CN85107441A - Coal tar hydrogenation catalyst carries out the method for coal tar hydrogenating and the method for being produced super needle coke by the hydrogenation products of coal tar with this catalyzer - Google Patents
Coal tar hydrogenation catalyst carries out the method for coal tar hydrogenating and the method for being produced super needle coke by the hydrogenation products of coal tar with this catalyzer Download PDFInfo
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- CN85107441A CN85107441A CN85107441.3A CN85107441A CN85107441A CN 85107441 A CN85107441 A CN 85107441A CN 85107441 A CN85107441 A CN 85107441A CN 85107441 A CN85107441 A CN 85107441A
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Abstract
This paper describes a kind of catalyzer of handling coal tar with hydrogen, be characterized in that molybdenum oxide accounts for 10～30% of total catalyst weight as catalyzer first component, nickel and (or) cobalt accounts for 1～6% as catalyzer second component, and be stated from mainly and form on the porous inorganic matrix by aluminum oxide or silicon.Another characteristics are the about 8-18 millimicrons of the mean sizes in its aperture, and the pore size distribution situation is respectively described in specification sheets and the claim, and the total surface area in these holes is above 100 meters
2/ gram.This paper has also described the use catalyzer and has carried out the method for hydrogen processing and the method that production is applicable to the super acicular coke of preparation Graphite Electrodes, and this method is to make winterized stearin handled and delayed coking by hydrogen.
Description
The present invention relates to coal tar and with the hydrogenation catalyst of the coal-tar pitch separated in the coal tar or the heavy oil that from coal and other similar resource, obtains; Relate to this catalyzer and carry out the method for hydrogenation and relate to by hydrogenation products and produce high-quality needle coke or super needle coke.
In Japanese publication communique (122585/1984), stated the hydrogen addition technology of coal tar, by the high material of hydrogenation products productive value, for example be used to make the coke of Graphite Electrodes.Under the ultra high power operation and Flashmelt operational condition of electric furnace, kind electrode can have good performance.
For example, in Japanese publication communique (13670/1976), stated that the catalyzer of forming with various metals makes the improvement technology of the raw material denitrogenation of taking from coal tar.
, the there does not relate to the toxic action of basic nitrogen compound to catalyzer, and these compounds for example, when pyridine, quinoline or acridine are taken from the raw material of coal tar in employing, must be paid attention to.For example can people can worry keep stable katalysis in the long-term operation process.
In Japanese patent gazette (19878/1982) as the method for the material of hydrotreatment pitch shape, also stated relevant catalyzer, it can suppress the hydrogenation Decomposition of aromatic hydrocarbons nuclear itself to lesser extent, and can be decomposed into low molecular weight product to condensed aromatics selectively.Therefore, this situation is distinctive, because hydrogenation does not take place the intermediate-coal tar of pitch shape material.
Usually 430 °-470 ℃ of coking temperatures or about scope in, raw material is carried out coking handles the carbon material that makes, as the thick needle coke or the needle coke of giving birth to, by the hexagonal crystal system, the trickle brilliant aggregate of graphite-like constitutes, median size is 1nm.Be used for making the required needle coke of high-quality Graphite Electrodes, its character depends on the orientation of these crystallites in known mode and acts on the bonding force of these microcrystals.
The formation of these crystallites is subjected to having the influence that optically anisotropic mesophase ball generates state significantly in known mode.By the heating of coking raw material, bead is coalescent and generate loose intermediate phase, obtains the predecessor of coke at last.
On the other hand, mesophase ball is subjected to the influence of some factors, and for example the composition of coking raw material hinders the impurity that mesophase ball increases, and pyrogenic condition.Therefore in order to obtain high-quality needle coke, determine unique condition and structure, anything but a nothing the matter.
Therefore, the primary condition of the needle coke of the high-grade Graphite Electrodes that is used for the ultra high power operation of preparation is: classification carefully or selection and refining coking raw material.
For example, in Japanese patent gazette (78201/1977), stated by selecting and the ratio of coal-tar pitch blended aromatic solvent and the conventional delayed coking coke cleaning gained material by the preparation needle coke, quinoline insolubles in the coal-tar pitch is separated or removed.In Japanese publication communique (28501/1977), stated with solvent the quinoline insolubles component has been removed from the hydrocarbon polymer that contains above-mentioned quinoline insolubles and condensed cyclic hydrocarbon compounds.Accounting for percent by volume is 95(ASTM) the boiling point of solvent be lower than 330 ℃, its BMCI value is in the scope of 5-70.By conventional producing needle coke by utilizing delay coking charcoal, remove the material that desolvates and generated then.
Be noted that the method for stating is as removing quinoline insolubles in these two patent gazettes.When the coking raw material that utilizes these two kinds of method preparations is produced coke, might obtain high-grade needle coke aspect thermal expansivity., when preparing Graphite Electrodes, find to have our undesirable expansion or puffing according to vertical greying system.
Also there is this puffing for needle coke.Needle coke basically be that the coke that raw material makes has identical grade by the coking raw material that obtains in the petroleum resources.But for petroleum coke, this puffing mainly is owing to contain sulphur in coke, and in general, makes anti-puffing agent by adding ferric oxide, is easy to control this puffing.
Everybody also knows, is that the Graphite Electrodes of the excellent needle coke manufacturing that makes of material that resource obtains has excellent mechanical intensity with the coal.But, and to compare with the similar products like of petroleum resources manufacturing, the toughness of Graphite Electrodes is relatively poor.
Although be not the definite clear reason that causes these defectives, it is generally acknowledged, be included in heteroatoms in the coke such as nitrogen, oxygen or the desorption gas of sulphur formation and the structure of carbon material and in the graphitizing process of electrode, play a part certain.
