CA2012627C - Tandem quench - Google Patents
Tandem quenchInfo
- Publication number
- CA2012627C CA2012627C CA002012627A CA2012627A CA2012627C CA 2012627 C CA2012627 C CA 2012627C CA 002012627 A CA002012627 A CA 002012627A CA 2012627 A CA2012627 A CA 2012627A CA 2012627 C CA2012627 C CA 2012627C
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- Prior art keywords
- effluent
- temperature
- feedstock
- lowered
- quench
- Prior art date
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- Expired - Fee Related
Links
- 238000010791 quenching Methods 0.000 title claims description 80
- 239000006229 carbon black Substances 0.000 claims abstract description 91
- 235000019241 carbon black Nutrition 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000000197 pyrolysis Methods 0.000 claims abstract description 40
- 238000002347 injection Methods 0.000 claims abstract description 29
- 239000007924 injection Substances 0.000 claims abstract description 29
- 239000000567 combustion gas Substances 0.000 claims abstract description 28
- 239000012530 fluid Substances 0.000 claims description 34
- 230000000171 quenching effect Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LTUJKAYZIMMJEP-UHFFFAOYSA-N 9-[4-(4-carbazol-9-yl-2-methylphenyl)-3-methylphenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C(=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C)C(C)=C1 LTUJKAYZIMMJEP-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012485 toluene extract Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000276498 Pollachius virens Species 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012632 extractable Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- -1 tint Chemical compound 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- FAKJFAMIABOKBW-UHFFFAOYSA-N 1-(2,4-dichloro-5-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC(F)=C(Cl)C=C1Cl FAKJFAMIABOKBW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/50—Furnace black ; Preparation thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
- Beans For Foods Or Fodder (AREA)
- Telephone Function (AREA)
- Confectionery (AREA)
Abstract
A method for controlling the aggregate size and structure of the carbon blacks produced by a furnace carbon black reactor by lowering the temperature of, but not stopping pyrolysis in, the effluent (the mixture of combustion gases and feedstock in which pyrolysis is occurring), preferably up to about 800 degrees F, at a residence time between about 0.0 second and about 0.002 second downstream from the furthest downstream point of injection of feedstock.
Description
FIELD OF THE INVENTION
The present invention relates to a method for controlling the aggregate size and structure of carbon blacks.
BACKGROUND
Carbon blacks are generally produced in a furnace-type reactor by pyrolyzing a hydrocarbon feedstock with hot combustion gases to produce combustion products containing particulate carbon black.
In one type of a furnace carbon black reactor, such as shown in US Patent N 3,401,020 to Kester et al., or US Patent N 2,785,964 to Pollock, herein-after "Kester" and "Pollock" respectively, a fuel, preferably hydrocarbonaceous, and an oxidant, preferably air, are injected into a first zone and react to form hot combustion gases. A hydrocarbon feedstock in either gaseous, vapor or liquid form is also injected into the first zone whereupon pyrolysis of the hydrocarbon feedstock commences. In this instance, pyrolysis refers to the thermal decomposition of a hydrocarbon. The resulting combustion gas mixture, in which pyrolysis is occurring, then passes into a reaction zone where ,,, "~, 20~Z6Z7 ._ completion of the carbon black forming reaction occurs.
In another type of a furnace carbon black reactor, a liquid or gaseous fuel is reacted with an oxidant, preferably air, in the first zone to form hot combustion gases. These hot combustion gases pass from the first zone, downstream through the reactor, into a reaction zone and beyond. To produce carbon blacks, a hydrocarbonaceous feedstock is injected at one or more points into the path of the hot combustion gas stream. The hydrocarbonaceous feedstock may be liquid, gas or vapor, and may be the same or different than the fuel utilized to form the combustion gas stream. The first (or combustion) zone and the reaction zone may be divided by a choke or zone of restricted diameter which is smaller in cross section than the combustion zone or the reaction zone. The feedstock may be injected into the path of the hot combustion qases upstream of, downstream of, and/or in the restricted diameter zone. Furnace carbon black reactors of this type are generally described in U.S. Patent Reissue No. 28,974 and U.S. Patent No. 3,922,335.
Although two types of furnace carbon black reactors and processes have been described, it should be understood that the present invention can be used in any other furnace carbon black reactor or process in which carbon black is produced by pyrolysis and/or incomplete combustion of hydrocarbons.
In both types of processes and reactors described above, and in other generally known reactors and processes, the hot combustion gases are at a temperature sufficient to effect pyrolysis of the hydrocarbonaceous feedstock injected into the combustion gas stream. In one type of reactor, such as disclosed in Kester, feedstock is injected, at one or more points, into the same zone where combustion gases are being formed. In other type reactors or processes the injection of the feedstock occurs, at one or more points, after the combustion gas stream has been formed. In either type of reactor, since the hot combustion gas stream is continually flowing downstream through the reactor, pyrolysis continually occurs as the mixture of feedstock and combustion gases passes through the reaction zone. The mixture of feedstock and combustion gases in which pyrolysis is occurring is hereinafter referred to, throughout the application, as "the effluent". The residence time of the effluent in the reaction zone of the reactor is sufficient, and under conditions suitable, to allow the formation of carbon blacks. "Residence time" refers to the amount of time which has elapsed since the initial contact between the hot combustion gases and the feedstock. After carbon blacks having the desired properties are formed, the temperature of the effluent is further lowered to stop pyrolysis. This lowering of the temperature of the effluent to stop pyrolysis may be accomplished by any known manne~, such as by injecting a quenching fluid, through a quench, into the effluent. As generally known to those of ordinary skill in the art, pyrolysis is stopped when the desired carbon black products have been produced in the reactor. One way of determining when pyrolysis should be stopped is by sampling the effluent and measuring its toluene extract level.
Toluene extract level is measured by ASTM Dl618-83 "Carbon ~lack Extractables - Toluene Discoloration~. The quench is generally located at the point where the toluene extract level of the effluent reaches an acceptable level for the desired carbon black product bein~ produced in the reactor. After pyrolysis is stopped, the effluent generally passes through a bag filter system to separate and collect the carbon blacks.
~- Generally a single quench is utilized. Kester, however, discloses the use of two quenches to control certain propertieS of carbon blacks. Kester relates to controlling the modulus-imparting properties of carbon blacks by heat treatment. This heat treatment is achieved by regulating the water flow rates to two water spray quenches, positioned in series, in the effluent smoke in a carbon black furnace. The modulus of a carbon black relates to the performance of the carbon black in a rubber product. As explained in the article by Schaeffer and Smith, ~Effect of Heat Treatment on Reinforcing Properties of Carbon Black~ (Industrial and Engineering Chemistry, Vol. 47, No. 6; June 1955, page 1286), hereinafter "Schaeffer", it is generally known that heat treatment will effect the modulus-imparting properties of carbon black.
However, as further explained in Schaeffer, the change in the modulus-imparting properties of carbon blacks produced by heat treating results from a change in the surface chemistry of the carbon blacks. Therefore, positioning the quenches as suggested by Kester, in order to subject the combustion gas stream to different temperature conditions, affectS the modulus-imparting properties of carbon black apparently by changing the surface chemistry of the carbon blacks rather than by affecting the morphology of the carbon blacks in any discernible way. Moreover, in Kester, both quenches are located in a position in the reaction zone where significant pyrolysis of the feedstock has already occurred. Thus, it would appear that, in Kester's process, by the time the effluent reaches the first quench, the CTAB, tint, DBP and Sto~es diameter properties of the carbon blacks have been defined. This supports the conclusion that the change in the modulus-imparting properties in Kester does not result from a change in the morphological properties of the carbon blacks.
Still further, Kester does not attach any significance to the position of the first quench, relative to the point of injection of feedstoc~ or residence time, and does not disclose means for selecting the position of the first quench.
U.S. Patent No. 4,230,670 to Forseth, hereinafter Forseth, suggests the use of two quenches to stop pyrolysis. The two quenches are located inches apart at the point where a single quench would be located. The purpose of the two quenches is to more completely fill the reaction zone with quenching fluid to more effectively stop pyrolysis. In Forseth however, by the time the effluent reaches the quenches, the CTAB, Tint, DBP
_ 2012627 and Stokes diameter properties of the carbon blacks have been defined.
