Carbon black with strontium and / or barium additives and method of making same

Abstract

The present invention relates, in part, to a method for producing carbon black utilizing at least a feedstock additive that is or includes strontium, barium, or a combination thereof. Optional additional feedstock additives can be used in combination with the strontium and / or barium. The present invention further relates to carbon black produced by one or more of the methods of the present invention. The present invention also relates to a method for producing carbon black utilizing at least a feedstock additive that is or includes strontium, barium, or a combination thereof. 2 / g~2,500m 2 / g Nitrogen BET surface area (N2SA) and a concentration (ppm) of Group IIA element in the carbon black of 4.3*N2SA-2150 or less, wherein the additive is or includes strontium, barium, or a combination thereof. Formulations, articles, and devices containing the carbon black are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to carbon black and methods for making the same. More specifically, the present invention relates to carbon black having or including a strontium and / or barium additive. Furthermore, the present invention relates to carbon black, such as etched carbon black, containing strontium and / or barium, optionally with one or more other additives.

[0002] The present invention is based in part on a currently recognized need to develop a class of carbon blacks that can be produced utilizing reduced overall combustion (OAC). Overall combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor. By reducing the OAC and still producing the same or essentially the same carbon black (based on parameters such as nitrogen surface area and / or COAN), safer operation of the process to produce carbon black can be achieved, and / or more environmentally friendly operation of producing carbon black can be achieved, and / or more reactor-friendly operation of producing carbon black can be achieved.

[0003] The present invention is also based in part on an improved replacement for calcium as an additive to raw materials for purposes such as etching in carbon black during formation. U.S. Patent No. 8,895,142 discloses the use of calcium as an additive, particularly when etching is desired in carbon black production. One problem with calcium is that it requires high ppm levels, high OAC, or both to achieve the desired effect.

[0004] The present invention therefore provides a method for solving and / or addressing the problem defined above and achieving the aims and advantages set out herein.

[0005] More specifically, a feature of the present invention is to provide carbon blacks with a particular surface area using high OAC but utilizing fewer feedstock additives.

[0006] Another feature of the present invention is to provide carbon blacks with higher surface areas that are produced with fewer feedstock additives at a given OAC.

[0007] Yet another feature of the present invention is to provide carbon blacks having a particular surface area but which are produced utilizing a reduced OAC for a given amount of feedstock addition, which are produced with fewer feedstock additives for a given OAC, or which are produced with both a reduced OAC and fewer feedstock additives.

[0008] A further feature of the present invention is to provide a feedstock additive that can at least partially or completely replace calcium as a feedstock additive.

[0009] A further feature of the present invention is to provide a feedstock additive that can not only replace calcium but also provide one or more beneficial properties, including, but not limited to, using less to achieve the same effect in the carbon black, and / or requiring less OAC to achieve the same or similar effect in the resulting carbon black, and / or producing a lower ash content.

[0010] Another feature of the present invention is to provide a method for producing carbon black utilizing specific feedstock additives and specific OAC and reactor configurations based on the desired surface area and OAC to achieve a carbon black useful in one or more end uses, such as reinforcing regions and / or polymeric conductive formulations.

[0011] Additional features and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the description and appended claims.

[0012] To achieve these and other advantages, and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates to a method for producing carbon black. The method includes introducing a heated gas stream into a carbon black reactor. The method further includes combining at least one feed additive with at least one carbon black feedstock to form a feed mixture. In the method, the feed additive is or includes strontium or barium, or a combination thereof. One or more other optional feed additives may also be utilized. The method also includes feeding the feed mixture to at least one feed introduction point of the carbon black reactor, and combining the at least the feed mixture through the at least one introduction point to the carbon black reactor with the heated gas stream to form a reaction stream in which carbon black is formed. The formed carbon black can be produced in an amount of 800 m3 or more. 2 / g~2,500m 2 The carbon black has a nitrogen BET surface area of ​​1 / g. The method then includes recovering the carbon black in the reaction stream. The method includes operating the carbon black reactor at an overall acid combustion (OAC) of 28% to 50%. Further, the method includes configuring the carbon black reactor so that OAC≦[(1350 + N2SA - 244 * ln(additive ppm + 1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area measured as described below. "Additive ppm" refers to the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive.

