CN1592777A - Electrode binder - Google Patents

Electrode binder Download PDF

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Publication number
CN1592777A
CN1592777A CN02823501.0A CN02823501A CN1592777A CN 1592777 A CN1592777 A CN 1592777A CN 02823501 A CN02823501 A CN 02823501A CN 1592777 A CN1592777 A CN 1592777A
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cracking
binders
electrodes
thermo
content
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CN100350016C (en
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M·布特勒
C·K·普尔斯
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a process for the preparation of an electrode binder, which process comprises: - (a) thermally cracking a non-hydrotreated thermal tar feedstock having an aromatic content of less than 65 % wt; (b) separating the thermally cracked product of step (a) in a separator, into at least a top fraction and a bottom fraction, and (c) subjecting the bottom fraction from step (b) to vacuum distillation, to yield, as a vacuum distillation residue, an electrode binder, and an anode binder obtainable by said process for use in aluminium production.

Description

Binders for electrodes
Technical field
The present invention relates to the preparation method of binders for electrodes and the binders for electrodes that obtains with this method.
Background of invention
Electrode is used in and is used to produce metal such as aluminium and steel in the melting pond, and nearly all primary aluminum all is by electrolysis of aluminum oxide (Al in electrolyzer at present 2O 3) produce.In the electrolyzer of producing aluminium, the al deposition of fusion form discharges oxygen simultaneously on the charcoal negative electrode, and the anode consumption of electrolyzer falls the most at last.Electrode prepares by petroleum coke particles is mixed with binding agent.Refinery coke comprises almost purified charcoal, passes through high temperature carbonisation of heavy residues is formed in the crude refining process.
In aluminium electrolysis cell, use two kinds of main anodes, i.e. prebaked anode and the so-called Soederberg anode that is used in the Soederberg pond.In the Soederberg pond, in the continuous mixture adding pond with refinery coke and binding agent, anode is cured then and there with the heat that produces in the pond.Prebaked anode prepares with following method: with the mixture extrusion molding of petroleum coke particles and binding agent, then anode is cured or carbonization, so that binding agent is converted into charcoal.
The binding agent that uses when producing kind electrode is coal-tar pitch normally.Coal-tar pitch is the rectifying product of coal tar, and coal tar is the coal carbonizing product, and coal tar is formed by hydrocarbon ils, phenol derivatives with such as the alkaline matter of pyridine and quinoline etc.With coal-tar pitch is because its carbon content and aromatic content height this means that the electrode that contains coal-tar pitch binder contains seldom non-carbon impurity after carbonization as binding agent.This is very important for electrode performance and life-span, because the impurity (as metal such as vanadium, nickel etc.) in the electrode equally may polluted product, increases the air of electrode and the reactivity of carbonic acid gas, thereby reduces its work-ing life.But in coal tar, the ratio of polynuclear aromatic compound (PAC) is high, and the content of PAC in coal-tar pitch generally is about 100000ppm.Have some to have carinogenicity in these molecules, for the EHS reason, if can enough a kind of equivalent material replace coal-tar pitch as binders for electrodes, and PAC content wherein is low as far as possible, and then this situation is useful.
Recent rules trend towards making as far as possible the PAC content in the Industrial materials to keep minimum value, and this has just increased the needs that replace coal-tar pitch day by day.Have a large amount of PAC molecules at present.In Europe, some material (as coal deutero-material such as coal-tar pitch) is classified according to its specific PAC content.Such PAC is benzo [a] pyrene for one kind, can think that benzo [a] pyrene is the useful marker of PAC total content in a kind of material.Therefore, aspect carinogenicity, the classification of these products is based on generally that their benzo [a] pyrene content carries out.
Studied with non-refinable crude residual oil as binders for electrodes.But can't think that so far this binding agent is the substitute of industrial acceptable coal-tar pitch, because compare with coal-tar pitch, their performances on some important parameters such as their carbon content and density and all can not be satisfactory with the air reactive and the carbon dioxide reaction of the electrode of this adhesive preparation.In addition, report in order to a few methods for preparing gratifying binders for electrodes in, the aromatic content height of petroleum causes the PAC content of product very high, considers that from the EHS aspect this binding agent is not desirable.
For example, EP-A0378326 has described a kind of being applicable to and has prepared the binder pitch that is used in the Graphite Electrodes in the electric furnace arrangement for producing steel, and its preparation method is: with the petroleum aromatic mineral oil hydrotreatment; Aromatic mineral oil thermo-cracking with hydrotreatment; With the rectifying of thermo-cracking residual oil, be that the fine of 1-40 μ m divides the sintering high-quality burnt particle mixing again with top residual oil and mean diameter then.This with prepare steel-making with the relevant especially method of binder pitch in, must use hydrotreatment aromatic mineral oil raw material, i.e. the pretreated raw material of usefulness hydrogen in the presence of catalyzer.
