is water-soluble or sour inorganic sulfur to achieve the purpose that desulfurization, but this method meeting in petroleum coke
Generate a large amount of waste water.Dielectric gas desulfurization refers to that petroleum coke, which is placed in constant temperature in desulfurization dielectric gas, for a period of time, makes petroleum coke
In sulphur and dielectric gas interact and achieve the purpose that desulfurization, but this method energy consumption is high and risk is big.Solvent extraction process
It is that the sulphur in petroleum coke is extracted into solvent using the method for organic solvent extraction, to achieve the purpose that desulfurization, but the party
Method desulfurization degree is low, and most of organic solvent is toxic, inflammable and explosive, higher cost.As can be seen from the above analysis, stone is utilized
Oil coke is raw material, carries out desulfurization directly against petroleum coke, difficulty is larger, and higher cost, and effect is limited.
In view of this, the present invention is specifically proposed.
Summary of the invention
Core of the invention is to find, sulfur in petroleum coke content depends primarily in the raw material i.e. residual oil of production petroleum coke
Sulfur content and sulfur speciation by changing the sulfur speciation in residual oil so that it becomes the sulfide easily removed carrying out pyrogenetic reaction
It is preceding to deviate from sulfide in advance, the petroleum coke of low sulfur content can be obtained.Meanwhile present inventor has further discovered that utilizing metal
Alkali or metal carbonate can change the existence form of sulphur in residual oil, it is made to change into the sulfide easily removed.
The first object of the present invention is to provide a kind of sulfur method, to alleviate at least one of above problem.
The second object of the present invention is to provide a kind of preparation method of petroleum coke, to alleviate in the prior art directly to stone
Oil coke carries out big, the at high cost and poor desulfurization effect technical problem of sulfur removal technology difficulty.
The third object of the present invention is to provide a kind of production equipment of petroleum coke, and the production equipment is utilized to produce petroleum
Coke can obtain to obtain low sulfur petroleum coke.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of slag oil desulfurization method, comprising the following steps:
S1 residual oil) is provided as reaction raw materials, residual oil is mixed with pretreating agent, residual oil is pre-processed；Wherein,
The pretreating agent includes metal base and/or metal carbonate；
S2) preconditioned mixture obtained by step S1) is placed in electrostatic field after carrying out Electrostatic Absorption desulfurization process and completes slag
The desulfurization of oil, obtains the residual oil of low sulfur content.
Further, the metal base includes sodium hydroxide, potassium hydroxide and/or calcium hydroxide；
The metal carbonate includes sodium carbonate and/or potassium carbonate.
Further, in the mixture of residual oil and pretreating agent, the mass fraction of pretreating agent is 0.5%~20%, excellent
It is selected as 1%~10%, further preferably 1%~5%.
Further, step S1) in pretreated reaction temperature be 50~350 DEG C, preferably 100~300 DEG C, further
Preferably 150~250 DEG C；Reaction time is 0.1~5h, preferably 0.5~2h, further preferably 0.5~1.5h.
Further, step S2) in, the temperature of preconditioned mixture is 50~300 DEG C, preferably 100~250 DEG C, into
One step is preferably 100~150 DEG C.
Further, step S2) in, the electric field strength of the electrostatic field is 500~15000V/cm, preferably 1500~
10000V/cm, further preferably 2000~5000V/cm.
Further, the electrostatic field is AC field, DC electric field or AC-DC alternating electric field, preferably direct current
?.
A kind of preparation method of petroleum coke, comprising the following steps:
Residual oil after the desulfurization obtained according to above-mentioned slag oil desulfurization method obtains petroleum coke after coking is handled.
Further, coking processing in pyrogenetic reaction temperature be 450~550 DEG C, preferably 450~500 DEG C, further
Preferably 460~500 DEG C；The pyrogenetic reaction time is 0.5~8h, preferably 2~6h, further preferably 3~5h.
A kind of production equipment for realizing above-mentioned petroleum coke, including the pretreatment tank, electrostatic treatment tank and coke being sequentially communicated
Tower.