Therefore, can infer at the coal tar of no quinoline insolubles or not have in the coal-tar pitch of quinoline insolubles that it is very important that the influence of some composition can become.These compositions help the formation and the growth of the measured intermediate phase of matter under lower coking temperature, make intermediate phase be grown to serve as to have the loose intermediate phase of fibrous texture simultaneously.But when the rising coking temperature, speed at the coal tar of no quinoline insolubles or the coking speed of not having these components in the pitch of quinoline insolubles, their hinder and produce the loose intermediate phase with fibrous texture.
In Japanese patent gazette (11442/1974), stated the method for improving coal-tar pitch, the asphalt stock that is about to have certain chemical structure carries out hydrogenation, and this chemical structure may produce easy graphited needle coke., even the material of Sheng Chaning is as coking raw material in this way, also can not produce super needle coke.
In Japanese patent gazette (41129/1971), stated the method for producing pitch coke by petroleum tar pitch and coal-tar pitch.According to this method, the at first alkylation of raw tar bituminous.In the presence of hydrogenation catalyst, tar-bitumen is carried out modification then.
Yet, use these methods, still comprise the quinoline insolubles component in the coking raw material, therefore can not obtain to be used for producing among the present invention the coking raw material of super needle coke.
In general, comprise the coal tar of no quinoline insolubles or do not have the shortening speed or the speed of response of various materials of the coal-tar pitch of quinoline insolubles, be somewhat dependent upon the speed of reactant to the catalyst pores diffusion.
From as can be known above, bigger aperture helps reactant and looses to the active site of hole, and this will be very desirable.On the other hand, the aperture of catalyzer is big more, and the active surface area of hole becomes more little, inevitably like this can reduce total reaction rate.
In addition, the high and high oil (for example coal tar) of aromaticity (fa) for asphalt content, the space is constantly stopped up by carbonaceous deposit material in the hole, and the result further reduces to enter the diffusibility of hole.Therefore, can not in the longer time, continue to keep the gratifying efficient of catalyzer in the initial stage.In principle, it is feasible increasing wide aperture size activity of such catalysts surface-area by the volume that increases hole.Increase volume of voids and can reduce the catalyst strength performance, thereby in the process of reactor that catalyzer is packed into, can cause the fragmentation of catalyzer, in operating process, because wearing and tearing, and make the catalyzer efflorescence.Thereby make it often can not obtain industrial application.
Summary of the present invention
Main purpose of the present invention provides coal tar, and it is the raw material of preparation coke.The coke that makes should be uniformly, its resistance, and thermal expansivity and Young's modulus are all low; The hydrotreatment or the process of hydrogenation catalyst and this catalyzer of use are provided; The method that is prepared coal tar by the winterized stearin that generates is provided.
For the problem of mentioning below getting rid of, the present inventor has carried out various investigation and research, and has obtained coal tar or coal-tar pitch and coal tar no quinoline insolubles or do not had the hydrotreating catalyst of the coal-tar pitch of quinoline insolubles.Here, molybdenum is as first catalyst component, and nickel and/or cobalt are stated from the porous inorganic oxide matrix as second catalyst component.This matrix is made of aluminum oxide or oxidation sial basically.Here, the metal oxide of first catalyst component accounts for the 10-30% of total catalyst weight, and the metal oxide of second catalyst component accounts for the 1-6% of total catalyst weight.The average pore size of catalyzer is about 8-18nm, and the distribution of pore dimension is as follows:
Pore dimension (nm) specific volume (cc/g)
3.5-5.0 ＜0.1
5.0-8.0 ＜0.3
8-10 0.2-0.5
18-30 ＜0.2
More than 30＜0.1
Total pore surface area amount is approximately greater than 100M
2/ g.Also obtain using this catalyzer and under specific hydroconversion condition, carried out the hydroprocessing process and the method that has obtained by the feedstock production super needle coke of (no quinoline insolubles) coal tar or (no quinoline insolubles) coal-tar pitch.
Especially when the average pore size of catalyzer is not in about 8-18nm scope, for example less than 8nm, reactant diffuses into the hole difficulty especially that becomes, and has therefore lost effective catalyst activity.Because the rate of diffusion of reactant determines speed of reaction just.In addition, to having the oil of very high aromaticity (fa) and very high asphalt content, the coal tar of coal tar or coal-tar pitch and no quinoline insolubles or do not have the coal-tar pitch of quinoline insolubles for example is because the deposition and the accumulation of carbonaceous material have reduced pore dimension.So more seriously hinder reactant and spread, because sedimentary carbonaceous material has stopped up the space of hole to hole.
On the other hand, when average pore size during greater than 18nm, to diffusion is favourable, but increase along with pore dimension, the surface-area of hole reduces, make the catalyst hydrogenation activity of per unit volume descend, and prolonged the carbonaceous predecessor such as the residence time of bituminous matter in hole, thereby increased the deposition of carbonaceous material at pore surface.Because the toxic action of carbonaceous material makes the activity of pore surface descend.
For the above reasons with various experimental datas, pore dimension is approximately less than 3.5nm, specific volume approximately less than 0.1cc/g and pore dimension scope at 5-8nm, specific volume is preferential desirable less than the catalyzer of 0.3cc/g approximately.
About the catalyzer of macrovoid size, the specific volume that preferably makes the catalyzer of pore dimension in about 18 to 30nm scopes is less than 0.2cc/g, make pore dimension greater than the specific volume of the catalyzer of 30nm less than 0.1cc/g.
In over a long time, just used about 4000 hours, catalyzer can continous-stable is in enough activity, and this will pay the utmost attention to.
In the context of the present invention, the value of average pore size is provided by following formula:
Average pore size (nm)=4 * PV * 1/SA
In the formula
PV represents the summation (cc/g) of the volume of voids of 3.5nm hole in the catalyzer per unit weight.
SA represents the summation (M of 3.5nm pore surface area in the catalyzer per unit weight
2/ g).