Canada publication CA2009121 has described a kind of with aromatic raw material production high quality petroleum tar bituminous method, and it comprises the steps: that (a) provides a kind of fresh aromatic raw material; (b) in temperature is about 380-480 ℃ stove with described raw materials pretreatment; (c) described heating raw is added reactor, under controlled condition, in described reactor, handle described raw material, thereby promote polycondensation; (d) make described processing raw material through a separation column, in separation column, raw material is fractionated into (1) gas, (2) light distillate and (3) bottom fraction logistics; (e) described bottom fraction logistics is divided into recirculation stream and the logistics of cracking cut; (f) described cracking cut logistics is added the rectification under vacuum tower, in the rectification under vacuum tower, described light cracking cut is fractionated into (1) light gas oil, (2) heavy gas oil and (3) high quality petroleum tar pitch again.
Raw material in the CA2009121 technology is the logistics of high aromaticity content, and its aromatic content is 65-85wt% (1-4 is capable for page 4, and the 6th page the 21st is walked to the 7th page of the 5th row).In the work embodiment that provides, the raw material that uses is catalytic pyrolysis decant (clarification) oil of aromatic content as 85wt%.In addition, in order to obtain the suitable binder pitch of performance, must should be noted in the discussion above that the asphalt performance optimization in order to obtain with recirculation stream with heavily cracking cut recirculation of a part, recirculation is (the 10th page of 1-5 is capable) that extremely needs.Therefore, those of ordinary skills can obtain following conclusion from the instruction of CA2009121: when preparing binders for electrodes with the petroleum residual oil thermo-cracking and by petroleum residual oil, must use the raw material of high aromatic content, even need be with a part of recirculation of thermo-cracking residual oil.
EP-A1130077 has described a kind of production method of so-called uncontamination petroleum pitch: petroleum fractions or residual oil are heat-treated being lower than under the temperature of 20 atmospheric pressure and 350-470 ℃, heat treatment time is less than 120 minutes.The raw material that uses is the decanted oil that obtains by catalytic pyrolysis and the residual oil that obtains when producing ethene with petroleum naphtha.But the pitch that obtains still contains a large amount of polynuclear aromatic compounds, particularly benzo [a] pyrene, and the content of benzo [a] pyrene in pitch generally is higher than 1000ppm.
If there is a kind of method can enough petroleum base feedstock production not only to have industrial acceptable performance but also had the binders for electrodes of low PAC content, then will be useful.
Summary of the invention
It has surprisingly been found that now and can prepare binders for electrodes with petroleum residual oil, the performance of this binders for electrodes is approaching with the performance of the binders for electrodes for preparing with coal-tar pitch, and its PAC content is significantly less than existing petroleum base binding agent.
The invention provides a kind of preparation method of binders for electrodes, this method comprises:
(a) aromatic content is lower than the thermal tar feedstock thermo-cracking of the not hydrotreatment of 65wt%,
(b) in separator, the thermo-cracking product of step (a) is separated at least overhead fraction and bottom fraction and
(c) bottom fraction of step (b) is carried out rectification under vacuum, thereby obtain binders for electrodes as rectification under vacuum residual oil.
Detailed Description Of The Invention
The present invention relates to aromatic content is lower than the thermal tar feedstock thermo-cracking [step (a)] of the not hydrotreatment of 65wt%.The aromatic content of thermal tar feedstock preferably is lower than 60wt%, more preferably less than 55wt%, most preferably is lower than 50wt%, aromatic content is with testing method SMS2783-95 (Research Disclosure 451104, November calendar year 2001,451 phases, 1918-1922 page or leaf) 1-6 that measures +The total amount of aromatic substance.The aromatic content of thermal tar feedstock is 25-65wt% preferably, more preferably 30-60wt%, most preferably 30-50wt%.
Thermal tar is the residue product of heavy hydrocarbon feeds thermo-cracking; Thermo-cracking is hydrocarbon to be heated to make the technology that is decomposed into the high temperature (as 400-550 ℃) than small molecules than long chain hydrocarbon molecule instability.In refinery, the heavy hydrocarbon feeds thermo-cracking mainly is used in viscosity breaking (promptly reducing viscosity) and hot gas oil production aspect.