Compared with the prior art, the invention has the following beneficial effects:
The present invention has found that residual oil can contain with metal base or metal carbonate reactant salt to change in residual oil under study for action
The form of sulphur compound.In slag oil desulfurization method provided by the invention, using metal base or metal carbonate as pretreating agent pair
Residual oil is pre-processed, to change the existing forms of sulphur in residual oil；Then pass through the coalescence of electrostatic field, absorption, settling character again
Sulfur-containing compound is separated, realizes the desulfurization of residual oil, to obtain a kind of residual oil of low sulfur content.
The preparation method of petroleum coke provided by the invention, from the raw material of petroleum coke, the feed residue of use is through pre-
The residual oil that the low sulfur content of sulfur-containing compound is removed after processing and electrostatic coalescence absorption, by using the residual oil of low sulfur content, system
Standby to obtain the petroleum coke of low sulfur content, the preparation for low sulfur petroleum coke provides a new thinking.The preparation method and tradition
The reprocessing desulfurization of high sulfur petroleum coke is compared, and energy consumption significantly reduces, and technical process is simple, easy to operate, may be implemented continuous
Metaplasia produces, remarkable in economical benefits.
The production equipment of petroleum coke provided by the invention, including the pretreatment tank, electrostatic treatment tank and coke being sequentially communicated
Tower.In production process, residual oil and pretreating agent is placed in pretreatment tank carries out hybrid reaction first, change Containing Sulfur in residual oil
The form of object is closed, then by pretreated residual oil by electrostatic treatment tank, by the coalescence, absorption, settling character of electrostatic field,
Separate the sulfur-containing compound in residual oil, realize the desulfurization of residual oil, finally by the residual oil after desulfurization be passed into coke drum into
Low sulfur petroleum coke can be obtained in row pyrogenetic reaction.By the production equipment, the continuous metaplasia of low sulfur petroleum coke can be directly realized by
It produces, high production efficiency.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is a kind of production equipment structural schematic diagram of petroleum coke of the present invention；
Fig. 2 is the preparation technology flow chart of the petroleum coke of one embodiment of the present invention.
Icon: 10- pre-processes tank；20- electrostatic treatment tank；30- coke drum.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood as the case may be
Concrete meaning in the present invention.
A kind of slag oil desulfurization method, comprising the following steps:
S1 residual oil) is provided as reaction raw materials, residual oil is mixed with pretreating agent, residual oil is pre-processed；Wherein,
The pretreating agent includes metal base and/or metal carbonate；
S2) preconditioned mixture obtained by step S1) is placed in electrostatic field after carrying out Electrostatic Absorption desulfurization process and completes slag
The desulfurization of oil, obtains the residual oil of low sulfur content.
The present invention has found that residual oil can contain with metal base or metal carbonate reactant salt to change in residual oil under study for action
The form of sulphur compound.In slag oil desulfurization method provided by the invention, using metal base or metal carbonate as pretreating agent pair
Residual oil is pre-processed, to change the existing forms of sulphur in residual oil；Then pass through the coalescence of electrostatic field, absorption, settling character again
Sulfur-containing compound is separated, realizes the desulfurization of residual oil, to obtain a kind of residual oil of low sulfur content.
Sulfur-containing compound in residual oil generates for example, chemical reaction occurs for mercaptan or thioether and pretreating agent insoluble in oil
Sulfur-containing compound, under the action of electric field, coalescence, absorption can occur for these sulfur-containing compounds to realize the de- of residual oil sulphur
It removes.
In certain embodiments of the present invention, the metal base includes sodium hydroxide, potassium hydroxide and/or hydroxide
Calcium；The metal carbonate includes sodium carbonate and/or potassium carbonate.
Experiment proves that when metal base is sodium hydroxide, potassium hydroxide and/or calcium hydroxide, alternatively, working as metal carbonate
When salt is sodium carbonate and/or carbonic acid, desulfurization effect is more preferable.
In the above-described embodiment, metal base includes the hydroxide of metal and the mixture of metal base, metal base
It can be such as the combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide and potassium hydroxide and sodium hydroxide and hydroxide
The combination of calcium.Metal carbonate for example can be the mixture of sodium carbonate, potassium carbonate or sodium carbonate and potassium carbonate.
In certain embodiments of the present invention, in the mixture of residual oil and pretreating agent, the mass fraction of pretreating agent
It is 0.5%~20%, in further preferred embodiment, the mass fraction of pretreating agent is 1%~10%, more into one
It walks in preferred embodiment, the mass fraction of pretreating agent is 1%~5%.