The pore dimension that more than provides, volume and surface-area record with automatic porosity meter (commodity are called Micromollifios Autopore 9200) and mercury penetration method (sees E.W.Washburn, Proc, Nat ' L.Acad.Sci., Vol.7,115(1921); H.L.Ritfer and L.E.Drake, Ind.Eng.Chem.Anal., VoL 17,782-787(1945); L.C.Drake, Ind.Eng.Chom.VoL.41,780(1949); H.P.Grace, J.Amor.Inst.Chem.Eng ' rs.VoL.2,307(1956)).
In fact, measurement is performed such: the surface tension of mercury (r) is 4.8 * 10
-5The N/m(480 dynes per centimeter), work contact angle (Q) is greater than 140 °, and absolute mercury pressure arrives 4200kg/cm at 0.098-412MPa(1
2(absolute pressure)) the interior variation of scope.
The pore size values that provides greater than 3.5nm is-the absolute mercury pressure of 4rcosQ/.
The catalyzer that the present invention uses is made up of one or more metals with hydride key, is stated from the porous matrix that aluminum oxide or alumino silica gel are main component.
Porous matrix can comprise various porous metal oxides, mainly contains aluminum oxide, alumino silica gel, aluminum oxide and aluminum oxide titanium.These often water the type of being cast as with the clay as the 3rd component.
Can from comprise metals such as chromium, molybdenum, tungsten, iron, cobalt and nickel, select to have the metal of hydrogenation activity.For example nickel molybdenum or nickel cobalt are stated from the aluminum oxide.
Be actually nitrate, vitriol, muriate, metal acid salt, complex salt soluble metallic salt compound dissolutions such as (complexing salts) in appropriate solvent, for example water, methyl alcohol and acetone, then by dipping, precipitation, kneading or ion-exchange, they are stated from the matrix, carry out drying according to a conventional method and dry.
The catalyzer that makes in this manner will carry out pre-treatment, to obtain the catalytic activity of appropriateness.
When adopting fixed bed catalyst, the coal-tar pitch of preferably selecting the coal tar of no quinoline insolubles for use or not having quinoline insolubles is as raw material, with the choking phenomenon that prevents catalyst surface with cause too early inactivation.When adopting fluidised bed system, raw material is unrestricted, can use arbitrarily raw material and can not give rise to trouble.
The temperature of reaction that coal tar hydrogenating is handled is 300-420 ℃, and hydrogen pressure is 3.92-17.6MPa, and liquid hourly space velocity is 0.2-2.0 hour
-1
The hydrogenated oil that produces adds tubular oven by this way, and when pressure for example was 2.45-3.92MPa, temperature out was 470-520 ℃, and heat scission reaction takes place in stove.From thermal cracking oil, remove light component and non-volatilization component like this.Under pressurization and 445-470 ℃ of condition, salvage stores is carried out delayed coking obtain required coke.
Here, if wish to obtain super needle coke, the selection of temperature is crucial.And temperature determine should be taken into account volatile combustible matter and other factors in the raw coke, for example, thermal expansivity, physical strength and Young's modulus of elasticity.Temperature range is preferably selected 445-470 ℃, better selects 450-465 ℃.
Coking pressure is generally enough at 0.196-0.98MPa, and the pyrogenic time is about 24 hours, about sometimes 36 hours.
In more detail, be benchmark with the raw material, its nitrogen content (to call the denitrogenation ratio in the following text) reduces＞15%, just as above generates winterized stearin.Along with this winterized stearin further carries out thermo-cracking in tubular oven, temperature out be 470-520 ℃ of pressure less than 3.92MPa, the cold residence time is 60-360 second.Further hot tearing of heavy-tailed fraction quilt in the winterized stearin like this, and be converted into lighter component.Then, thermal cracking oil added flashing tower when institute was generated, in temperature greater than 510 ℃ of pressure at 0.0049-0.294MPa(0.05-3.0kg/cm
2(pounds per square inch absolute (psia))) carry out flash distillation under the condition.Lightweight component in the thermal cracking oil is from the top extraction of flashing tower, and boiling point is in the bottom extraction from tower of 520-538 ℃ or higher non-volatile component, and obtains middle distillate.Fraction obtains the very high coking raw material of productive rate thus, so that carry out delayed coking.
According to practice of the present invention, can obtain following result:
I) in use, catalyzer of the present invention is stable, and in greater than 4000 hours, keep active to be higher than present level work-ing life at least.
II) catalyzer of the present invention can be used for preparing part or the hydrotreatment of the compound of hydrogenation fully that is contained in coal tar.
III) thermal expansivity of coke might remain on the thermal expansivity level suitable with super needle coke, and might be than producing under the much higher coking temperature condition of preparation high-grade needle coke.Therefore, in raw coke, might obtain desirable volatile fuel content.
IV) in the lower scope of denitrogenation ratio, may obtain the better anti-brilliant effect that expands than the method that only includes only hydrogenation.
V) can cause improving the whole homogeneity of coke more than, obtain preparing the coke more efficient methods.
The brief description of legend
Fig. 1 is illustrated in the hydrogenation process of coal-tar pitch of no quinoline insolubles, and sequence number is 1,2,3,4, and 5,6,7 change with the time correlation of 8 the relative hydrogenation activity of catalyzer.
It is that sequence number is 3,4,5,6, the relative hydrogenation activity of 7 and 8 catalyzer and the relation between the average pore size under 4000 hours situations that Fig. 2 is illustrated in oil-filled total time.
Fig. 3 represents not have the typical proton N MR(nucleus magnetic resonance of the coal-tar pitch winterized stearin of quinoline insolubles) spectrum.
Fig. 4 is illustrated in the coal-tar pitch hydrogenation process of no quinoline insolubles, and sequence number is 9 to change with the time correlation of the relative hydrogenation activity of 10 catalyzer.
Fig. 5 represents to be prepared by winterized stearin the process flow sheet of super needle coke.
The explanation of the concrete grammar of recommending
Example 1
Use eight kinds of different catalyzer (seeing hereinafter form for details) of forming, carry out hydrotreatment and have the coal-tar pitch of the no quinoline insolubles of routine character down.