[0013] The present invention further relates to a method for producing carbon black, comprising introducing a heated gas stream into a carbon black reactor and feeding at least one carbon black feedstock to at least one feed point into the carbon black reactor. The method also comprises feeding at least one feedstock additive to the at least one feedstock additive into the carbon black reactor. Again, the feedstock additive is or comprises strontium or barium or a combination thereof. One or more other optional feedstock additives may also be utilized. The method also comprises combining the at least one carbon black feedstock and the at least one feedstock additive with the heated gas stream in the carbon black reactor to generate a carbon black mixture of 800 m 2 / g~2,500m 2 The method includes forming a reaction stream in which carbon black having a nitrogen BET surface area of ​​1 / g is formed. The method then includes recovering the carbon black in the reaction stream. In this method, as with the other methods, the method includes operating the carbon black reactor at an overall combustion rate (OAC) of 28% to 50%. Further, the carbon black reactor is configured such that OAC ≤ [(1350 + N2SA - 244 * ln(additive ppm + 1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area measured as described below. "Additive ppm" refers to the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive.

[0014] In addition, the present invention 2 / g~2,500m 2The carbon black has a nitrogen BET surface area (N2SA) of 1 / g and a Group IIA concentration (ppm) that is <4.3*N2SA-2150. The Group IIA concentration includes at least strontium, or barium, or a combination thereof. The carbon black further optionally has an ash content (%) that is ≦0.0012*N2SA-0.24. N2SA is the nitrogen BET surface area measured as described below. The Group IIA concentration is in ppm and is the total ppm (ppm by weight) of all Group IIA elements present in the carbon black, including at least barium and / or strontium. The ash content (%) is measured according to ASTM D1506.

[0015] Unless otherwise specified, ppm amounts stated herein are ppm by weight.

[0016] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the invention as claimed.

[0017] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate some of the embodiments of the invention and, together with the detailed description, serve to explain the principles of the invention. [Brief explanation of the drawings]

[0018] [Figure 1A] 1 is a graph showing nitrogen BET surface area in relation to OAC for examples of inventive carbon blacks (utilizing Sr (open symbols), Ba (filled symbols), or a Sr-Ca blend (stippled triangles) feed additive) and comparative carbon blacks (utilizing Ca only as a feed additive; stippled circles and diamonds) at various concentrations in the feed (squares—250 ppm, triangles—700 ppm, circles—1000 ppm, diamonds—1500 ppm). Also shown is a series of equation lines (striped symbols: squares—250 ppm, triangles—700 ppm, circles—1000 ppm, diamonds—1500 ppm) representing the nitrogen surface area resulting from the inventive furnace operating conditions and the comparative carbon black conditions. [Figure 1B] 1 is a graph showing nitrogen BET surface area in relation to OAC for examples of inventive carbon blacks (utilizing Sr (open symbols), Ba (filled symbols), or a Sr-Ca blend (stippled triangles) feed additive) and comparative carbon blacks (utilizing Ca only as a feed additive; stippled circles and diamonds) at various concentrations in the feed (squares—250 ppm, triangles—700 ppm, circles—1000 ppm, diamonds—1500 ppm). Also shown is a series of equation lines (striped symbols: squares—250 ppm, triangles—700 ppm, circles—1000 ppm, diamonds—1500 ppm) representing the nitrogen surface area resulting from the inventive furnace operating conditions and the comparative carbon black conditions.

[0019] [Figure 2] FIG. 1 is a schematic diagram of a portion of one type of carbon black reactor that can be used to produce the carbon black of the present invention.