Pretreating agent additive amount increases, and can improve desulfurization effect.But when the increase of pretreating agent additive amount to a certain extent
Afterwards, then increase additive amount, desulfurization degree increase degree is limited, will cause the waste of pretreating agent instead；And pretreating agent additive amount
It is very few, then it will affect the desulfurization effect of residual oil.
, both can be excessive to avoid pretreating agent by limiting the dosage of pretreating agent, influence subsequent electrostatic separation and stone
The coking of oil coke production process is handled, and can also effectively be carried out desulfurization, be improved the desulfurization effect of residual oil.
In the above-described embodiment, in the mixture of residual oil and pretreating agent, the mass fraction of pretreating agent for example can be with
It is 0.5%, 1%, 2%, 3%, 5%, 7%, 8%, 10%, 12%, 15%, 17% or 20%.
In some embodiments in the present invention, in preprocessing process, pretreated reaction temperature is 50~350
DEG C, the reaction time is 0.1~5h；In further preferred embodiment of the present invention, pretreated reaction temperature be 100~
300 DEG C, the reaction time is 0.5~2h；In the embodiment of the present invention still more preferably, pretreated reaction temperature is
150~250 DEG C, the reaction time is 0.5~1.5h.
By limiting pretreated reaction temperature, residual oil can be effectively prevented, coking occurs, while making residual oil and pretreatment
The reaction of agent sufficiently carries out, and realizes desulfurization.
In certain embodiments of the present invention, step S2) in, the temperature of preconditioned mixture is 50~300 DEG C, at this
In invention further preferred embodiment, the temperature of preconditioned mixture is 100~250 DEG C, of the invention further
In preferred embodiment, the temperature of preconditioned mixture is 100~150 DEG C.
On the one hand, the tendency of itself coking of the excessively high residual oil of temperature increases, once residual oil generates coke, will increase the de- process of electricity
In electric current；On the other hand, even if residual oil noncoking, temperature is excessively high, the electric current in Electrostatic Absorption sweetening process also be will increase.Cause
This, needs to control temperature into the even running for guaranteeing the de- tank of electricity in the reasonable scope during electricity is de-.
The temperature of the preconditioned mixture obtained after pretreatment reaction is controlled and carries out Electrostatic Absorption again at 50~300 DEG C,
The temperature of preconditioned mixture can be heated up or be cooled down by way of heat exchange.
In certain embodiments of the present invention, step S2) in, the electric field strength of the electrostatic field is 500~15000V/
Cm, in further preferred embodiment of the present invention, the electric field strength of the electrostatic field is 1500~10000V/cm, at this
It invents in further preferred embodiment, the electric field strength of the electrostatic field is 2000~5000V/cm.
During electrostatic treatment, electric field strength needs to control in zone of reasonableness, and the excessively high electrostatic that will cause of electric field strength is set
The phenomenon that standby electric current is excessive, is frequent tripping causes electrostatic apparatus can not even running；But electric field is too low, Containing Sulfur
It closes object and is unable to rapid coalescence, absorption, influence the removal effect of sulfur-containing compound.
In certain embodiments of the present invention, the electrostatic field is AC field, DC electric field or friendship-value stream alternation electricity
Field, preferably DC electric field.
On the other hand, the present invention provides a kind of preparation methods of petroleum coke, comprising the following steps:
Residual oil after the desulfurization obtained according to above-mentioned slag oil desulfurization method obtains petroleum coke after coking is handled.
The preparation method of petroleum coke provided by the invention, from the raw material of petroleum coke, the feed residue of use is through pre-
The residual oil that the low sulfur content of sulfur-containing compound is removed after processing and electrostatic coalescence absorption, by using the residual oil of low sulfur content, system
Standby to obtain the petroleum coke of low sulfur content, the preparation for low sulfur petroleum coke provides a new thinking.The preparation method and tradition
The reprocessing desulfurization of high sulfur petroleum coke is compared, and energy consumption significantly reduces, and technical process is simple, easy to operate, may be implemented continuous
Metaplasia produces, remarkable in economical benefits.
In certain embodiments of the present invention, the pyrogenetic reaction temperature in coking processing is 450~550 DEG C, preferably
450~500 DEG C, further preferably 460~500 DEG C；The pyrogenetic reaction time be 0.5~8h, preferably 2~6h, further it is excellent
It is selected as 3~5h.