U.S. Patent No. 4,265,870, to Mills et al., and U.S. Patent No. 4,316,876, to Mills et al., suggest using a second quench located downstream of the first quench to prevent damage to the filter system. In both patents the first quench completely stops pyrolysis and is located at a position generally known to the art, and by the time the effluent reaches the first quench, the CTAB, Tint, DBP and Stokes diameter properties of the carbon blacks have been defined. The second quench further reduces the temperature of the combustion gas stream to protect the filter unit.
U.S. Patent No. 4,358,289, to Austin, hereinafter "Austin", also relates to preventing damage to the filter system by the use of a heat exchanger after the quench. In this patent also, the quench completely stops pyrolysis and is located at a position generally known to the art. In Austin, by the time the effluent reaches the first quench, the CTAB, tint, DBP
and Stokes diameter properties of the carbon blacks have been defined.
U.S. Patent No. 3,615, 211 to Lewis, hereinafter Lewis, --~ 2012627 relates to a method for improving the uniformity of carbon blacks produced by a reactor, and for extending the life of a reactor. To improve uniformity and extend reactor life, Lewis suggests using a plurality of quenches, located throughout the reaction zone, to maintain a substantially constant temperature in the reaction zone. A certain quantity of quenching fluid is injected at the quench located furthest upstream in the reactor, with a greater amount of quenching fluid injected at each subsequent downstream quench. The quench located furthest downstream stops pyrolysis. By maintaining a constant temperature in the reaction zone the apparatus of Lewis promotes uniformity int he carbon blacks produced by the apparatus. However, the plurality of quenches does not control the morphology of carbon blacks produced by the apparatus.
It is generally desirable, however, to be able to control the morphology of carbon blacks such that carbon blacks well suited to a particular end use may be produced. It is also desirable to increase the aggregate size and structure of carbon blacks for a given surface area, since increased aggregate size and structure, as represented by higher DBP, ` 8 lower tint, and larger Stokes Diameter, makes the carbon blacks better suited for certain end uses.
Accordingly an object of the present invention is to provide a method for controlling the aggregate size and structure of carbon blacks.
An additional object of the present invention is to produce carbon blacks having larger aggregate size and higher structure for a given surface area.
SUMMARY OF T~E INVENTION
We have discovered a method which achieves these desirable objects. We have discovered that we can control the morphology of carbon blacks produced in a furnace carbon black process, ~y lowering the temperature of the effluent without stopping pyrolysis, preferably up to about 800 degrees F, within a specified residence time of up to about 0.002 second downstream from the furthest downstream point of injection of feedstock. The lowering of the temperature may be accomplished by locating a first quench at or within about 4 feet downstream of the furthest downstream point of injection of feedstock and injecting quenching fluid.
According to the present invention the production of carbon 20~2627 blacks may be controlled to produce carbon blacks having specific morphological properties such as larger aggregate size and increased structure as shown by higher DBP, lower tint, and increased Stokes diameter for a given surface area (CTAB). We have further discovered that these morphological propertieS of carbon blacks may be further controlled by varying the amount by which the temperature of the effluent is lowered and/or varying the residence time from the time of the furthest downstream injection of feedstock until the temperature of the effluent is lowered.
In more detail, the present invention relates to a method for controlling the aggregate size and structure of the carbon blacks produced by a furnace carbon black reactor by lowering the temperature of, but not stopping pyrolysis in, the effluent (the mixture of combustion gases and feedstock in which pyrolysis is occurring) at a residence time between about 0.0 second and about 0.002 second, preferably between a~out 0.0 and about 0.0015 second, downstream from the furthest downstream point of injection of feedstock. The temperature of the effluent is lowered, within the above specified residence time, preferably up to about 800 degrees F and more ZO~X6Z7 preferably between about 50 and about 800 degrees F. The temperature of the effluent may be lowered by a quench, preferably a quench injecting quenching fluid into the effluent, located at point in the reactor whereby the effluent is quenched between about o.o and 0.002 second, preferably between about 0.0 and a~out 0.0015 second, downstream from the furthest downstream point of injection of feedstock.
Typically, in order for the effluent to be quenched within the specified residence time, the quench will be located at or within about 4 feet from the furthest downstream point of injection of feedstock. The quench lowers the temperature of the effluent, preferably up to about 800 degrees F, and more preferably between about 50 and about 800 degrees F, but does not stop pyrolysis. According to the present invention, the amount by which the temperature of the effluent is lowered and the residence time at which the lowering of the temperature of the effluent occurs may be varied.
- independently or simultaneously to control the aggregate size and structure of carbon blacks being produced by the reactor.
In a reactor using a quench, injecting a quenching fluid, to lower the temperature of the effluent within the specified residence times, this varying of the amount the temperature of the effluent is lowered and the residence time at which the lowering of the temperature of the effluent occurs may be accomplished by varying the quantity of quenching fluid injected from the quench and varying the location of the quench respectively. After carbon blacks with the desired properties have been formed pyrolysis is stopped.
The present invention allows the production of a carbon black product having larger aggregate size and structure for a given surface area than the carbon black products produced by a similar process wherein the temperature of the effluent is not lowered within the specified residence time.
An advantage of the process of the present inventiQn is that the aggregate size and structure of carbon blacks may be controlled.
Another advantage of the process of the present invention is that carbon blacks having larger aggregate size and structure, as shown by higher DBP's, lower tints, and increased Stokes' diameters, for a given surface area, as shown by CTAB, may be produced.
Other advantages of the present invention will become ;~O~Z6Z7 apparent from the following description and claims.
The figure is a cross sectional view of one embodiment of the present invention in a carbon black reactor, showing the location of a first and a second quench.
DETAILED DESCRIPTION OF T~E INVENTION
The figure depicts one possible embodiment of the present invention. Although a portion of one type of carbon black reactor is depicted in the figure, as previously explained the present invention can be used in any carbon black furnace reactor in which carbon black is made by pyrolysis and/or incomplete combustion of hydrocarbons. Further, although the following description explains an embodiment of the present invention utilizing a quench, injecting a quenching fluid, to lower the temperature of the effluent, as will be understood by those of ordinary skill in the art, the present invention encompasses any method for lowering the temperature of the effluent, preferably by the amounts specified, within the specified residence times from the point of injection of feedstock nearest the reaction zone. Similarly, although the following description describes using a second quench to stop pyrolysis, as will be understood by those of ordinary skill in the art, the present invention encompasses any method for stopping pyrolysis.
In the figure, a portion of a carbon black reactor 10, having, for example, a reaction zone 12, and a zone of restricted diameter 20, is equipped with a first quench 40, located at point 60, and a second quench 42, located at point 62, for injecting quenching fluid 50. The quenching fluid 50 may be the same or different for each quench. The direction of flow of the hot combustion gas stream through reactor 10, and zones 12 and 20 is shown by the arrow. Quenching fluid 50 can be injected by first quench 40 and second quench 42 counter-currently, or preferably co-currently, to the direction of the combustion gas stream. Point 14, is the furthest downstream point of injection of feedstock 30. As will be understood by those having ordinary skill in the art, 14, the furthest downstream point of injection of feedstock can be varied. The distance from 14, the furthest downstream point of injection of feedstock, to the point of the first quench 60 is r~presented by L-l and the distance from the furthest downstream point of injection of feedstock, 14 to the point of t~e second quench 62 is represented by L-2.
According to the depicted embodiment of the present invention, the first quench 60 is positioned to lower the temperature of the effluent (the mixture of combustion gases and feedstock in which pyrolysis is occurring~ no later than 0.002 second, and preferably between 0.0 and 0.0015 second, residence time from the furthest downstream point of injection of feedstock. Typically, in order for the effluent to be quenched within the specified residence time, the first quench will be located at or within about 4 feet from the furthest downstream point of injection of feedstock.
Therefore L-1 will be between about o.0 and about 4 feet.
Quenching fluid is injected through the first quench 60 in order to lower the temperature of the effluent, preferably by an amount up to 800 degrees F, more preferably by an amount between about 50 and about 800 degrees F, provided, however, that the quenching fluid injected through first quench 60 will not stop pyrolysis.