[0020] [Figure 3] 1 is a graph showing Group IIA element concentration in relation to nitrogen BET surface area for examples of inventive carbon blacks (made with Sr or Ba feed additives, solid symbols) and comparative carbon blacks (made with Ca feed additives only, open symbols), and further shows equations illustrating the properties of the inventive carbon blacks from the properties of the comparative carbon blacks.

[0021] [Figure 4] 1 is a graph showing ash content (wt %) in relation to nitrogen BET surface area for examples of inventive carbon black (made with Sr or Ba feed additives, solid symbols) and comparative carbon black (made with Ca feed additive only, open symbols), and further shows an equation illustrating the properties of the inventive carbon black from the properties of the comparative carbon black. DETAILED DESCRIPTION OF THE INVENTION

[0022] New and unique methods for producing carbon black are provided utilizing one or more specific feedstock additives. Carbon blacks produced from one or more of these methods are also provided. The resulting carbon blacks contain one or more unique properties or relationships.

[0023] Nitrogen BET surface area is measured according to ASTM standard D6556 using samples degassed at 300°C for 1 hour under nitrogen flow, over a nitrogen partial pressure range of 0.05 to 0.1 P / Po.

[0024] With respect to the method of the present invention, the method includes utilizing a feedstock additive that is or contains strontium, or that is or contains barium, or that is or contains a combination of strontium and barium, which can be introduced as a pre-blended mixture or introduced separately. Additionally, optionally, other feedstock additives, such as calcium, can also be used.

[0025] More particularly, in one method of the present invention, a process for producing carbon black consists of, consists of, or includes introducing a heated gas stream into a carbon black reactor.

[0026] The method consists of, consists of, or includes combining at least one feedstock additive with at least one carbon black feedstock to form a feedstock mixture, wherein the at least one feedstock additive is, comprises, or consists of strontium or barium or a combination thereof.

[0027] The method comprises, consists of, or includes feeding a feed mixture to at least one feed introduction point of a carbon black reactor.

[0028] The method includes combining at least a feedstock mixture with a heated gas stream through at least one point of introduction into a carbon black reactor to form a carbon black reactor having a flow rate of 800 m 2 / g~2,500m 2 forming a reaction stream in which carbon black having a nitrogen surface area of ​​1 / g is formed.

[0029] The method comprises, consists of, or includes recovering carbon black in the reaction stream.

[0030] The method comprises, consists of, or includes operating a carbon black reactor at an overall attack rate (OAC) of 28% to 50%, e.g., 33.5% to 46.5%, wherein the carbon black reactor is configured such that OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), and the additive comprises strontium, barium, or both, e.g., 50 to 1500 ppm strontium, barium, or both, as a percentage of the total feedstock. N2SA is the nitrogen BET surface area, measured as above. "Additive ppm" refers to the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive.

[0031] In another method, a method for producing carbon black comprises, consists of, or includes introducing a heated gas stream into a carbon black reactor.

[0032] The method comprises, consists of, or includes feeding at least one carbon black feedstock to at least one feedstock introduction point into a carbon black reactor.

[0033] The method comprises, consists of, or includes feeding at least one feedstock additive to at least one point of entry into the carbon black reactor (e.g., separately from the carbon black feedstock), where, as previously mentioned, the at least one feedstock additive is, comprises, or consists of strontium or barium, or a combination thereof.

[0034] The at least one feedstock introduction point and the at least one introduction point may be the same or different, and may be located at the same location, approximately the same location, or different locations, or may overlap at one or more points if desired.

[0035] The method comprises combining at least one carbon black feedstock and at least one feedstock additive with a heated gas stream in a carbon black reactor over a temperature of 800 m 2 / g~2,500m 2 forming a reaction stream in which a carbon black having a nitrogen surface area of ​​1 / g is formed, the nitrogen surface area being measured as described above.

[0036] The method comprises, consists of, or includes recovering carbon black in the reaction stream.