In another aspect, the present invention provides a kind of production equipment for realizing above-mentioned petroleum coke, including the pre- place being sequentially communicated
Manage tank, electrostatic treatment tank and coke drum.
The production equipment of petroleum coke provided by the invention, as shown in Figure 1, including pretreatment tank 10, the electrostatic being sequentially communicated
Process tank 20 and coke drum 30.In production process, residual oil is placed in pretreatment tank 10 with pretreating agent mix instead first
It answers, changes the form of sulfur-containing compound in residual oil, pretreated residual oil is then passed through into electrostatic field by electrostatic treatment tank 20
Coalescence, absorption, settling character, separate the sulfur-containing compound in residual oil, realize the desulfurization of residual oil；It finally will be after desulfurization
Residual oil be passed into coke drum 30 carry out pyrogenetic reaction, pyrogenetic reaction generate oil gas product from the top of coke drum 30 be discharged,
The coke of generation is discharged from the bottom of coke drum 30, and low sulfur petroleum coke can be obtained.By the production equipment, can be directly realized by
The continuous production of low sulfur petroleum coke, high production efficiency.
Below in conjunction with embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
The present embodiment is a kind of preparation method of petroleum coke, and process flow chart is as shown in Figure 2, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium hydroxide 90:10 in mass ratio and is reacted, is reacted
Temperature is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: the residual oil after pretreatment reaction enters DC electric field intensity after heat exchange is cooled to 300 DEG C and is
Desulfurization process is carried out in the electrostatic treatment tank of 5000V/cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 2
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium hydroxide 99:1 in mass ratio and is reacted, reaction temperature
Degree is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: it is 1500V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 150 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 3
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium hydroxide 95:5 in mass ratio and is reacted, reaction temperature
Degree is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 4
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium hydroxide 95:5 in mass ratio and is reacted, reaction temperature
Degree is 250 DEG C, reaction time 2h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 5
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with potassium hydroxide 99:1 in mass ratio and is reacted, reaction temperature
Degree is 300 DEG C, reaction time 1h；
S2) Electrostatic Absorption: it is 3000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 200 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 6
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with potassium hydroxide 95:5 in mass ratio and is reacted, reaction temperature
Degree is 250 DEG C, reaction time 2h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 7
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium carbonate 85:15 in mass ratio and is reacted, reaction temperature
Degree is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 8
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium carbonate 95:5 in mass ratio and is reacted, reaction temperature
It is 300 DEG C, reaction time 1h；
S2) Electrostatic Absorption: it is 1500V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 150 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 9
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium carbonate 95:5 in mass ratio and is reacted, reaction temperature
It is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 10
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with sodium carbonate 95:5 in mass ratio and is reacted, reaction temperature
It is 350 DEG C, reaction time 1.5h；
S2) Electrostatic Absorption: it is 3000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 250 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 11
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with potassium carbonate 99:1 in mass ratio and is reacted, reaction temperature
It is 300 DEG C, reaction time 1h；
S2) Electrostatic Absorption: it is 1500V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 150 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Embodiment 12
The present embodiment is a kind of preparation method of petroleum coke, comprising the following steps:
S1 it) pre-processes: residual oil being mixed in pretreatment tank with potassium carbonate 95:5 in mass ratio and is reacted, reaction temperature
It is 250 DEG C, reaction time 2h；
S2) Electrostatic Absorption: it is 5000V/ that the residual oil after pretreatment reaction, which is exchanged heat to DC electric field intensity is entered after 300 DEG C,
Desulfurization process is carried out in the electrostatic treatment tank of cm；
S3) pyrogenetic reaction: the residual oil after desulfurization process enters in coke drum after heat exchange is warming up to 490 DEG C to carry out
Pyrogenetic reaction, pyrogenetic reaction time are 4h, obtain the petroleum coke of low sulfur content after reaction.
Comparative example 1
This comparative example is a kind of preparation method of petroleum coke, directly directly heats residual oil to 490 DEG C in the preparation method
After be passed through in coke drum and react 4h, obtain petroleum coke.