Additionally, according to the present invention the residence time from the furthest.downstream point of in`jection of feedstock until the tèmperature of the effluent ~-- 2012627 (the mixture of combustion gases and feedstock in which pyrolysis is occurring) is initially lowered, and the amount by which the temperature of the effluent is lowered, may be varied independently or simultaneously to control the aggregate size and structure of the carbon blacks produced by the reactor. In the embodiment of the present invention shown in the figure, varying L-1 will vary the residence time from the time of the furthest downstream injection of feedstock to the time at which the temperature of the effluent is lowered. By varying the amount of quenching fluid injected the amount by which the temperature of the effluent is lowered may be varied.
As explained in the preceding paragraph, in the embodiment of the present invention shown in the figure, depending on the aggregate size and structure desired typically L-1 ranges from about 0.0 feet to about 4 feet. Quenching fluid 50 lowers the temperature of the effluent, preferably by an amount up to about 800 degrees F, more preferably by an amount between about 50 and about 800 degrees F, provided, however, that pyrolysis will not be stopped at first quench 60 by the quenching fluid 50.
Z~2~Z7 After carbon blacks with the desired properties have been produced pyrolysis is stopped at point 62 by quench 42.
Point 62 is a point at which carbon blacks having the desired properties have been produced by the reactor. As previously explained, point 62 may be determined in any manner known to the art, for selecting the position of a quench which stops pyrolysis. One method for determining the position of the quench which stops pyrolysis is by determining the point at which an acceptable toluene extract level for carbon black products desired from the reaction is achieved. Toluene extract level may be measured by using ASTM Test D1618-83 "Carbon Black Extractables - Toluene Discoloration". L-2 will vary according to the position of point 62.
The effectiveness and advantages of the present invention will be further illustrated by the following example.
EXAMPLE
To demonstrate the effectiveness of the present invention experiments were conducted in a carbon black production process utilizing two quenches and varying the residence time from the time of the furthest downstream injection of feedstock until the time the temperature of the 20~2627 , effluent was lowered and the amount by which the temperature of the effluent was lowered. This residence time was ~raried by varying L-l. The process variables for, and the results of, the two sets of carbon black runs in the experiments, are summarized in the Table set forth below. Set I comprises runs 1, 2, and 3 and Set II comprises runs 4, 5, and 6.
TABLE
Temp. Temp. T mp.
R- . Bet. 1 st Att. 2nd An.
nme 1~ 0 Ci 1st O Ci 2nd O ~d. D~t flut~
RUN SET (sec) oF n. F n. F CTAS Tint Dlsc. CDBP nm DPiP
--- 2520 ----- 2620 4 21350 109 2 120.5 68 109.5 98.8 186 2 1 .0007 2620 1 4 2220 17.0 1350100.7 1106 45 110.0 109.6 205 3 .0005 2620 1.0 2220 20.0 135094.3 102.2 73 113.4 126.9 232 4 - 2570 ---- 25~0 15.01350 91.6 114.6 77 95.2 94.1 148 11 .0004 2570 1 0 2270 34.0 135093.4 106 1 78 106.4 101.5 213 6 .0004 2570 1.0 2170 36.0 135091 4 1050 41 107.1 103.3 220 SET 1 Prehest . 900O F: GAS. 7.2 ksc~h: Air ~ 80 itacih Air/G~u . 11.11 Prlmary Comi~siion . 123~: CL ' a Zone Vol. . .
~s ~t ':
Inlectlon Zone Olameter - 4.2 In. Injection Zone ~ength 8 12 ~n. C~ n GaS Veioaty In Inlection Zon- . 2000 n.hec.:
oil . 125 gph Oil Inlection i res~ure . 230 pslg ~ o~ oo tips . 4 Oil ~ip d~ameter = 0.042 In. Reectlon Zone Oiameter . 13.5 In.
ll e liquid teedstock (oil) had tile ~ollowing c . 1~ .. H/C Ra~io . .91: Hydroqen . 6.89 wt % 7.00 wi.%:
Caroon 91.1 wt.% 90.8 wt.% Suitur . 1.1 wt.~ API Gravlty 15.6/15.6 C(60f) . 5.0: PiMCI (Vl~c-Gravl 141 Sf~ Il: Preheal . 11000 F GaS . 7 5 kscrh Air . 50 itllClh: Air/Gas . 10 6 Primary C~ . 118%: C- - ~n Zon- vol. -.85t.J.
. Inj~ctlon Zon Oiameter . 4.2 In. Inje~ion Zone Length . 12 In.; C~ Gaa V-icK ~ty In In~ on Zon- . 2300 n.h c.:
oii 136 gph: Oil In;ection Pre~ure . 270 ~ig ~ o~ oil ~ID- . 4; Oil ~p di~me~r~r . 0.042 In. Reaetlon Zone iDiameter 6 In.
The iiquid hed~tock (oli) had the toiiowing c .~ ~. R/C Ratio . t.06 I-iydrogen . 7.99 wt.% 7.99wt.%:
Carbon . 89.7 wt.% 89.5 wt.%: SuHur . 0.5 wt.%: API Gravity 1S.6/15.6 C(60F) . 0.5: iSMCI (~GGrov) . 123 In ~ S~t I and Sat ll the nuld tuei uti02ed In the ~ ... . ~ reaction was netural gr~. having e meth~ ne eontent ot 95.'4%
and a wot heating value o~ 925 FiTU/SCF.
201262~
- As will be generally understood by those of ordinary skill in the art, the process variables set forth in the Table represent the variable at one point in the reactor and are determined in the manner generally known. Each set of carbon black runs was made in a carbon black reactor similar to the reactor disclosed in Example 1 of U.S. Patent No. 3,922,335 with the exceptions as noted in the Table.
In the Table, Q refers to Quench. 1st Q ft. refers to L-l, the distance from the furthest downstream point of injection of feedstock to the first quench. Temperature Before 1st Quench (Temp. Bef. 1st Q) refers to the temperature of the effluent before the 1st quench, and Temperature After 1st Quench (Temp. Aft. 1st Q) and Temperature After 2nd Quench (Temp. Aft. 2nd Q) refer to the temperature of the effluent after the 1st quench, and the temperature of the mixture of feedstock and combustion gases after the 2nd quench, respectively. All temperatures relatinq to quenching are calculated by con~entional, well known, thermodynamic techniques. Residence Time (Res. Time), in the Table , refers to the amount of time after furthest downstream point of in3ection of feedstock, which elapsed before the temperature of the effluent was initially lowered. 2nd Q ft., refers to L-2 and was empirically determined using the toluene extract level. After each run the carbon blacks produced were collected and analyzed to determine CTAB, tint, Dst(median Stokes diameter), CDBP, Fluffy DBP and Toluene Discoloration. The results for each run, are shown in the Table.
CTAB was determined according to ASTM Test Procedure D3765-85. Tint was determined according to ASTM Test Procedure D3265-85a. DBP of the fluffy blacks was determined according to the procedure set forth in ASTM D2414-86. CDBP was determined accord-ing to the procedure set forth in ASTM D3493-86.
Toluene Discoloration was determined according to ASTM Test Procedure D1618-83.
Dst(median Stokes Diameter) was determined with disc centrifuge photosedimentometry according to the following description. The following procedure is a modification of the procedure described in the Instruction Manual for the Joyce-Loebl Disc Centrifuge, File Ref. DCFA.008, published 1 Feb. 1985, available from Joyce-Loebl Company, (Maquisway, Team Valley, Gateshead, Tyne & Wear, England). The procedure is ., -as follows. 10 mg (milligrams) of a carbon black sample are weighed in a weighing vessel, then added to 50 cc of a solution of 10% absolute ethanol, 90% distilled water which is made 0.05% NONIDET P-40 surfactant (NONIDET P-40 is a registered trademark for a surfactant manufactured and sold by Shell Chemical Co.). The suspension is dispersed by means of ultrasonic energy for 15 minutes using Sonifier Model No. W
385, manufactured and sold by Heat Systems Ultrasonics Inc., Farmingdale, New York. Prior to the disc centrifuge run the following data are entered into the computer which records the data from the disc centrifuge:
1. The specific gravity of carbon black, taken as 1.86 g/cc:
2. The volume of the solution of the carbon black dispersed in a solution of water and ethanol, which in this instance is 0.5 cc.;
3. The ~olume of spin fluid, which in this instance is 10 cc of water:
4. The viscosity of the spin fluid, which in this instance is taken as 0.933 centipoise at 23 degrees C;
The present invention relates to a method for controlling the aggregate size and structure of carbon blacks.