The character of the coal-tar pitch of no quinoline insolubles
Proportion (15/4 ℃) 1.2381
mc7-I
1wt% 19.3
Kang La (carbon residue) is worth (wt%) 38.5
TI（wt%） 9.06
C，（wt%） 91.86
H，（wt%） 4.93
S，（wt%） 0.49
N，（wt%） 1.13
NC
7-1: N.heptane insolubles; TI: toluene insolubles.
As a hydrotreater, adopted catalyst fixed bed equipment, equipment mainly is made up of the stainless steel reaction pipe of the long 1000mm of internal diameter 25mm, and external diameter is that the thermowell of 8mm is passed down through reaction tubes with the center.And reaction tubes can be controlled pressure, temperature and flow rate automatically.
Reactor design becomes to have the type of heating of control.Heating is to realize by the aluminium block that is divided into six sections.
Stock oil measures with the integral form under meter, and oil after metering adds reactor by a compound reciprocation pump, and solution-air is in reactor and flow to current downflow.
Catalyst packing is 200cc, has 30cc inertia alumina balls, is packed into the top and the bottom of catalyst layer.The reaction zone effluent imports gas-liquid separator.Liquid is collected in the liquid product receptor through pressure controlled valve, and gas measures with wet flow indicator through behind the pressure controlled valve, discharge system after the technological process gas chromatographic analysis.
List the catalyzer in the table below in, in advance with the about 1%(wt of sulfur-bearing) and be added with about 24 hours of the Khafji oil treatment of di-t-butyl sulphur, temperature is 300 ℃, and pressure is 13.72MPa, and liquid hourly space velocity is 1.0 hours
-1, hydrogen/oil be 1000 standard liters/liter.
Therefore, using vulcanized catalyzer and changing hydroconversion condition is 360 ℃, 13-72MPa(140kg/cm
2Gauge pressure) liquid hourly space velocity is 0.5 hour
-1, hydrogen/oil be 1000 standard liters/liter.The hydrogenation activity of various catalyzer is compared, and its result is illustrated among Fig. 1 and 2.
Hydrogenation activity uses the relative response speed of calculating according to following formula (Kfa) to represent.This representation is next according to the hypothesis derivation of the obedience of the variation between the aromaticity of the aromaticity (fa) of product in hydrogenation process and stock oil first order kinetics.Aromaticity (fa) is regarded as the hydrogenation parameter, and available proton N MR spectrometry.
Kfa-LHSV
＊ln（fa，F/fa，P）
(fa, F) aromaticity of expression stock oil in the formula; (fa, P) aromaticity of expression product oil.
The JNM-GX270 type pulse Fourier transformation proton magnetic resonance (PMR) instrument that Japan Denshi limited-liability company makes is as the device of proton N MR, and data processing is to be undertaken by the robot calculator that is contained in the instrument.
In actual measurement, sample CS
2Solvent is mixed with about 3%(wt) concentration, use tetramethylsilane and 100% deuteriochloroform respectively as interior grade standard just and tacking agent synchronously again.
Condition determination is: 270, and 05MH
2Resonant frequency and 45 ° of pulses (pulse width is 6.8 μ Sec.), the 32K data point, observed spectral width is 4000H
2, pulse width is 3Sec., long-pending and time number is 8-10.(see K.Mullen and P.S.Precosin, " Fourier Transform NMR Technigues; Acaaemic Press; Inc.(London) Lta.(1976); T.C.Furrav and E.D.Beoker. " Pnlse and Fourier Tvansf-ovm NMR. " Academic Press Ic.(London) Ltd.(1971), fov pulse Fourier Transform Profon NMR Unifs).
In proton N MR spectrum, the identification of all kinds of hydrogen bondings is to determine according to the chemical shift (δ) that following formula is determined.
δ＝（H
r-H
β）/H
r
H in the formula
rAnd H
βThe resonant frequency of difference representative sample and tetramethylsilane.Though the δ value itself is nondimensional, it represents with PPm usually, because its expression is when being zero with respect to tetramethylsilane, and ppm of variation of resonant frequency.
Fig. 3 represents not have the coal-tar pitch of quinoline insolubles and the exemplary of winterized stearin NMR (Nuclear Magnetic Resonance) spectrum.These winterized stearin are to be core with condensed ring shape aromatic hydrocarbons, the mixture of chemical compound lot.Can be divided into following four groups, and each group has the specified range of the δ value relevant with the various bonding modes of hydrogen.According to the present invention, the spectral position of pure typical material is determined according to following document: and K.D.Bartie etc. (Fuel, voL.44,109(1965), and Fuel, VoL.54,226(1975), and Chem.Ind., VoL.5,313(1975); Anal.Cham.VoL.51,2189(1979)) and Mae Kawa etc. (NiKKashi, № 6,908(1980)).
The scope symbol hydrogen bond of δ (PPm)
0.5-1.0 H
rThe terminal methyl group of paraffinic hydrocarbons or be right after aromatic ring
R on the side chain or elevated hydrogen more.
1.0-2.0 H
βBe right after β on the side chain of aromatic ring or higher
The methylene radical hydrogen bond of position or the methylene of paraffinic hydrocarbons
Base or methyne hydrogen bond.
Naphthenic hydrocarbon hydrogen bond or be right after the β of aromatic ring or more
Naphthenic hydrocarbon hydrogen bond on the high position.
2.0-4.2 H
αThe methyl hydrogen bond of side chain on next-door neighbour's aromatic ring α position.
Be right after side chain on the aromatic ring α position methylene radical or
The methyne hydrogen bond, or be right after on the aromatic ring α position
The naphthenic hydrocarbon hydrogen bond.
6.2-9.2 H
αThe aromatic hydrocarbon ring hydrogen bond.