Comparative example 2
This comparative example is a kind of preparation method of petroleum coke, comprising the following steps:
S1) residual oil is heated to being passed into after 300 DEG C in the electrostatic treatment tank that ac electric field strength is 1500V/cm and is carried out
Desulfurization process；
S2) residual oil after electrostatic treatment is passed into coke drum after being heated to 490 DEG C reacts 4h, obtains petroleum coke.
Comparative example 3
This comparative example is a kind of preparation method of petroleum coke, comprising the following steps:
S1) residual oil is heated to being passed into after 200 DEG C in the electrostatic treatment tank that DC electric field intensity is 5000V/cm and is carried out
Desulfurization process；
S2) residual oil after electrostatic treatment is passed into coke drum after being heated to 490 DEG C reacts 4h, obtains petroleum coke.
Comparative example 4
S1) residual oil is heated to being passed into after 150 DEG C in the electrostatic treatment tank that ac electric field strength is 15000V/cm and is carried out
Desulfurization process；
S2) residual oil after electrostatic treatment is passed into coke drum after being heated to 490 DEG C reacts 4h, obtains petroleum coke.
Illustrate, the amount containing lithium in reaction raw materials residual oil used in embodiment 1-12 and comparative example 1-4 is identical.
The sulfur content in the petroleum coke of testing example 1-12 and comparative example 1-4, test result are listed in table 1 respectively.
1 test result of table
It can be seen that from the data in table 1 when the pretreating agent used is identical, change the ratio of residual oil and pretreating agent
Example, or change pretreatment temperature and time, or the intensity of temperature and electrostatic field during change Electrostatic Absorption can be to desulfurization
Effect generates certain influence.Sulfur content when the mutual cooperation of each condition reaches more excellent state, in finally obtained petroleum coke
0.3% can be down to.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of slag oil desulfurization method, which comprises the following steps:
S1 residual oil) is provided as reaction raw materials, residual oil is mixed with pretreating agent, residual oil is pre-processed；Wherein,
The pretreating agent includes metal base and/or metal carbonate；
S2) preconditioned mixture obtained by step S1) is placed in electrostatic field after carrying out Electrostatic Absorption desulfurization process and completes residual oil
Desulfurization obtains the residual oil of low sulfur content.
2. slag oil desulfurization method according to claim 1, which is characterized in that the metal base includes sodium hydroxide, hydrogen-oxygen
Change potassium and/or calcium hydroxide；
The metal carbonate includes sodium carbonate and/or potassium carbonate.
3. slag oil desulfurization method according to claim 1, which is characterized in that in the mixture of residual oil and pretreating agent, in advance
The mass fraction of inorganic agent is 0.5%~20%, preferably 1%~10%, further preferably 1%~5%.
4. slag oil desulfurization method according to claim 1, which is characterized in that step S1) in pretreated reaction temperature be
50~350 DEG C, preferably 100~300 DEG C, further preferably 150~250 DEG C；Reaction time be 0.1~5h, preferably 0.5
~2h, further preferably 0.5~1.5h.
5. slag oil desulfurization method according to claim 1, which is characterized in that step S2) in, the temperature of preconditioned mixture
It is 50~300 DEG C, preferably 100~250 DEG C, further preferably 100~150 DEG C.
6. slag oil desulfurization method according to claim 1, which is characterized in that step S2) in, the electric-field strength of the electrostatic field
Degree is 500~15000V/cm, preferably 1500~10000V/cm, further preferably 2000~5000V/cm.
7. slag oil desulfurization method according to claim 6, which is characterized in that the electrostatic field is AC field, direct current
Field or AC-DC alternating electric field, preferably DC electric field.
8. a kind of preparation method of petroleum coke, which comprises the following steps:
Residual oil after the desulfurization obtained according to the described in any item slag oil desulfurization methods of claim 1-7 obtains after coking is handled
Petroleum coke.
9. preparation method according to claim 8, which is characterized in that coking processing in pyrogenetic reaction temperature be 450~
550 DEG C, preferably 450~500 DEG C, further preferably 460~500 DEG C；The pyrogenetic reaction time be 0.5~8h, preferably 2~
6h, further preferably 3~5h.
10. a kind of production equipment for the petroleum coke for realizing the preparation method of claim 8 or 9, which is characterized in that including successively
Pretreatment tank, electrostatic treatment tank and the coke drum of connection.
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| CN112442391A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of low-sulfur petroleum coke |
| CN112442390A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur petroleum coke from residual oil |
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