BACKGROUND
Carbon blacks are generally produced in a furnace-type reactor by pyrolyzing a hydrocarbon feedstock with hot combustion gases to produce combustion products containing particulate carbon black.
In one type of a furnace carbon black reactor, such as shown in US Patent N 3,401,020 to Kester et al., or US Patent N 2,785,964 to Pollock, herein-after "Kester" and "Pollock" respectively, a fuel, preferably hydrocarbonaceous, and an oxidant, preferably air, are injected into a first zone and react to form hot combustion gases. A hydrocarbon feedstock in either gaseous, vapor or liquid form is also injected into the first zone whereupon pyrolysis of the hydrocarbon feedstock commences. In this instance, pyrolysis refers to the thermal decomposition of a hydrocarbon. The resulting combustion gas mixture, in which pyrolysis is occurring, then passes into a reaction zone where ,,, "~, 20~Z6Z7 ._ completion of the carbon black forming reaction occurs.
In another type of a furnace carbon black reactor, a liquid or gaseous fuel is reacted with an oxidant, preferably air, in the first zone to form hot combustion gases. These hot combustion gases pass from the first zone, downstream through the reactor, into a reaction zone and beyond. To produce carbon blacks, a hydrocarbonaceous feedstock is injected at one or more points into the path of the hot combustion gas stream. The hydrocarbonaceous feedstock may be liquid, gas or vapor, and may be the same or different than the fuel utilized to form the combustion gas stream. The first (or combustion) zone and the reaction zone may be divided by a choke or zone of restricted diameter which is smaller in cross section than the combustion zone or the reaction zone. The feedstock may be injected into the path of the hot combustion qases upstream of, downstream of, and/or in the restricted diameter zone. Furnace carbon black reactors of this type are generally described in U.S. Patent Reissue No. 28,974 and U.S. Patent No. 3,922,335.
Although two types of furnace carbon black reactors and processes have been described, it should be understood that the present invention can be used in any other furnace carbon black reactor or process in which carbon black is produced by pyrolysis and/or incomplete combustion of hydrocarbons.
In both types of processes and reactors described above, and in other generally known reactors and processes, the hot combustion gases are at a temperature sufficient to effect pyrolysis of the hydrocarbonaceous feedstock injected into the combustion gas stream. In one type of reactor, such as disclosed in Kester, feedstock is injected, at one or more points, into the same zone where combustion gases are being formed. In other type reactors or processes the injection of the feedstock occurs, at one or more points, after the combustion gas stream has been formed. In either type of reactor, since the hot combustion gas stream is continually flowing downstream through the reactor, pyrolysis continually occurs as the mixture of feedstock and combustion gases passes through the reaction zone. The mixture of feedstock and combustion gases in which pyrolysis is occurring is hereinafter referred to, throughout the application, as "the effluent". The residence time of the effluent in the reaction zone of the reactor is sufficient, and under conditions suitable, to allow the formation of carbon blacks. "Residence time" refers to the amount of time which has elapsed since the initial contact between the hot combustion gases and the feedstock. After carbon blacks having the desired properties are formed, the temperature of the effluent is further lowered to stop pyrolysis. This lowering of the temperature of the effluent to stop pyrolysis may be accomplished by any known manne~, such as by injecting a quenching fluid, through a quench, into the effluent. As generally known to those of ordinary skill in the art, pyrolysis is stopped when the desired carbon black products have been produced in the reactor. One way of determining when pyrolysis should be stopped is by sampling the effluent and measuring its toluene extract level.
Toluene extract level is measured by ASTM Dl618-83 "Carbon ~lack Extractables - Toluene Discoloration~. The quench is generally located at the point where the toluene extract level of the effluent reaches an acceptable level for the desired carbon black product bein~ produced in the reactor. After pyrolysis is stopped, the effluent generally passes through a bag filter system to separate and collect the carbon blacks.
~- Generally a single quench is utilized. Kester, however, discloses the use of two quenches to control certain propertieS of carbon blacks. Kester relates to controlling the modulus-imparting properties of carbon blacks by heat treatment. This heat treatment is achieved by regulating the water flow rates to two water spray quenches, positioned in series, in the effluent smoke in a carbon black furnace. The modulus of a carbon black relates to the performance of the carbon black in a rubber product. As explained in the article by Schaeffer and Smith, ~Effect of Heat Treatment on Reinforcing Properties of Carbon Black~ (Industrial and Engineering Chemistry, Vol. 47, No. 6; June 1955, page 1286), hereinafter "Schaeffer", it is generally known that heat treatment will effect the modulus-imparting properties of carbon black.
However, as further explained in Schaeffer, the change in the modulus-imparting properties of carbon blacks produced by heat treating results from a change in the surface chemistry of the carbon blacks. Therefore, positioning the quenches as suggested by Kester, in order to subject the combustion gas stream to different temperature conditions, affectS the modulus-imparting properties of carbon black apparently by changing the surface chemistry of the carbon blacks rather than by affecting the morphology of the carbon blacks in any discernible way. Moreover, in Kester, both quenches are located in a position in the reaction zone where significant pyrolysis of the feedstock has already occurred. Thus, it would appear that, in Kester's process, by the time the effluent reaches the first quench, the CTAB, tint, DBP and Sto~es diameter properties of the carbon blacks have been defined. This supports the conclusion that the change in the modulus-imparting properties in Kester does not result from a change in the morphological properties of the carbon blacks.
Still further, Kester does not attach any significance to the position of the first quench, relative to the point of injection of feedstoc~ or residence time, and does not disclose means for selecting the position of the first quench.
U.S. Patent No. 4,230,670 to Forseth, hereinafter Forseth, suggests the use of two quenches to stop pyrolysis. The two quenches are located inches apart at the point where a single quench would be located. The purpose of the two quenches is to more completely fill the reaction zone with quenching fluid to more effectively stop pyrolysis. In Forseth however, by the time the effluent reaches the quenches, the CTAB, Tint, DBP
_ 2012627 and Stokes diameter properties of the carbon blacks have been defined.
U.S. Patent No. 4,265,870, to Mills et al., and U.S. Patent No. 4,316,876, to Mills et al., suggest using a second quench located downstream of the first quench to prevent damage to the filter system. In both patents the first quench completely stops pyrolysis and is located at a position generally known to the art, and by the time the effluent reaches the first quench, the CTAB, Tint, DBP and Stokes diameter properties of the carbon blacks have been defined. The second quench further reduces the temperature of the combustion gas stream to protect the filter unit.
U.S. Patent No. 4,358,289, to Austin, hereinafter "Austin", also relates to preventing damage to the filter system by the use of a heat exchanger after the quench. In this patent also, the quench completely stops pyrolysis and is located at a position generally known to the art. In Austin, by the time the effluent reaches the first quench, the CTAB, tint, DBP
and Stokes diameter properties of the carbon blacks have been defined.
U.S. Patent No. 3,615, 211 to Lewis, hereinafter Lewis, --~ 2012627 relates to a method for improving the uniformity of carbon blacks produced by a reactor, and for extending the life of a reactor. To improve uniformity and extend reactor life, Lewis suggests using a plurality of quenches, located throughout the reaction zone, to maintain a substantially constant temperature in the reaction zone. A certain quantity of quenching fluid is injected at the quench located furthest upstream in the reactor, with a greater amount of quenching fluid injected at each subsequent downstream quench. The quench located furthest downstream stops pyrolysis. By maintaining a constant temperature in the reaction zone the apparatus of Lewis promotes uniformity int he carbon blacks produced by the apparatus. However, the plurality of quenches does not control the morphology of carbon blacks produced by the apparatus.
It is generally desirable, however, to be able to control the morphology of carbon blacks such that carbon blacks well suited to a particular end use may be produced. It is also desirable to increase the aggregate size and structure of carbon blacks for a given surface area, since increased aggregate size and structure, as represented by higher DBP, ` 8 lower tint, and larger Stokes Diameter, makes the carbon blacks better suited for certain end uses.