Four of hydrogen kinds of different bonding states can the quantitative percentage ratio that is estimated as hydrogen richness in the sample.This percentage ratio is calculated by the corresponding separately area of the chemical shift of above-mentioned proton N MR and gets.Also can infer and relevant coal tar or coal-tar pitch, the coal tar of no quinoline insolubles or do not have the coal-tar pitch of quinoline insolubles and the average chemical structural unit of winterized stearin (is seen J.K. Brown and W.R.Iandner, Fuol, VoL.39,79(1960); Fuel, VoL.39,87(1960); Takeya Nenryo Kagaku Kaishi, VoL.43,837(1964); R.B.Williams.ASTM STP 224,168(1958); J.G.Spreight, Fuel, Vol.49,76(1970); Fuel, Vol.50,102(1971).
In coal tar wet goods hydrogenation process aromaticity reduce available below formula quantitatively obtain:
f
a＝〔C/N-H
α/X-（H
β+H
α）/Y〕/（C/H）
C/H represents the ratio of hydrocarbon atom in the formula.In this case for proton 1
HBe converted into 13
C, parameter X and Y value can be assumed to and equal 2.
Example 2
Be numbered two kinds of catalyzer of 9 and 10 and be used to the coal-tar pitch that hydrotreatment does not have quinoline insolubles.It with example 1 in the coal-tar pitch of used no quinoline insolubles have identical physical properties.The average pore size of these two kinds of catalyzer and the volume of voids almost catalyzer with numbering 5 used in example 1 are identical, and different void distribution is only arranged, and the character of catalyst system therefor provides with the form of tabulation, and its catalytic performance also provides in Fig. 4.
The prevulcanized of catalyzer is identical with example 1 with hydroconversion condition.We can observe and be numbered 5 and 9 catalyzer and all be better than being numbered 10 catalyzer aspect active level and work-ing life.
Example 3
The production super needle coke device of representing in Fig. 5 can be used for coking.
In this device, the coal-tar pitch of no quinoline insolubles is by pipeline 1, through interchanger 2 heating, with the hydrogen that enters compressor room's 4 superchargings by pipeline 3 pipeline 6 and purity be 99.9%, the hydrogen mixing of interchanger 5 heating.Then, the mixture of formation is in the processing condition of process furnace 7 internal heating to hydrogenator.
Deliver to the top of hydrogenator 10 through the mixture of the coal-tar pitch of raw material-no quinoline insolubles of heating and hydrogen by coil pipe 8 and pipeline 9, be downward through beds then.Therefore because reaction is heat release,, by pipeline 19 and 20 cold hydrogen is added in the space between the beds and goes in order to cool off the temperature with controlling reactor.
The effluent of reactor 10 is 11 extraction by the road, send into preheater 2, deliver to hot flash tank 12 then.Effluent is separating liquid component and gas composition here.
Hot gas by the road 13 and interchanger 5 is sent into cold flash tank 16 after being cooled in air-cooler 14.Washing water are 15 upper reaches one sides that enter air-cooler 14 by the road.In cold flash tank 16, acidiferous water vapour is separated with liquid components.
Enter interchanger 27 heating from the winterized stearin of stripping tower 24 bottom extraction through pipeline 26, so that under above said condition, cracking in pyrocrack furnace 28.Thermal cracking oil is through coil pipe 29, pipeline 30 and pressure control valve 31 flash distillation in flash tank 32.Non-volatile component 33 is separated extraction by the road from flashing tower 32 bottoms, and light constituent adds the bottom of components training 35 through pipeline 34.
Coking furnace basin effluent adds the bottom of combination training 35 through pipeline 41.These two strands of materials are through fractionation, and heavy component is from pipeline 36 extraction.As the coking furnace charging, to for keeping the needed sufficient temp of pyrogenic reaction, join drum 40 through pipeline 39 then and carry out delayed coking at coil pipe 38 internal heating of coking heater 37.These drums 40 rotated on the basis at 24 hours and drive.
From the tail gas (pipeline 33) of combination training 35 top extraction, tar light oil (pipeline 44) and waste water (pipeline 45) reclaim through condenser.
Light ends reclaims through pipeline 46, and further is separated into carbolic oil, bitter edible plant oil and washing oil in separation system (this system does not show in the drawings).
Partly washing oil is used for the cooling heat cracked oil in pipeline 47, and the part heavy oil that takes out from pipeline 48 joins drum 40 extraction pipelines as refrigerant through pipeline 49.
The present invention will carry out pyrogenic concrete instance and illustrate because of the device of above statement.
The coal-tar pitch of no quinoline insolubles is as raw material, and its proportion is 1.2381(15/4 ℃), quinoline insolubles＜0.1%(wt), toluene insolubles is 9.06%(we), N.heptane insolubles is 19.3%(wt), sulphur is 0.49%(wt), nitrogen is 1.13%(wt), aromaticity is 0.96.Under following condition, carry out hydrogenation with the catalyzer (seeing Table 1) of numbering 5.
Hydroconversion condition
Hydrogen/stock oil NL/L 1000
Temperature of reaction ℃ 360
Reaction pressure MPa 17.64
Liquid hourly space velocity h
-1 r1.0
Below be the character of the hydrogenated liquid product that obtains:
The character that adds winterized stearin
Proportion (15/4 ℃) 1.1668
Quinoline insolubles wt% 0
N.heptane insolubles wt% 10.9
Toluene insolubles wt% 3.85
Sulphur wt% 0.11
Nitrogen wt% 0.79
Aromaticity 0.730
By these results as can be known, than being not contain quinoline insolubles in 30.1 the winterized stearin, but contain N.heptane insolubles and toluene insolubles for denitrogenation.All these components all are included in the heavy fraction that boiling point is higher than 459 ℃ unlimitedly.This heavy fraction accounts for the 48.5%(wt of winterized stearin) (N.heptane insolubles 23.5%(wt), toluene insolubles 7.36%(wt).Only managing the denitrogenation ratio is 30.1, and N.heptane insolubles and toluene insolubles are not all removed by hydrogenation.