Thermal tar feedstock of the present invention preferably heavy hydrocarbon feeds more preferably obtains by thermo-cracking under 450-520 ℃ temperature at 400-550 ℃.Thermal tar feedstock preferably atmospheric distillation residual oil (long residuum), rectification under vacuum residual oil (vacuum residuum), weight or the waxy fraction of crude oil obtains by thermo-cracking.
Particularly preferably, thermal tar feedstock of the present invention is that double distilled goes out raw material, the residual oil that preferred wax overhead product raw material obtains by thermo-cracking.The wax overhead product is that boiling spread is 220 ℃-650 ℃ a rectifying cut.Long residuum is carried out rectification under vacuum or can be easy to obtain the wax overhead product with hot gas oil unit.This thermal tar feedstock is preferred, because for example compare with the thermal tar that the pyrolysis residue raw material obtains, their metals content impurity is lower.
The residual oil that the preferably hot gas oil unit of thermal tar feedstock is produced.Most preferably, thermal tar feedstock of the present invention be in hot gas oil unit with heavy, preferred wax overhead product raw material thermo-cracking obtains.
In a preferred embodiment of the invention, thermal tar feedstock obtains in two sections hot gas oil unit, this method comprises: i) with the residual oil raw material thermo-cracking, ii) cracking stock is separated into gas fraction and liquid distillate, iii) in fractionator, be divided into gas oil fraction and wax overhead product cut to major general's gas fraction, iv) with wax overhead product cut thermo-cracking with v) the wax overhead product cut of thermo-cracking is separated into thermal tar as residual oil.Can be easily in step I fractionator ii) the wax overhead product cut of thermo-cracking be separated.
In this preferred embodiment, preferably 400-500 ℃ of the thermo-cracking temperature of residual oil raw material, more preferably 430-480 ℃: residual oil raw material is vacuum residuum preferably.Can in pyrolyzer raw material be heated to cracking temperature easily with the residual oil raw material cracking in pyrolyzer or soaking drum unit, then it be transferred to soaking drum (reaction chamber), most of scission reactions are carried out in soaking drum.Cracking stock can be separated into gas fraction and liquid distillate at least with any equipment easily, and is very convenient when still carrying out in cyclonic separator.Those of ordinary skills can understand, and the temperature that enters the pyrolysis residue of separating device depends on the temperature of using in the thermo-cracking step, but preferably 370-470 ℃ of this temperature, more preferably 400-440 ℃.The fractionator of the step I of preferred embodiment in ii) be atmospheric fractionator preferably, preferably 350-450 ℃ of the temperature that wax overhead product cut is extracted out from fractionator, more preferably 370-420 ℃.The wax overhead product is cracking under the temperature higher than residual oil raw material temperature preferably, preferably 470-550 ℃ of this temperature, more preferably 500-520 ℃.
Thermal tar feedstock of the present invention is the raw material of not hydrotreatment." the not raw material of hydrotreatment " represents the hydrogen processing of no use of this raw material, for example, handles in the catalytic hydroprocessing device.Raw material is carried out the hydrotreatment meeting reduce its carbon content and density.Can think that this is disadvantageous for producing binders for electrodes, because binders for electrodes preferably has very high carbon content and obtains high density therefrom.
In step of the present invention (a), thermal tar feedstock is carried out thermo-cracking.Those of ordinary skills can understand, and the cracking condition of step (a) can change with the kind of thermal tar feedstock, the equipment that thermo-cracking is used.But thermo-cracking is preferably carried out under 400-550 ℃ cracking temperature.
Can be in pyrolyzer easily with the thermal tar feedstock cracking.When using pyrolyzer, preferably raw material is heated to 400-550 ℃, more preferably 450-500 ℃.The residence time in pyrolyzer can change with raw material and cracking temperature, but when refining operation, the suitable residence time is 1-10 minute, preferred 1-5 minute.
The thermo-cracking of step (a) is preferably carried out in the soaking drum unit.The soaking drum unit comprises pyrolyzer and soaking drum (reaction chamber).When cracking in the soaking drum unit, in pyrolyzer, thermal tar is heated to cracking temperature, then it is transferred to soaking drum (reaction chamber), most of scission reactions are carried out in soaking drum.When using the soaking drum unit, in pyrolyzer, preferably raw material is heated to 400-500 ℃, more preferably 450-500 ℃, most preferably 475-500 ℃, it is transferred in the reactor of soaking drum then.Preferably the reactor pressure with soaking drum is controlled to be 100kPa-1000kPa, more preferably 150kPa-500kPa, most preferably 200kPa-300kPa; The preferably 10-120 minute residence time, more preferably 15-60 minute, most preferably 20-40 minute.