Accordingly an object of the present invention is to provide a method for controlling the aggregate size and structure of carbon blacks.
An additional object of the present invention is to produce carbon blacks having larger aggregate size and higher structure for a given surface area.
SUMMARY OF T~E INVENTION
We have discovered a method which achieves these desirable objects. We have discovered that we can control the morphology of carbon blacks produced in a furnace carbon black process, ~y lowering the temperature of the effluent without stopping pyrolysis, preferably up to about 800 degrees F, within a specified residence time of up to about 0.002 second downstream from the furthest downstream point of injection of feedstock. The lowering of the temperature may be accomplished by locating a first quench at or within about 4 feet downstream of the furthest downstream point of injection of feedstock and injecting quenching fluid.
According to the present invention the production of carbon 20~2627 blacks may be controlled to produce carbon blacks having specific morphological properties such as larger aggregate size and increased structure as shown by higher DBP, lower tint, and increased Stokes diameter for a given surface area (CTAB). We have further discovered that these morphological propertieS of carbon blacks may be further controlled by varying the amount by which the temperature of the effluent is lowered and/or varying the residence time from the time of the furthest downstream injection of feedstock until the temperature of the effluent is lowered.
In more detail, the present invention relates to a method for controlling the aggregate size and structure of the carbon blacks produced by a furnace carbon black reactor by lowering the temperature of, but not stopping pyrolysis in, the effluent (the mixture of combustion gases and feedstock in which pyrolysis is occurring) at a residence time between about 0.0 second and about 0.002 second, preferably between a~out 0.0 and about 0.0015 second, downstream from the furthest downstream point of injection of feedstock. The temperature of the effluent is lowered, within the above specified residence time, preferably up to about 800 degrees F and more ZO~X6Z7 preferably between about 50 and about 800 degrees F. The temperature of the effluent may be lowered by a quench, preferably a quench injecting quenching fluid into the effluent, located at point in the reactor whereby the effluent is quenched between about o.o and 0.002 second, preferably between about 0.0 and a~out 0.0015 second, downstream from the furthest downstream point of injection of feedstock.
Typically, in order for the effluent to be quenched within the specified residence time, the quench will be located at or within about 4 feet from the furthest downstream point of injection of feedstock. The quench lowers the temperature of the effluent, preferably up to about 800 degrees F, and more preferably between about 50 and about 800 degrees F, but does not stop pyrolysis. According to the present invention, the amount by which the temperature of the effluent is lowered and the residence time at which the lowering of the temperature of the effluent occurs may be varied.
- independently or simultaneously to control the aggregate size and structure of carbon blacks being produced by the reactor.
In a reactor using a quench, injecting a quenching fluid, to lower the temperature of the effluent within the specified residence times, this varying of the amount the temperature of the effluent is lowered and the residence time at which the lowering of the temperature of the effluent occurs may be accomplished by varying the quantity of quenching fluid injected from the quench and varying the location of the quench respectively. After carbon blacks with the desired properties have been formed pyrolysis is stopped.
The present invention allows the production of a carbon black product having larger aggregate size and structure for a given surface area than the carbon black products produced by a similar process wherein the temperature of the effluent is not lowered within the specified residence time.
An advantage of the process of the present inventiQn is that the aggregate size and structure of carbon blacks may be controlled.
Another advantage of the process of the present invention is that carbon blacks having larger aggregate size and structure, as shown by higher DBP's, lower tints, and increased Stokes' diameters, for a given surface area, as shown by CTAB, may be produced.
Other advantages of the present invention will become ;~O~Z6Z7 apparent from the following description and claims.
The figure is a cross sectional view of one embodiment of the present invention in a carbon black reactor, showing the location of a first and a second quench.
DETAILED DESCRIPTION OF T~E INVENTION
The figure depicts one possible embodiment of the present invention. Although a portion of one type of carbon black reactor is depicted in the figure, as previously explained the present invention can be used in any carbon black furnace reactor in which carbon black is made by pyrolysis and/or incomplete combustion of hydrocarbons. Further, although the following description explains an embodiment of the present invention utilizing a quench, injecting a quenching fluid, to lower the temperature of the effluent, as will be understood by those of ordinary skill in the art, the present invention encompasses any method for lowering the temperature of the effluent, preferably by the amounts specified, within the specified residence times from the point of injection of feedstock nearest the reaction zone. Similarly, although the following description describes using a second quench to stop pyrolysis, as will be understood by those of ordinary skill in the art, the present invention encompasses any method for stopping pyrolysis.
In the figure, a portion of a carbon black reactor 10, having, for example, a reaction zone 12, and a zone of restricted diameter 20, is equipped with a first quench 40, located at point 60, and a second quench 42, located at point 62, for injecting quenching fluid 50. The quenching fluid 50 may be the same or different for each quench. The direction of flow of the hot combustion gas stream through reactor 10, and zones 12 and 20 is shown by the arrow. Quenching fluid 50 can be injected by first quench 40 and second quench 42 counter-currently, or preferably co-currently, to the direction of the combustion gas stream. Point 14, is the furthest downstream point of injection of feedstock 30. As will be understood by those having ordinary skill in the art, 14, the furthest downstream point of injection of feedstock can be varied. The distance from 14, the furthest downstream point of injection of feedstock, to the point of the first quench 60 is r~presented by L-l and the distance from the furthest downstream point of injection of feedstock, 14 to the point of t~e second quench 62 is represented by L-2.
According to the depicted embodiment of the present invention, the first quench 60 is positioned to lower the temperature of the effluent (the mixture of combustion gases and feedstock in which pyrolysis is occurring~ no later than 0.002 second, and preferably between 0.0 and 0.0015 second, residence time from the furthest downstream point of injection of feedstock. Typically, in order for the effluent to be quenched within the specified residence time, the first quench will be located at or within about 4 feet from the furthest downstream point of injection of feedstock.
Therefore L-1 will be between about o.0 and about 4 feet.
Quenching fluid is injected through the first quench 60 in order to lower the temperature of the effluent, preferably by an amount up to 800 degrees F, more preferably by an amount between about 50 and about 800 degrees F, provided, however, that the quenching fluid injected through first quench 60 will not stop pyrolysis.
Additionally, according to the present invention the residence time from the furthest.downstream point of in`jection of feedstock until the tèmperature of the effluent ~-- 2012627 (the mixture of combustion gases and feedstock in which pyrolysis is occurring) is initially lowered, and the amount by which the temperature of the effluent is lowered, may be varied independently or simultaneously to control the aggregate size and structure of the carbon blacks produced by the reactor. In the embodiment of the present invention shown in the figure, varying L-1 will vary the residence time from the time of the furthest downstream injection of feedstock to the time at which the temperature of the effluent is lowered. By varying the amount of quenching fluid injected the amount by which the temperature of the effluent is lowered may be varied.
As explained in the preceding paragraph, in the embodiment of the present invention shown in the figure, depending on the aggregate size and structure desired typically L-1 ranges from about 0.0 feet to about 4 feet. Quenching fluid 50 lowers the temperature of the effluent, preferably by an amount up to about 800 degrees F, more preferably by an amount between about 50 and about 800 degrees F, provided, however, that pyrolysis will not be stopped at first quench 60 by the quenching fluid 50.
Z~2~Z7 After carbon blacks with the desired properties have been produced pyrolysis is stopped at point 62 by quench 42.
Point 62 is a point at which carbon blacks having the desired properties have been produced by the reactor. As previously explained, point 62 may be determined in any manner known to the art, for selecting the position of a quench which stops pyrolysis. One method for determining the position of the quench which stops pyrolysis is by determining the point at which an acceptable toluene extract level for carbon black products desired from the reaction is achieved. Toluene extract level may be measured by using ASTM Test D1618-83 "Carbon Black Extractables - Toluene Discoloration". L-2 will vary according to the position of point 62.
The effectiveness and advantages of the present invention will be further illustrated by the following example.