Then, winterized stearin adds the thermo-cracking pipe.The pressure of thermo-cracking pipe is 2.45MPa(25kg/cm
2Gauge pressure), temperature is 500 ℃ (the cold residence time is 130 seconds).Then oil is added to flashing tower, keeping temperature is 500 ℃, and pressure is normal pressure.The extraction at the bottom of the tower of non-volatile component is separated from winterized stearin and boiling point is lower than 300 ℃ light component.Winterized stearin is then obtained by the steam cooling of cat head.Remaining oil is as coking raw material.Its character is as described below:
The character of coking raw material
Proportion (15/4 ℃) 1.1134
Quinoline insolubles wt% 0
N.heptane insolubles wt% 0.0
Toluene insolubles wt% 0
The coking raw material that makes like this is 455 ℃ of temperature, and pressure is 0.637MPa(6.5kg/cm
2Gauge pressure) and reflux ratio be under 0.7 the condition, to handle through delayed coking in 24 hours.
Handle in order to carry out delayed coking, the oil of packing into is used steam flushing later routinely.Reclaim then and obtain living coke (greew coke).In raw material, the productive rate of green coke charcoal is 30%(wt), volatile combustible content is 9.0%.
Then, the green coke charcoal then carries out fragmentation and grinding routinely 1000 ℃ of roastings 1.0 hours, adds pitch as tackiness agent, is kneaded into product.Extrude through the mixture of mediating and to be pressed into rod,, become graphite product 2700 ℃ of following greyings 1000 ℃ of bakings down.Below be physical properties through the graphite product of roasting:
Coke nature
Baked coke
True density (15/4 ℃) g/cc 2.152
Graphite product
Thermal expansivity (w.g.) * 10
-6/ ℃ 0.83
Magnetoresistance (MR), % 13.2
Flexural strength MPa 13.4
Young's modulus of elasticity kg/cm
280.85
Find out that from last table the true density of the coke that obtains through roasting is higher than 2.15, the coefficient of expansion of its graphite product is especially low, and the magnetoresistance height has good graphitizability and especially low Young's modulus of elasticity.With having Young's modulus of elasticity is 86.24-98MPa(880-1000kg/cm
2) or higher graphite product by petroleum resources production compare, more than these character be suitable.By the graphite product of petroleum resources production and the product of the present invention of following statement, the coefficient of expansion with same order.
In order to measure dynamic puffing (DP), above-mentioned baked coke is pulverized, filter out particle size distribution range respectively at the 35-65 order with less than 200 purpose particles, then by 67%(wt) 35-65 order and 33%(wt) the sample less than 200 purpose granulometric composition, after adding an amount of bonding pitch (pressure is 86.1MPa), be cast into core rod.The internal diameter of core rod is 4 English inch.Downcutting internal diameter is 1 English inch, the core pieces of long 1 English inch.
After prior size with micrometer measurement mode pellet, it is placed on the expander, in temperature 1200-2700 ℃ scope with its dimensional change of speed measurement of 14 ℃ of per minute temperature rises, to measure dynamic puffing (DP).(the △ L%'s when △ L% when △ L% represents top temperature and minimum temperature is poor for the DP value; △ L% represents the temperature variant percentage ratio of length), be meant negative percentage ratio at this paper, we can say that perhaps its expression does not have puffing.
The productive rate of the non-volatilization component of flasher is 18.7%(wt), quinoline insolubles component＜0.1%(wt) wherein.
Example 4
Except changing 460 ℃ of coking temperatures into 440 ℃ (A), 450 ℃ (B), 455 ℃ (C), 465 ℃ (D) and 470 ℃ (E) in addition, the process in this example is identical with example 1.It the results are shown in following table:
Coke property
Test number green coke charcoal graphite finished product
Volatile fuel wt% thermal expansivity, * 10
-6/ ℃; Magnetoresistance %
A 16.5 0.77 13.8
B 12.0 0.84 13.4
C 10.3 0.85 13.6
＊ 8.2 0.83 13.2
D 8.0 0.94 3.1
E 7.0 1.02 13.0
* be the data of example 4.
A, B and C represent to adopt that coking raw material is 440 ℃ at coking temperature in the example 1 in the last table, the result when 450 ℃ and 455 ℃.Because the coking speed of coking raw material is very slow, for the complete coking of material is become green coke charcoal state, 24 hours delayed coking is not enough.
For this reason, the volatile fuel in the green coke charcoal is fluctuation significantly in drum, and its mean value is higher than 10%(wt), this is for not being met the requirement of super needle coke to volatile combustible matter.
, all become the green coke charcoal with the bottom, therefore take out this part coke and measure its thermal expansivity and magnetoresistance at the middle part of drum.
Therefore, under these coking temperature conditions, though A, B and C sample industrial be worthless, it shows has removed the unwanted component of formation super needle coke.
Example 5
Except adopting following hydroconversion condition to replace in the example 4 those conditions, repeat the process of example 4.
Hydroconversion condition
Hydrogen/stock oil NL/L 1000
Temperature of reaction ℃ 360
Reaction pressure MPa(kg/cm
2Gauge pressure) 4.9(50)
Liquid hourly space velocity hr
-10.75
Below be the winterized stearin that makes and the character of coking raw material (the denitrogenation ratio is 15%).
The character of winterized stearin and coking raw material
The winterized stearin coking raw material
Proportion (15/4 ℃) 1.1922 1.1552
Quinoline insolubles wt.% 00
N.heptane insolubles wt.% 14.9 0.50
Toluene insolubles wt.% 5.40 0
Sulphur wt.% 0.19-
Nitrogen wt.% 0.96-
Thermal expansivity of graphite product (W.G.) and magnetoresistance are respectively 1.08 * 10
-6/ ℃ and 12.2%, these can be compared with excellent coke.
DP(△ L%) be positive 0.08.