In the method for the invention, when raw material be hot gas oil unit produce thermal tar the time, it is effective especially to carry out thermo-cracking in the soaking drum unit.
Thermo-cracking product with step (a) in separator is separated into overhead fraction and bottom fraction [step (b)] at least.
Separator of the present invention can be the thermo-cracking product separation can be become overhead fraction and bottom fraction, promptly comprises the lighter fraction (overhead fraction) of light molecule and comprises any device of the residue oil fraction (bottom fraction) of weight molecule.The example that can be used as the device of separator comprises atmospheric distillation unit and cyclonic separator.No matter the type of the separator that uses how, bottom fraction preferably includes the component that the atmospheric boiling point of 80wt% at least is at least 300 ℃.Separating step (b) is a key character of the present invention, because only remove a part before than light material in rectification under vacuum step (c), just may prepare and has industrial acceptable performance and the low binders for electrodes of PAC content.
The separator of step (b) is cyclonic separator preferably.When using cyclonic separator, the thermo-cracking product separation of step (a) becomes gas fraction (overhead fraction) and liquid distillate (bottom fraction).Preferably with the thermo-cracking product separation of cyclonic separator with step (a), because the viscosity height of this material (instant heating cracked thermal tar), when adding rectifier unit, the thermo-cracking product may stop up rectifier unit, even coking in rectifier unit.
Those of ordinary skills can understand, and the temperature that enters the cracking material of separator depends on cracking condition.But when using cyclonic separator in the separating step (b), enter preferably 350-450 ℃ of the temperature of the thermo-cracking product of cyclonic separator, more preferably 380-430 ℃.Preferably 30 seconds-20 minutes the residence time in cyclonic separator, more preferably 30 seconds-8 minutes, even more preferably 1-6 minute.
Useful feature of the present invention is not need any part recirculation with the bottom fraction of separating step (b) by thermo-cracking step (a).Therefore, in preferred version of the present invention, the bottom fraction of separating step (b) is not carried out recirculation by thermo-cracking step (a).
The bottom fraction that separator produces is carried out rectification under vacuum, and the residual oil of this rectification under vacuum is exactly binders for electrodes of the present invention [step (c)].
Those of ordinary skills can understand, and the condition of rectification under vacuum can change with the type and the performance of raw material properties and the binders for electrodes that will produce, in order to set up best rectifying condition, need carry out experiment to a certain degree.But the optimum condition of rectification under vacuum is to make them corresponding to 450-550 ℃, more preferably 480-520 ℃ atmospheric boiling point, wherein, the conversion of atmospheric boiling point and low pressure boiling point is according to Ind.Eng.Chem., 49 (1957), the Maxwell-Bonell relational expression described in the pp1187-1196 is carried out.
In general, the rectification under vacuum of bottom fraction can be carried out under the pressure of 0.3-16kPa easily, and this pressure is more preferably 1-10kPa, even more preferably 1-8kPa, most preferably 3-7kPa; Preferably 310-400 ℃ of rectification temperature, more preferably 350-390 ℃.
Those of ordinary skills can understand, and the carbon content of binders for electrodes should be high as far as possible.This is because when the preparation electrode, binding agent will be converted into charcoal.Therefore, preferably the condition of using in thermo-cracking, separation and the rectification under vacuum step is optimized, makes that the remaining experiment of little carbon (MCRT) value of binders for electrodes is 45wt% at least; More preferably be 50wt% (measuring) at least according to DIN EN ISO 10370.
Binders for electrodes of the present invention can comprise the rectification under vacuum residual oil from the single process-stream of the present invention, also can comprise two or more mixture of this rectification under vacuum residual oil easily.Also can use the mixture of two or more different rectification under vacuum residual oil prepared in accordance with the present invention easily, to optimize the performance of binders for electrodes.
Compare with foregoing petroleum base binding agent with coal-tar pitch, a useful feature of the present invention is that this binders for electrodes includes only a small amount of PAC molecule.Benzo in the binders for electrodes of the present invention [a] pyrene content preferably is lower than 200ppm, more preferably less than 100ppm, most preferably is lower than 50ppm, and this benzo [a] pyrene content is measured according to IP BN/93.
The PAC content of binders for electrodes preferably is lower than 2000ppm, more preferably less than 1000ppm, most preferably is lower than 750ppm, and this PAC content is the PAC molecular assay enumerated based on embodiment 1-4 according to IP BN/93.
The sulphur content that another preferred feature of the present invention is a binders for electrodes is low, and the sulphur content of binders for electrodes preferably is lower than 2wt%, and more preferably less than 1wt%, this sulphur content is measured according to ASTM 2622-94.