EXAMPLE
To demonstrate the effectiveness of the present invention experiments were conducted in a carbon black production process utilizing two quenches and varying the residence time from the time of the furthest downstream injection of feedstock until the time the temperature of the 20~2627 , effluent was lowered and the amount by which the temperature of the effluent was lowered. This residence time was ~raried by varying L-l. The process variables for, and the results of, the two sets of carbon black runs in the experiments, are summarized in the Table set forth below. Set I comprises runs 1, 2, and 3 and Set II comprises runs 4, 5, and 6.
TABLE
Temp. Temp. T mp.
R- . Bet. 1 st Att. 2nd An.
nme 1~ 0 Ci 1st O Ci 2nd O ~d. D~t flut~
RUN SET (sec) oF n. F n. F CTAS Tint Dlsc. CDBP nm DPiP
--- 2520 ----- 2620 4 21350 109 2 120.5 68 109.5 98.8 186 2 1 .0007 2620 1 4 2220 17.0 1350100.7 1106 45 110.0 109.6 205 3 .0005 2620 1.0 2220 20.0 135094.3 102.2 73 113.4 126.9 232 4 - 2570 ---- 25~0 15.01350 91.6 114.6 77 95.2 94.1 148 11 .0004 2570 1 0 2270 34.0 135093.4 106 1 78 106.4 101.5 213 6 .0004 2570 1.0 2170 36.0 135091 4 1050 41 107.1 103.3 220 SET 1 Prehest . 900O F: GAS. 7.2 ksc~h: Air ~ 80 itacih Air/G~u . 11.11 Prlmary Comi~siion . 123~: CL ' a Zone Vol. . .
~s ~t ':
Inlectlon Zone Olameter - 4.2 In. Injection Zone ~ength 8 12 ~n. C~ n GaS Veioaty In Inlection Zon- . 2000 n.hec.:
oil . 125 gph Oil Inlection i res~ure . 230 pslg ~ o~ oo tips . 4 Oil ~ip d~ameter = 0.042 In. Reectlon Zone Oiameter . 13.5 In.
ll e liquid teedstock (oil) had tile ~ollowing c . 1~ .. H/C Ra~io . .91: Hydroqen . 6.89 wt % 7.00 wi.%:
Caroon 91.1 wt.% 90.8 wt.% Suitur . 1.1 wt.~ API Gravlty 15.6/15.6 C(60f) . 5.0: PiMCI (Vl~c-Gravl 141 Sf~ Il: Preheal . 11000 F GaS . 7 5 kscrh Air . 50 itllClh: Air/Gas . 10 6 Primary C~ . 118%: C- - ~n Zon- vol. -.85t.J.
. Inj~ctlon Zon Oiameter . 4.2 In. Inje~ion Zone Length . 12 In.; C~ Gaa V-icK ~ty In In~ on Zon- . 2300 n.h c.:
oii 136 gph: Oil In;ection Pre~ure . 270 ~ig ~ o~ oil ~ID- . 4; Oil ~p di~me~r~r . 0.042 In. Reaetlon Zone iDiameter 6 In.
The iiquid hed~tock (oli) had the toiiowing c .~ ~. R/C Ratio . t.06 I-iydrogen . 7.99 wt.% 7.99wt.%:
Carbon . 89.7 wt.% 89.5 wt.%: SuHur . 0.5 wt.%: API Gravity 1S.6/15.6 C(60F) . 0.5: iSMCI (~GGrov) . 123 In ~ S~t I and Sat ll the nuld tuei uti02ed In the ~ ... . ~ reaction was netural gr~. having e meth~ ne eontent ot 95.'4%
and a wot heating value o~ 925 FiTU/SCF.
201262~
- As will be generally understood by those of ordinary skill in the art, the process variables set forth in the Table represent the variable at one point in the reactor and are determined in the manner generally known. Each set of carbon black runs was made in a carbon black reactor similar to the reactor disclosed in Example 1 of U.S. Patent No. 3,922,335 with the exceptions as noted in the Table.
In the Table, Q refers to Quench. 1st Q ft. refers to L-l, the distance from the furthest downstream point of injection of feedstock to the first quench. Temperature Before 1st Quench (Temp. Bef. 1st Q) refers to the temperature of the effluent before the 1st quench, and Temperature After 1st Quench (Temp. Aft. 1st Q) and Temperature After 2nd Quench (Temp. Aft. 2nd Q) refer to the temperature of the effluent after the 1st quench, and the temperature of the mixture of feedstock and combustion gases after the 2nd quench, respectively. All temperatures relatinq to quenching are calculated by con~entional, well known, thermodynamic techniques. Residence Time (Res. Time), in the Table , refers to the amount of time after furthest downstream point of in3ection of feedstock, which elapsed before the temperature of the effluent was initially lowered. 2nd Q ft., refers to L-2 and was empirically determined using the toluene extract level. After each run the carbon blacks produced were collected and analyzed to determine CTAB, tint, Dst(median Stokes diameter), CDBP, Fluffy DBP and Toluene Discoloration. The results for each run, are shown in the Table.
CTAB was determined according to ASTM Test Procedure D3765-85. Tint was determined according to ASTM Test Procedure D3265-85a. DBP of the fluffy blacks was determined according to the procedure set forth in ASTM D2414-86. CDBP was determined accord-ing to the procedure set forth in ASTM D3493-86.
Toluene Discoloration was determined according to ASTM Test Procedure D1618-83.
Dst(median Stokes Diameter) was determined with disc centrifuge photosedimentometry according to the following description. The following procedure is a modification of the procedure described in the Instruction Manual for the Joyce-Loebl Disc Centrifuge, File Ref. DCFA.008, published 1 Feb. 1985, available from Joyce-Loebl Company, (Maquisway, Team Valley, Gateshead, Tyne & Wear, England). The procedure is ., -as follows. 10 mg (milligrams) of a carbon black sample are weighed in a weighing vessel, then added to 50 cc of a solution of 10% absolute ethanol, 90% distilled water which is made 0.05% NONIDET P-40 surfactant (NONIDET P-40 is a registered trademark for a surfactant manufactured and sold by Shell Chemical Co.). The suspension is dispersed by means of ultrasonic energy for 15 minutes using Sonifier Model No. W
385, manufactured and sold by Heat Systems Ultrasonics Inc., Farmingdale, New York. Prior to the disc centrifuge run the following data are entered into the computer which records the data from the disc centrifuge:
1. The specific gravity of carbon black, taken as 1.86 g/cc:
2. The volume of the solution of the carbon black dispersed in a solution of water and ethanol, which in this instance is 0.5 cc.;
3. The ~olume of spin fluid, which in this instance is 10 cc of water:
4. The viscosity of the spin fluid, which in this instance is taken as 0.933 centipoise at 23 degrees C;
5. The density of the spin fluid, which in this instance is ~2~27 0.9975 g/cc at 23 degrees C;
6. The disc speed, which in this instance is 8000 rpm;
7. The data sampling interval, which in this instance is 1 second.
The disc centrifuge is operated at 8000 rpm while the stroboscope is operating. 10 cc of distilled water are injected into the spinning disc as the spin fluid. The turbidity level is set to 0; and 1 cc of the solution of 10% absolute ethanol and 90% distilled water is injected as a buffer liquid. The cut and boost buttons of the disc centrifuge are then operated to produce a smooth concentration gradient between the spin fluid and the buffer liquid and the gradient is monitored visually. When the gradient becomes smooth such that there is no distinguishable boundary between the two fluids, 0.5 cc of the dispersed carbon black in aqueous ethanol solution is injected into the spinning disc and data collection is started immediately. If streaming occurs the run is aborted. The disc is spun for 20 minutes following the injection of the dispersed carbon black in aqueous ethanol solution. Following the 20 m,inutes of spinning, the disc is stopped, the temperature of the spin fluid is measured, and the average of the temperature of the spin fluid measured at the beginning of the run and the temperature of the spin fluid measured at the end of the run is entered into the computer which records the data from the disc centrifuge. The data is analyzed according to the standard Stokes equation and is presented using the following definitions:
Carbon black aggregate - a discrete, rigid colloidal entity that is the smallest dispersible unit: it is composed of extensively coalesced particles;
Stokes diameter - the diameter of a sphere which sediments in a viscous medium in a centrifugal or gravitational field according to the Stokes equation. A non-spherical object, such as a carbon black aggregate, may also be represented in terms of the Stokes diameter if it is considered as behaving as a smooth, rigid sphere of the same density, and rate of sedimentation as the object. The customary units are expressed as nm diameters.