Example 6
Prepare winterized stearin sample by hydroconversion condition in the Change Example 4 only: F, G, H and I with different denitrogenation ratios.Finally be prepared into graphite product with the method that repeats in the example 4.The character of these samples is as described below:
Coke property
Denitrogenation is than % thermal expansivity magnetoresistance % Young's modulus of elasticity
×10
-6/℃ MPa
F 23.1 0.91 13.0 72.52
＊ 34.5 0.83 13.2 80.85
G 37.6 0.84 13.4 84.28
H 42.5 0.85 14.0 88.2
I 76.1 0.78 13.8 110.74
* be the data of example 4
The unusual height of Young's modulus of elasticity value of test sample F-I is that we are undesirable.But the thermal expansivity of these samples and the value that the magnetoresistance value is seen super needle coke.Denitrogenation is higher more than low more magnetoresistance value, and the value of thermal expansivity is influenced hardly, and this is that we are desirable.
Comparison example
Employing has the stock oil (coal tar) of following character, without directly carrying out thermo-cracking as the hydrotreatment of carrying out in the example 4.The proportion of stock oil (15/4 ℃) is 1.1452, and quinoline insolubles＜0.1%(wt), toluene insolubles is 3.48%(wt), N.heptane insolubles is 11.0%(wt), sulphur is 0.44%(wt) and nitrogen be 0.98%(wt).In temperature is 480 ℃, and pressure is 2.45MPa(25kg/cm
2Gauge pressure) carries out thermo-cracking under the condition, enter flash tank then.The temperature of flash tank keeps 480 ℃, and pressure is normal pressure.Nonvolatile element is from the bottom extraction of flash tank, and from top extraction overhead product.Produce coking raw material from overhead product.The character of oil samples sees the following form:
The character of initial coking material
Proportion (15/4 ℃) 1.1638
Quinoline insolubles wt.% 0.1
N.heptane insolubles wt.% 3.2
Toluene insolubles wt.% 0.2
Sulphur wt.% 0.66
Nitrogen wt.% 1.10
5 differing tempss: 440,450,455,460 and 465 ℃ and pressure are 0.29MPa(3kg/cm
2Gauge pressure) respectively J, K, L, M and N sample are carried out delayed coking under the condition.The process of carrying out is identical with example 4 subsequently.
Coking condition and coke property
Test number J K L M N
Coking temperature ℃ 440 450 455 460 465
The green coke charcoal
Volatile fuel 16.4 10.0 9.7 8.3 7.0
wt.%
Graphite product
Thermal expansivity 0.93 1.06 1.17 1.20 1.43
×10
-6/℃
Magnetoresistance % 12.0 11.1 10.7 10.1 19.8
Be similar to example 6, the thermal expansivity of sample J and K and magnetoresistance are with the sample determination that takes out in the coking furnace in the last table.Wherein the high volatile fuel of content is removed.
Volatile fuel among sample L.M and the N is lower than 10%(wt), and the Coefficient of Thermal Expansion value of sample L and M is in the scope of high-grade needle coke Coefficient of Thermal Expansion value.Their magnetoresistance value is also lower.
The Coefficient of Thermal Expansion value of sample N is not less than the corresponding value of excellent needle coke.The difference of the thermal expansivity of sample J and N is big especially, equals 0.5.This explanation is just carried out thermo-cracking and flash distillation without hydrotreatment and is handled some the undesirable components can not sufficiently remove when coking raw material makes super needle coke.
Because the content of sulphur and nitrogen is changed in the process of coking raw material by raw material, do not change, therefore can not expect to reach the purpose of desulfurization and denitrogenation by thermo-cracking.Till the dynamic puffing of sample K (△ L%) 0.24%.
Example 7
The character of 280 of winterized stearin ℃ of heavy fractions is in example 4: proportion (15/4 ℃) 1.1219, quinoline insolubles 0.1%(wt), toluene insolubles 3.76%(wt), N.heptane insolubles 12.0%(wt) and, sulphur 0.11%(wt), nitrogen 0.75%(wt).This fraction temperature be 450 ℃ with pressure be 0.29MPa and other with example 4 in directly carry out delayed coking under the identical condition.It the results are shown in following table:
Coke property
The green coke charcoal
Volatile combustible matter wt.% 9.0
Graphite product
Thermal expansivity * 10
-6/ ℃ 1.11
Magnetoresistance % 11.5
Claims (9)
1, a kind of coal tar and hydrogen catalyst is characterized in that its first catalyst component is a molybdenum, second catalyst component be nickel and (or) cobalt, be stated from the matrix of porous inorganic oxide, matrix is made of aluminum chloride or alumino silica gel basically.Wherein first catalyst component (in metal oxide) accounts for the 10-30% (wt) of whole catalyzer, and second catalyst component (in metal oxide) accounts for 1-6% (wt).The average pore size of catalyzer is about 8-18nm, and pore size distribution sees the following form:
Pore dimension nm specific volume cc/g
3.5-5 ＜0.1
5-8 ＜0.3
8-18 0.2-0.5
18-30 ＜0.2
More than 30＜0.1
The total aperture surface area that records is approximately greater than 100m
2/ g.
2, according to the catalyzer described in the claim 1, it is characterized in that its first and second catalyst components are dissolved in water or other liquid medium, select then to be stated from the matrix with methods such as dipping, deposit, kneading or ion-exchanges.At 300 ℃, 13.7MPa(140kg/cm
2Gauge pressure), liquid hourly space velocity 1.0hr
-1, hydrogen/oil be 1000 standard liters/liter condition under the product that obtains is vulcanized.