The present invention also provides the binders for electrodes that can obtain with method of the present invention.
The present invention also provides and can produce the anode binding agent of aluminium and this anode binding agent in the application of producing aluminium with method of the present invention being used for of obtaining.
Can further understand the present invention by following exemplary embodiments.
In the following embodiments, if do not particularly point out, density value all is according to the determination of experimental method of DIN 52004 under 25 ℃; The remaining experiment of little carbon (MCRT) value is according to the determination of experimental method of DIN EN ISO10370; Sulphur content is according to the determination of experimental method of ASTM D 2622-94; Softening temperature is according to the determination of experimental method of DIN 52011; Viscosity number is measured with dynamic shear rheometer under specified temperature.
Total aromatic content is to measure according to Shell Method Series (SMS) 2783-95 (Research Disclosure 451104, November calendar year 2001,451 phases, 1918-1922 page or leaf), and based on existing 1-6 +The total amount of aromatic substance.SMS 2783-95 is based on the ultraviolet quantitative analysis method of ASTM E169-99.The ultraviolet spectrometer that uses is single bundle instrument (Varian Cary 50), and the bandwidth at the 220nm place is 1.0nm or littler; The luminosity repeatability is 0.5% transmissivity, and wavelength width of a slit is 2nm.Dispose the stopper silica cell that match of path length on the spectrograph through examining.Measure the light absorption ratio maximum value at three wavelength location places: 190-205nm (λ 1): 218-238nm (λ 2): 245-265nm (λ 3), these three positions correspond respectively to the absorption band of list, two and three aromatic substance.From the described crest maximum value of SMS 2783-95 λ 3Can infer the wavelength location of more senior aromatic substance.With the described method of SMS 2783-95, utilize No. 1 computation program that the data of the peaked specific absorption of each light absorption ratio are associated with the data of the correcting sample of concentration known and can calculate the amount of every kind of aromatic substance.
Measure PAC content according to IP BN/93, wherein, laboratory sample is being filtered on the silicon-dioxide, filtering on silicon-dioxide with heptane with toluene successively; With high performance liquid chromatography (HPLC) the PAC material is separated with aliphatic series, cycloparaffin series, list and two aromatic hydrocarbons; With GC-MS each PAC material is identified and quantitative analysis then.When analyzing, use 12Deutorated benzo [a] pyrene as interior mark.The PAC material of measuring when measuring PAC content is as follows: fluoranthene; Pyrene; Benzo [a] fluorenes; Benzo [b+c] fluorenes; Benzo [b] naphtho-[2,1-d] thiophene; Benzo [g, h, i] fluoranthene; Benzo [a] anthracene; and benzophenanthrene; 1+2+3+4+5+6 methyl ; Benzo [b, j, k] fluoranthene; Benzo [e] pyrene; Benzo [a] pyrene; Perylene; Hexichol [a, j] anthracene; Indeno [1,2,3-c, d] pyrene; Hexichol [a, h+a, c] anthracene; Benzo [b] ; Benzo [g, h, i] perylene; Dibenzo pyrene is with guan.
Embodiment 1-4: preparation binders for electrodes
Prepare binders for electrodes (embodiment 1) with raw material of the present invention and method.In addition, prepare comparative binders (embodiment 2-4) with other types of feedstock.The raw material that embodiment 1-4 uses is:
Embodiment 1:(the present invention) raw material (A).Two sections thermal tars (aromatic content is 49.5wt%) that hot gas oil unit is produced.
Embodiment 2:(contrast) raw material (B).Clarified oil, this is a kind of high aromatic content oil (aromatic content is 76.0wt%), the residual oil of producing for the atmospheric fractionator of catalytic cracking unit.
Embodiment 3:(contrast) raw material (C).From the vacuum residuum of the North Sea (North Sea) crude oil, this is the unitary bottoms of rectification under vacuum (aromatic content is 30.4wt%).
Embodiment 4:(contrast) raw material (D).Ethylene cracking device residual oil (ECR), this is from the residual oil of the unitary atmospheric fractionator of ethylene cracking device (aromatic content is 70.7wt%).
The performance of raw material A-D is shown in table 1.