Median Stokes diameter (~tfor reporting purposes) - the point on the distribution curve of Stokes diameter where 50%
by weight of the sample is either larger or smaller. It therefore represents the median value of the determination.
ZOlZ627 - As shown in the Table the present invention allowed production of carbon blacks with increased CDBP's, fluffy DBP's and ~'s and decreased tints as compared to the carbon blacks produced by the control carbon black process runs, 1 and 4, utilizing a single quench. This indicates that carbon blacks of the present invention are characterized by increased aggregate size and structure. Further, as shown by the results for Set II, the present invention allowed for the production of carbon blacks having increased CDBP~s, fluffy DBP's and ~t's and decreased tints for a relatively constant CTAB. This indicates that the present invention produced carbon blacks with increased aggregate size and structure for a given CTAB.
As shown by the results for Set I, the present invention produced carbon blacks with increased CDBP's, fluffy DBP's and ~'s and decreased tints as compared to the carbon blacks produced by the control car~on black process run 1 at differing residence times at which the temperature of the effluent was initially lowered by the same amount.
Since the present invention relates to a process for controlling the aggregate size and structure of carbon blacks, nu~erous variations and modifications may obviously be made in the above described carbon black production runs without departing from the present invention.
Accordingly, it should be clearly understood that the forms of the present invention herein described, and shown in the figure, are illustrative only and are not intended to limit the scope of the invention. The present invention includes all modifications falling within the scope of the following claims.
The disc centrifuge is operated at 8000 rpm while the stroboscope is operating. 10 cc of distilled water are injected into the spinning disc as the spin fluid. The turbidity level is set to 0; and 1 cc of the solution of 10% absolute ethanol and 90% distilled water is injected as a buffer liquid. The cut and boost buttons of the disc centrifuge are then operated to produce a smooth concentration gradient between the spin fluid and the buffer liquid and the gradient is monitored visually. When the gradient becomes smooth such that there is no distinguishable boundary between the two fluids, 0.5 cc of the dispersed carbon black in aqueous ethanol solution is injected into the spinning disc and data collection is started immediately. If streaming occurs the run is aborted. The disc is spun for 20 minutes following the injection of the dispersed carbon black in aqueous ethanol solution. Following the 20 m,inutes of spinning, the disc is stopped, the temperature of the spin fluid is measured, and the average of the temperature of the spin fluid measured at the beginning of the run and the temperature of the spin fluid measured at the end of the run is entered into the computer which records the data from the disc centrifuge. The data is analyzed according to the standard Stokes equation and is presented using the following definitions:
Carbon black aggregate - a discrete, rigid colloidal entity that is the smallest dispersible unit: it is composed of extensively coalesced particles;
Stokes diameter - the diameter of a sphere which sediments in a viscous medium in a centrifugal or gravitational field according to the Stokes equation. A non-spherical object, such as a carbon black aggregate, may also be represented in terms of the Stokes diameter if it is considered as behaving as a smooth, rigid sphere of the same density, and rate of sedimentation as the object. The customary units are expressed as nm diameters.
Median Stokes diameter (~tfor reporting purposes) - the point on the distribution curve of Stokes diameter where 50%
by weight of the sample is either larger or smaller. It therefore represents the median value of the determination.
ZOlZ627 - As shown in the Table the present invention allowed production of carbon blacks with increased CDBP's, fluffy DBP's and ~'s and decreased tints as compared to the carbon blacks produced by the control carbon black process runs, 1 and 4, utilizing a single quench. This indicates that carbon blacks of the present invention are characterized by increased aggregate size and structure. Further, as shown by the results for Set II, the present invention allowed for the production of carbon blacks having increased CDBP~s, fluffy DBP's and ~t's and decreased tints for a relatively constant CTAB. This indicates that the present invention produced carbon blacks with increased aggregate size and structure for a given CTAB.
As shown by the results for Set I, the present invention produced carbon blacks with increased CDBP's, fluffy DBP's and ~'s and decreased tints as compared to the carbon blacks produced by the control car~on black process run 1 at differing residence times at which the temperature of the effluent was initially lowered by the same amount.
Since the present invention relates to a process for controlling the aggregate size and structure of carbon blacks, nu~erous variations and modifications may obviously be made in the above described carbon black production runs without departing from the present invention.
Accordingly, it should be clearly understood that the forms of the present invention herein described, and shown in the figure, are illustrative only and are not intended to limit the scope of the invention. The present invention includes all modifications falling within the scope of the following claims.
Claims (20)
1. A process for controlling the aggregate size and structure of carbon blacks comprising:
passing a stream of hot combustion gases through a reactor;
injecting feedstock into the stream of hot combustion gases at one or more points to form an effluent and start pyrolysis of the feedstock in the effluent;
lowering the temperature of the effluent at a first point within a time period of .002 second downstream from the furthest downstream point of injection of feedstock, without stopping the pyrolysis of the feedstock in the effluent.
passing a stream of hot combustion gases through a reactor;
injecting feedstock into the stream of hot combustion gases at one or more points to form an effluent and start pyrolysis of the feedstock in the effluent;
lowering the temperature of the effluent at a first point within a time period of .002 second downstream from the furthest downstream point of injection of feedstock, without stopping the pyrolysis of the feedstock in the effluent.
2. The process of claim 1 wherein the temperature of the effluent is lowered by an amount up to about 800 degrees F.
3. The process of claim 1 wherein the temperature of the effluent is lowered by an amount between about 50 and about 800 degrees F.
4. The process of claim 1 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
5. The process of claim 3 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
6. The process of claim 1 wherein the temperature of the effluent is lowered by injecting a quenching fluid.
7. The process of claim 6 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
8. The process of claim 6 wherein the quenching fluid lowers the temperature of the effluent up to about 800 degrees F.
9. The process of claim 6 wherein the quenching fluid lowers the temperature of the effluent between about 50 and about 800 degrees F.
10. The process of claim 7 wherein the quenching fluid lowers the temperature of the effluent between about 50 and about 800 degrees F.
11. A process for producing carbon blacks having controlled aggregate size and structure comprising:
passing a stream of hot combustion gases through a reactor;
injecting feedstock into the stream of hot combustion gases at one or more points to form an effluent and start pyrolysis of the feedstock in the effluent;
lowering the temperature of the effluent at a first point within a time period of .002 second downstream from the furthest downstream point of injection of feedstock, without stopping the pyrolysis of the feedstock in the effluent;
further lowering the temperature of the effluent at a second point, downstream of the first point, to stop pyrolysis of the feedstock in the effluent; and separating and collecting carbon black product.
passing a stream of hot combustion gases through a reactor;
injecting feedstock into the stream of hot combustion gases at one or more points to form an effluent and start pyrolysis of the feedstock in the effluent;
lowering the temperature of the effluent at a first point within a time period of .002 second downstream from the furthest downstream point of injection of feedstock, without stopping the pyrolysis of the feedstock in the effluent;
further lowering the temperature of the effluent at a second point, downstream of the first point, to stop pyrolysis of the feedstock in the effluent; and separating and collecting carbon black product.
12. The process of claim 11 wherein the temperature of the effluent is lowered by an amount up to about 800 degrees F.
13. The process of claim 11 wherein the temperature of the effluent is lowered by an amount between about 50 and about 800 degrees F.
14. The process of claim 11 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
15. The process of claim 13 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
16. The process of claim 11 wherein the temperature of the effluent is lowered by injecting a quenching fluid.
17. The process of claim 16 wherein the temperature of the effluent is lowered within a time period of between about 0.0 and about 0.0015 second from the furthest downstream point of injection of feedstock.
18. The process of claim 16 wherein the quenching fluid lowers the temperature of the effluent up to about 800 degrees F.
19. The process of claim 16 wherein the quenching fluid lowers the temperature of the effluent between about 50 and about 800 degrees F.