3, the characteristics of coal tar hydrogenating process are: hydroconversion condition is hydrogen pressure 3.92-17.64MPa(40-180kg/cm
2Gauge pressure), temperature 300-320 ℃, liquid hourly space velocity 0.2-2.0hr
-1, the consisting of of used catalyzer: molybdenum oxide about 10-30%(wt), about 1-6%(wt) nickel oxide and (or) cobalt oxide is stated from the matrix.The average pore size of catalyzer is about 8-18nm, and the maximum diameter of hole distributes as follows:
Pore dimension nm specific volume cc/g
3.5-5 ＜0.1
5-8 ＜0.3
8-18 0.2-0.5
18-30 ＜0.2
＞30 ＜0.1
Pore dimension is that the above aperture surface area of 3.5nm is approximately greater than 100m
2/ g.
4, the characteristics of the method for production super needle coke are: it was made of several steps.By hydrotreatment by containing quinoline insolubles less than 0.1%(wt) the material that obtains of coal tar make hydrogenated oil.Used catalyzer is by about 10-30%(wt) molybdenum oxide and about 1-6%(wt) nickel oxide and (or) cobalt oxide formation.It is as follows that its average pore size approximates 8-18nm maximum pore distribution of sizes:
Pore dimension nm specific volume cc/g
3.5-5 ＜0.1
5-8 ＜0.3
8-18 0.2-0.5
18-30 ＜0.2
＞30 ＜0.1
Pore dimension is that the above aperture surface area of 3.5nm is approximately greater than 100m
2/ g.The pressure of winterized stearin thermo-cracking is lower than 3.92MPa(40kg/cm
2Gauge pressure), outlet temperature is lower than 470-520 ℃, and the cold residence time is 60-350 second.After from thermal cracking products, removing non-volatile component, obtain being used for producing the fraction of coking raw material, then in the delayed coking system at 450-465 ℃ and 0.196-0.98MPa(2-10kg/cm
2Gauge pressure) carrying out the coking of this coking raw material under the condition handles.
5, the method for production super needle coke according to claim 4 is characterized in that with the raw material being benchmark, and the denitrogenation ratio of setting winterized stearin is higher than 19.0%.
6, the method for production super needle coke according to claim 4 is characterized in that with the raw material being benchmark, and the denitrogenation of setting winterized stearin is than in the 22.5-46.5% scope.
7, the method for production super needle coke according to claim 4 is characterized in that with the charge raw material being benchmark, and the denitrogenation of setting winterized stearin is than in the 23.7-37.4% scope.
8, the method for production super needle coke according to claim 4 is characterized in that the requirement coking temperature is in 455-465 ℃ of scope.
9, the method for production super needle coke according to claim 4 is characterized in that setting the actual density of super needle coke greater than 2.14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59-218697 | 1984-10-19 | ||
| JP59218697A JPS6197035A (en) | 1984-10-19 | 1984-10-19 | Catalyst for hydrogenating coal tar and hydrogenating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85107441A true CN85107441A (en) | 1986-04-10 |
| CN1012503B CN1012503B (en) | 1991-05-01 |
Family
ID=16723995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107441 Expired CN1012503B (en) | 1984-10-19 | 1985-10-09 | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke, from the hydrogenation product of coal tar |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6197035A (en) |
| CN (1) | CN1012503B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477310A (en) * | 2010-11-25 | 2012-05-30 | 邵素英 | Method using coal tar to produce fuel oil |
| CN102149791B (en) * | 2008-09-09 | 2013-06-12 | 吉坤日矿日石能源株式会社 | Process for producing needle coke for graphite electrode and stock oil composition for use in the process |
| WO2013104092A1 (en) | 2012-01-12 | 2013-07-18 | 易高环保能源研究院有限公司 | Process for producing mesophase pitch by hydrogenation of high-temperature coal tar |
| US8741125B2 (en) | 2008-12-26 | 2014-06-03 | Jx Nippon Oil & Energy Corporation | Raw oil composition for negative electrode material for lithium ion secondary battery |
| CN111971370A (en) * | 2018-03-26 | 2020-11-20 | 日铁化学材料株式会社 | Raw oil for needle coke and needle coke |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008298263A (en) * | 2007-06-04 | 2008-12-11 | Nsk Warner Kk | Control method and control device of starting clutch |
| EP3746219A4 (en) * | 2018-01-31 | 2021-10-27 | Advanced Refining Technologies, LLC | Hydroprocessing catalyst for the reduction of metals and sulfur in heavy feeds |
-
1984
- 1984-10-19 JP JP59218697A patent/JPS6197035A/en active Granted
-
1985
- 1985-10-09 CN CN 85107441 patent/CN1012503B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149791B (en) * | 2008-09-09 | 2013-06-12 | 吉坤日矿日石能源株式会社 | Process for producing needle coke for graphite electrode and stock oil composition for use in the process |
| US8715484B2 (en) | 2008-09-09 | 2014-05-06 | Jx Nippon Oil & Energy Corporation | Process for producing needle coke for graphite electrode and stock oil composition for use in the process |
| US8741125B2 (en) | 2008-12-26 | 2014-06-03 | Jx Nippon Oil & Energy Corporation | Raw oil composition for negative electrode material for lithium ion secondary battery |
| CN102477310A (en) * | 2010-11-25 | 2012-05-30 | 邵素英 | Method using coal tar to produce fuel oil |
| WO2013104092A1 (en) | 2012-01-12 | 2013-07-18 | 易高环保能源研究院有限公司 | Process for producing mesophase pitch by hydrogenation of high-temperature coal tar |
| US9994775B2 (en) | 2012-01-12 | 2018-06-12 | Eco Environmental Energy Research Institute Limited | Process for producing mesophase pitch by hydrogenation of high-temperature coal tar |
| CN111971370A (en) * | 2018-03-26 | 2020-11-20 | 日铁化学材料株式会社 | Raw oil for needle coke and needle coke |
| CN111971370B (en) * | 2018-03-26 | 2022-03-11 | 日铁化学材料株式会社 | Raw oil for needle coke and needle coke |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0380059B2 (en) | 1991-12-20 |
| JPS6197035A (en) | 1986-05-15 |
| CN1012503B (en) | 1991-05-01 |
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