Table 1
Raw material Thermal tar (A) Clarified oil (B) Vacuum residuum (C) ?ECR(D)
Density (g/cm 3) MCRT (wt%) sulphur (wt%) softening temperature (℃) viscosity (mm 80 ℃ times 2/ s) the total aromatic content (wt%) of PAC (ppm) vanadium (ppm) nickel (ppm) 1.029 12.5 0.72 liquid 248 6800＜5＜5 49.5 1.119 13.5 2.50 liquid 56 20,132 33 76.0 ?1.018 ?21.6 ?2.20 ?51.0 ?32718 ?34 ?95 ?25 ?30.4 ?1.137 ?25.0 ?0.23 ?44.5 ?5191 ?32472 ?＜1 ?＜1 ?70.7
With following method raw material A-D is made binders for electrodes.
Raw material is stored in the heavy oil weigh tank through after the filter manifold.Raw material is pumped into pyrolyzer from weigh tank.Pyrolyzer comprises eight isolating coil pipes, and each coil pipe all is immersed in the lead bath, and each lead bath is respectively with an electric heater heating.The cumulative volume of these coil pipes is about 3000cm 3The residence time of raw material in stove depended on material density and input speed, but input speed is when being 5kg/h, and the residence time is about 40 minutes, and when input speed was 2.5kg/h, the residence time was about 80 minutes.
Through behind the pyrolyzer, all thermo-cracking products all join in the flashing tower separator, and overhead vapours, butane and lighting end are removed.Bottom fraction (bottom fraction of fractionator) with separator adds vacuum column then, is divided into two cuts again by vacuum flashing, and promptly overhead fraction and residue oil fraction collect residue oil fraction as binders for electrodes.
The condition of using in the output of binders for electrodes and performance and pyrolyzer and the vacuum flasher is shown in table 2.For each raw material, with condition optimizing, to obtain the binders for electrodes that the MCRT value is 45wt% at least.In embodiment 1 (raw material (A)), moved twice, obtain two kinds of binding agents (A1) and (A2).Equally, in embodiment 2 (raw material (B)), moved twice, obtained two kinds of binding agents (B1) and (B2).
Table 2
Embodiment 1 Embodiment 2 (contrast) Embodiment 3 (contrast) Embodiment 4 (contrast)
Raw material Thermal tar (A) Clarified oil (B) Vacuum residuum (C) ECR(D)
Binding agent performance PAC (ppm) benzo [a] pyrene (ppm) MCRT (wt%) density (g/cm 3) softening temperature (℃) viscosity (mPas) sulphur (wt%) vanadium (ppm) nickel (ppm) 180 ℃ times ?A1 ?620 ?51 ?53.7 ?1.150 ?133.0 ?11818 ?0.74 ?＜10 ?＜10 ?A2 ?1390 ?120 ?46.4 ?1.142 ?110.0 ?116?3 ?0.74 ?＜10 ?14 ?B1 ?2050 ?200 ?63.4 ?1.203 ?159.0 ?NT ?2.3 ?＜10 ?26 ?B2 ?9748 ?590 ?41.4 ?1.222 ?97 ?118 ?2.5 ?＜10 ?24 ?C1 ?5 ?1 ?51.8 ?1.094 ?138.5 ?23961 ?2.5 ?245 ?81 ?D1 ?20000 ?1600 ?62.0 ?1.213 ?＞160 ?NT ?0.13 ?＜10 ?14
Operational condition
The highest coil temperature of feed rate (Kg/h) (℃) the vacuum column temperature (℃) vacuum column pressure (kPa) binding agent productive rate (%) ?2.5 ?465 ?363 ?1.6 ?29 ?2.5 ?457 ?362 ?1.6 ?33 ?2.5 ?438 ?347 ?2.5 ?25 ?2.5 ?440 ?349 ?3.3 ?25 ?5.0 ?487 ?373 ?1.1 ?40 ?2.5 ?443 ?347 ?6.1 ?46
NT=is test not
As can be seen from Table 2: binders for electrodes (A1) and sulphur content (A2) with the thermal tar feedstock preparation among the embodiment 1 are low, and PAC/ benzo [a] pyrene content is low.In this respect, it is than the binding agent (B1) of using the clarified oil feedstock production among the embodiment 2 and (B2) good, binding agent (B1) and sulphur content (B2) and PAC content height; It is better than the binders for electrodes (D1) with the preparation of ethylene cracking device residual oil raw material among the embodiment 4, and the PAC content of binding agent (D1) is higher; Though the PAC content of the binders for electrodes (C1) for preparing with vacuum residuum feed among the embodiment 3 is low, the density of the binding agent that obtains is very low.
Embodiment 5-9: preparation and test laboratory electrode
Binders for electrodes preparation experiment electrode with embodiment 1-4.