20. The process of claim 17 wherein the quenching fluid lowers the temperature of the effluent between about 50 and about 800 degrees F.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33414489A | 1989-04-06 | 1989-04-06 | |
| US334,144 | 1989-04-06 | ||
| US37072389A | 1989-06-23 | 1989-06-23 | |
| US370,723 | 1989-06-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2012627A1 CA2012627A1 (en) | 1990-10-06 |
| CA2012627C true CA2012627C (en) | 1995-08-08 |
Family
ID=26989058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012627A Expired - Fee Related CA2012627C (en) | 1989-04-06 | 1990-03-20 | Tandem quench |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPH0749541B2 (en) |
| KR (1) | KR930005684B1 (en) |
| CN (1) | CN1050855C (en) |
| AR (1) | AR245477A1 (en) |
| AU (1) | AU625117B2 (en) |
| BE (1) | BE1002548A3 (en) |
| BR (1) | BR9001575A (en) |
| CA (1) | CA2012627C (en) |
| CZ (1) | CZ284688B6 (en) |
| DE (1) | DE4010776A1 (en) |
| ES (1) | ES2020713A6 (en) |
| FR (1) | FR2645542B1 (en) |
| GB (1) | GB2232409B (en) |
| HU (1) | HUT55316A (en) |
| IT (1) | IT1240745B (en) |
| NL (1) | NL9000500A (en) |
| PE (1) | PE3991A1 (en) |
| PL (1) | PL163727B1 (en) |
| PT (1) | PT93676A (en) |
| RO (1) | RO113148B1 (en) |
| SE (1) | SE9001090L (en) |
| TR (1) | TR24400A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004281293A (en) * | 2003-03-18 | 2004-10-07 | Tokai Rubber Ind Ltd | Hose material for fuel cell system and hose for fuel cell system using the same |
| JP5027989B2 (en) * | 2004-03-25 | 2012-09-19 | 旭カーボン株式会社 | Manufacturing method of carbon black for tire tread |
| JP5697304B2 (en) * | 2008-12-17 | 2015-04-08 | 旭カーボン株式会社 | Production method of carbon black |
| JP2010144003A (en) * | 2008-12-17 | 2010-07-01 | Asahi Carbon Kk | Method of manufacturing carbon black, carbon black obtained by the method, and rubber composition containing the carbon black |
| JP2010144011A (en) * | 2008-12-17 | 2010-07-01 | Asahi Carbon Kk | Carbon black to be compounded with tire tread rubber, rubber composition for tire using the same and tire for automobile |
| JP5887096B2 (en) * | 2011-10-06 | 2016-03-16 | 旭カーボン株式会社 | Production method of carbon black |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2785964A (en) * | 1953-08-17 | 1957-03-19 | Phillips Petroleum Co | Process, apparatus, and system for producing, agglomerating, and collecting carbon black |
| US3211532A (en) * | 1962-03-12 | 1965-10-12 | Phillips Petroleum Co | Carbon black furnace |
| US3376111A (en) * | 1964-08-17 | 1968-04-02 | Phillips Petroleum Co | Production of high structure furnace carbon black |
| US3401020A (en) * | 1964-11-25 | 1968-09-10 | Phillips Petroleum Co | Process and apparatus for the production of carbon black |
| AU1991967A (en) * | 1967-04-05 | 1968-10-10 | Union Carbide Corporation | Manufacture of carbon black |
| DE1592864C3 (en) * | 1967-08-11 | 1975-05-22 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Method of making FurnaceruB |
| US3615211A (en) * | 1968-01-12 | 1971-10-26 | Ashland Oil Inc | Method and apparatus for manufacture of carbon black |
| DE2106912C2 (en) * | 1970-02-19 | 1986-06-05 | Cabot Corp., Boston, Mass. | Device for the production of furnace black |
| US3663172A (en) * | 1970-06-29 | 1972-05-16 | Cities Service Co | Carbon black production process |
| US3734999A (en) * | 1971-10-21 | 1973-05-22 | Phillips Petroleum Co | Control of carbon black quality |
| JPS5413233A (en) * | 1977-07-01 | 1979-01-31 | Toshiba Corp | Non-volatile semiconductor memory unit |
| DE2944855C2 (en) * | 1979-11-07 | 1986-10-16 | Degussa Ag, 6000 Frankfurt | Process for the production of furnace blacks with a lowered structure |
| DE3580634D1 (en) * | 1984-09-21 | 1991-01-03 | Mitsubishi Chem Ind | METHOD FOR THE PRODUCTION OF CARBON. |
-
1990
- 1990-02-27 ES ES9000566A patent/ES2020713A6/en not_active Expired - Fee Related
- 1990-03-02 NL NL9000500A patent/NL9000500A/en not_active Application Discontinuation
- 1990-03-13 PE PE1990166237A patent/PE3991A1/en unknown
- 1990-03-20 CA CA002012627A patent/CA2012627C/en not_active Expired - Fee Related
- 1990-03-26 SE SE9001090A patent/SE9001090L/en not_active Application Discontinuation
- 1990-04-02 CZ CS901615A patent/CZ284688B6/en not_active IP Right Cessation
- 1990-04-04 JP JP2088402A patent/JPH0749541B2/en not_active Expired - Fee Related
- 1990-04-04 AU AU52568/90A patent/AU625117B2/en not_active Ceased
- 1990-04-04 BR BR909001575A patent/BR9001575A/en unknown
- 1990-04-04 PL PL90284616A patent/PL163727B1/en unknown
- 1990-04-04 DE DE4010776A patent/DE4010776A1/en not_active Withdrawn
- 1990-04-05 TR TR90/0358A patent/TR24400A/en unknown
- 1990-04-05 RO RO144735A patent/RO113148B1/en unknown
- 1990-04-05 HU HU902100A patent/HUT55316A/en unknown
- 1990-04-05 FR FR9004388A patent/FR2645542B1/en not_active Expired - Fee Related
- 1990-04-05 PT PT93676A patent/PT93676A/en not_active Application Discontinuation
- 1990-04-05 GB GB9007714A patent/GB2232409B/en not_active Expired - Fee Related
- 1990-04-05 BE BE9000384A patent/BE1002548A3/en not_active IP Right Cessation
- 1990-04-06 AR AR90316579A patent/AR245477A1/en active
- 1990-04-06 CN CN90102031A patent/CN1050855C/en not_active Expired - Fee Related
- 1990-04-06 KR KR1019900004712A patent/KR930005684B1/en not_active Expired - Fee Related
- 1990-04-06 IT IT19959A patent/IT1240745B/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CZ161590A3 (en) | 1998-11-11 |
| AU625117B2 (en) | 1992-07-02 |
| RO113148B1 (en) | 1998-04-30 |
| IT9019959A0 (en) | 1990-04-06 |
| JPH0362858A (en) | 1991-03-18 |
| KR900016395A (en) | 1990-11-13 |
| TR24400A (en) | 1991-09-01 |
| KR930005684B1 (en) | 1993-06-24 |
| HU902100D0 (en) | 1990-07-28 |
| PE3991A1 (en) | 1991-03-06 |
| PT93676A (en) | 1990-11-20 |
| CA2012627A1 (en) | 1990-10-06 |
| AU5256890A (en) | 1990-10-11 |
| FR2645542B1 (en) | 1994-02-11 |
| IT1240745B (en) | 1993-12-17 |
| NL9000500A (en) | 1990-11-01 |
| BE1002548A3 (en) | 1991-03-19 |
| CZ284688B6 (en) | 1999-02-17 |
| SE9001090L (en) | 1990-10-07 |
| GB9007714D0 (en) | 1990-06-06 |
| IT9019959A1 (en) | 1991-10-06 |
| HUT55316A (en) | 1991-05-28 |
| FR2645542A1 (en) | 1990-10-12 |
| SE9001090D0 (en) | 1990-03-26 |
| JPH0749541B2 (en) | 1995-05-31 |
| ES2020713A6 (en) | 1991-09-01 |
| PL163727B1 (en) | 1994-04-29 |
| CN1046921A (en) | 1990-11-14 |
| GB2232409A (en) | 1990-12-12 |
| CN1050855C (en) | 2000-03-29 |
| GB2232409B (en) | 1992-10-14 |
| BR9001575A (en) | 1991-04-30 |
| AR245477A1 (en) | 1994-01-31 |
| DE4010776A1 (en) | 1990-10-11 |
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| EEER | Examination request | ||
| MKLA | Lapsed |