In embodiment 5 (the present invention), prepare electrode with binding agent (A1) and mixture (A2).Equally, in embodiment 6, prepare comparison electrode with binding agent (B1) and mixture (B2).In embodiment 8 can not preparation experiment chamber other electrode of level because D1 self is too sticking, so that binding agent (D1) mix with the overhead fraction (OH) that obtains by vacuum column on a small quantity.Prepare another kind of comparison electrode (embodiment 9) with coal-tar pitch binder.The composition and the performance that are used for the binding agent of preparation experiment electrode are shown in table 3.
With following method preparation experiment electrode.With the preheating of classification refinery coke, preheating temperature is higher 110 ℃ than the softening temperature of used binding agent at least.Then refinery coke is placed in the mixing tank of same preheating, the binding agent of cold pulverizing is sneaked in the preheated petroleum coke.Stir always,, then mixture transferred in the preheating punching block until obtaining uniform mixture, with water pressure engine with about 10 tons pressure with electrode moulding.Electrode comprises the binding agent of 14wt%, the coarse grain refinery coke of 19.7wt%, the middle grain refinery coke of 26.5wt%, the bird's eye gravel oil coke of 15.8wt% and the powder refinery coke of 24wt%.
With electric furnace baking process(of sulfonation) calcining electrode, be to cure 24 hours under 1190 ℃ the temperature in outlet temperature.In the process of curing, by covering refinery coke and not oxidated with the method guard electrode of nitrogen purging electric furnace.Then according to people such as Fischer W.K. at Journal of Metals39 (11), 43-45, the air reactive and the carbon dioxide reaction of the method test electrode described in 1987.According to testing method DIN 51919 its resistance of test.The results are shown in table 3.
Table 3
Embodiment 5 Embodiment 6 (contrast) Embodiment 7 (contrast) Embodiment 8 (contrast) Embodiment 9 (contrast)
Viscosity (mPas) softening temperature during 180 ℃ of binding agent PAC (ppm) benzo [a] pyrenes (ppm) (℃) MCRT (wt%) ?A1(85wt％) ?A2(15wt％) ?736 ?61 ?6.940 ?130.5 ?52.6 ?B1(55wt％) ?B2(45wt％) ?5514 ?376 ?2.850 ?135.5 ?54.8 ?C1(100wt％) ?5 ?1 ?12.381 ?131 ?50.3 ?D1(87wt％) ?OH(13wt％) ?20000 ?1600 ?7.640 ?129 ?53.6 Coal-tar pitch (100wt%) 97,800 10,900 1.032 115.5 54.7
Electrode air reactive (the remaining rate of %) a)CO 2Reactive (the remaining rate of %) b)Resistance (μ Ω m) ?92.5 ?85.2 ?70.4 ?94.3 ?86.4 ?69.0 ?73.2 ?82.3 ?80.9 ?92.7 ?83.5 ?79.5 ?92.7 ?82.3 ?78.5
A) air reactive=100 * (quality before the experiment/experiment back quality)
B) CO 2Reactive=100 * (quality before the experiment/experiment back quality)
NT=is test not
As shown in Table 3: among the embodiment 5 by the electrode of the present invention preparation with the low-down adhesive preparation of PAC/ benzo [a] pyrene content, its air reactive, carbon dioxide reaction and ohmically performance are all similar with the traditional electrode (embodiment 9) for preparing with coal-tar pitch.
Embodiment 6 and 8 electrode are with the high adhesive preparation of PAC/ benzo [a] pyrene content, consider from the EHS aspect that therefore they are not suitable for using.Though the electrode of embodiment 7 is to use the low adhesive preparation of PAC content, its air reactive is low, and therefore the electrode alternative coal-tar pitch in aluminium and steel industry with this adhesive preparation is unacceptable.
Embodiment 10
Thermal tar with the atmospheric fractionator bottom of taking from two sections hot gas oil unit (TGU) prepares binders for electrodes.The preparation method of binders for electrodes is as follows: by pyrolyzer (temperature is 480 ℃) with the thermal tar thermo-cracking, (pressure is 2.5bar (250kPa) through the reactor of soaking drum to make the thermo-cracking product, the residence time is 25-35 minute, temperature is 450 ℃), in cyclonic separator (temperature in is 390 ℃), the thermo-cracking product separation become overhead fraction and bottom fraction (residence time is 4-6 minute), in vacuum flasher (temperature is 370 ℃, and pressure is 55mbar (5.5kPa)), bottom fraction is carried out rectification under vacuum.Thermal tar feedstock is shown in table 4 with the performance of the binders for electrodes that obtains.
Prepare electrode with the method identical with the binders for electrodes of embodiment 10 with embodiment 5-9; The air reactive of test electrode, carbon dioxide reaction and resistance the results are shown in table 4 then.
As can be seen from Table 4: PAC/ benzo [a] the pyrene content of the binding agent of embodiment 10 is low, with air reactive, carbon dioxide reaction and the resistance of the electrode of this adhesive preparation and similar with the electrode of coal-tar pitch preparation.
Table 4
Embodiment 10 Thermal tar feedstock Binders for electrodes Electrode
PAC (ppm) benzo [a] pyrene (ppm) density (g/cm 3) MCRT (wt%) sulphur (wt%) softening temperature (℃) viscosity (mPas) during 180 ℃ of total aromatic contents (wt%) 1,163 86 1.001 11.5 1.11 liquid, 34 NT ?622 ?73 ?1.167 ?51.6 ?1.2 ?127 ?NT ?4.468 ?NT ?NT ?NT ?NT ?NT ?NT ?NT ?NT
Air reactive (the remaining rate of %) CO 2Reactive (the remaining rate of %) resistance (μ Ω m) ?NT ?NT ?NT ?NT ?NT ?NT ?91.8(92.7)* ?84.1(82.3)* ?79.8(78.5)*
* the value in the bracket is to use the value (embodiment 9) of the electrode of the binders for electrodes preparation that is prepared by coal-tar pitch

Claims (10)

1, a kind of preparation method of binders for electrodes, this method comprises:
(a) aromatic content is lower than the thermal tar feedstock thermo-cracking of the not hydrotreatment of 65wt%;
(b) in separator, the thermo-cracking product of step (a) is separated into overhead fraction and bottom fraction at least; With
(c) bottom fraction of step (b) is carried out rectification under vacuum, thereby obtain binders for electrodes as rectification under vacuum residual oil.
2, according to the process of claim 1 wherein that thermal tar feedstock is come the residual oil of self-heating gas oil unit.
3, according to the method for claim 1 or 2, wherein, thermal tar feedstock is the thermo-cracking residual oil of wax overhead product raw material.
4, according to each method of claim 1-3, wherein, the separator of step (b) is a cyclonic separator.
5, according to each method of claim 1-4, wherein, thermal tar feedstock is carried out thermo-cracking in the soaking drum unit.
6, according to each method of claim 1-5, wherein, the sulphur content of binders for electrodes is lower than 2wt%.
7, according to each method of claim 1-6, wherein, the PAC content of binders for electrodes is lower than 1000ppm.
8, according to each method of claim 1-7, wherein, the benzo of electrode sticky agent [a] pyrene content is lower than 200ppm.
9. the binders for electrodes that obtains according to each method of claim 1-8.
10. the application of anode binding agent in aluminium is produced that obtains according to each method of claim 1-8.
CNB028235010A 2001-11-26 2002-11-26 Electrode binder Expired - Fee Related CN100350016C (en)

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US1379423A (en) * 1919-09-18 1921-05-24 Leslie E Trimm Automobile-wheel-locking device
US2772219A (en) * 1954-10-05 1956-11-27 Exxon Research Engineering Co Production of binders for carbon electrodes from petroleum sources
US3318801A (en) * 1963-10-01 1967-05-09 Monsanto Co Production of petroleum base pitch and aromatic oils
US3537976A (en) * 1968-09-30 1970-11-03 Monsanto Co Process for preparing binder pitches
GB1178528A (en) * 1968-10-03 1970-01-21 Shell Int Research Combined Preparation of Electrode Binder Pitch and Carbon Black Feedstock
US3725240A (en) * 1971-05-13 1973-04-03 Mobil Oil Corp Process for producing electrode binder asphalt
JPS5281321A (en) * 1975-12-09 1977-07-07 Koa Oil Co Ltd Method of manufacturing binder pitch from petroleum heavy hydrocarbons
NL190815C (en) * 1978-07-07 1994-09-01 Shell Int Research Process for the preparation of gas oil.
US4522701A (en) * 1982-02-11 1985-06-11 E. I. Du Pont De Nemours And Company Process for preparing an anisotropic aromatic pitch
JPS61103989A (en) * 1984-10-29 1986-05-22 Maruzen Sekiyu Kagaku Kk Production of pitch for manufacture of carbon product
JPS61163992A (en) * 1985-01-16 1986-07-24 Fuji Standard Res Kk Continuously producing pitch suitable for use as raw material of carbon fiber
US4931162A (en) * 1987-10-09 1990-06-05 Conoco Inc. Process for producing clean distillate pitch and/or mesophase pitch for use in the production of carbon filters

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