[0037] The method comprises, consists of, or includes operating a carbon black reactor at an overall combustion rate (OAC) of 28% to 50%, wherein the carbon black reactor is configured such that OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), and the additive comprises strontium, barium, or both. OAC is as defined above. N2SA is the nitrogen BET surface area of ​​the resulting carbon black formed in the carbon black reactor. "Additive ppm" refers to the total amount of metal elements added to the feedstock, excluding residual impurities in the feedstock additive, by weight, relative to the total amount of feedstock.

[0038] Unless otherwise stated, any detail or option described herein may be utilized in any of the methods of the present invention.

[0039] With respect to the nitrogen surface area (i.e., nitrogen BET surface area or N2SA) that can be achieved with the method of the present invention, N2SA is 800 m 2 / g~2,500m 2 / g, e.g., 900m 2 / g~2,400m 2 / g, or 850m 2 / g~2,400m 2 / g, or 825m 2 / g~2,500m 2 / g, or 850m 2 / g~2,500m 2 / g, or 875m 2 / g~2,500m 2 / g, or 900m 2 / g~2,500m 2 / g, or 925m 2 / g~2,500m 2 / g, or 950m 2 / g~2,500m 2 / g, or 1,000m 2 / g~2,500m 2 / g, or 1,100m 2 / g~2,500m 2 / g, or 1,200m 2 / g~2,500m 2 / g, or 1,250m 2 / g~2,500m 2 / g, or 1,300m 2 / g~2,500m 2 / g, or 800m 2 / g~2,450m 2 / g, or 800m 2 / g~2,400m 2 / g, or 800m 2 / g~2,350m 2 / g, or 800m 2 / g~2,300m 2 / g, or 800m 2 / g~2,250m 2 / g, or 800m2 / g~2,200m 2 / g, or 800m 2 / g~2,150m 2 / g, or 800m 2 / g~2,100m 2 / g, or 800m 2 / g~2,050m 2 / g, or 800m 2 / g~2,000m 2 / g, or 800m 2 / g~1,950m 2 / g, or 800m 2 / g~1,900m 2 / g, or 800m 2 / g~1,800m 2 / g, or 800m 2 / g~1,700m 2 / g, or any N2SA below or above any of these ranges, or any combination of one endpoint of one range with the other endpoint of the other range.

[0040] In the process of the present invention, the carbon black reactor is configured for or operated at an overall combustion rate (OAC) of 28% to 50%, or 28.5% to 50%, or 29% to 50%, or 29.5% to 50%, or 30% to 50%, or 30.5% to 50%, or 31% to 50%, or 31.5% to 50%, or 32% to 50%, or 32.5% to 50%, or 33% to 50%, or 33.5% to 50%, or 34% to 50%, or 34.5% to 50%, or 35% to 50%. , or 35.5% to 50%, or 36% to 50%, or 36.5 to 50%, or 37% to 50%, or 37.5% to 50%, or 38% to 50%, or 38.5% to 50%, or 39% to 50%, or 39.5% to 50%, or 40% to 50%, or 41% to 50%, or 42% to 50%, or 45% to 50%, or 28% to 49.5%, or 28 % to 49%, or 28% to 48.5%, or 28% to 48%, or 28% to 47.5%, or 28% to 47%, or 28% to 46.5%, or 33.5% to 47%, or 33.5% to 46.5%, or 33.5% to 46%, or 33% to 47%, or 28% to 46%, or 28% to 45.5%, or 28% to 45%, or 28% to 44%, or 28 % to 43%, or 28% to 43%, or 28% to 42%, or 28% to 41%, or 28% to 40%, or 28% to 38%, or 28% to 36%, or 28% to 34%, or 28% to 32%, or other OACs above or below any one of these ranges, or any combination of one endpoint of one range with the other endpoint of the other range.

[0041] As shown, the carbon black reactor is configured such that OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5) [Equation 1]. The carbon black reactor can be configured such that OAC<[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5).

[0042] Referring to Equation 1, the OAC can be at least 1% lower than the value obtained from Equation 1, or at least 2%, 3%, 5%, 7%, 10%, 15%, 20%, or 25% lower than the value obtained from Equation 1, for example, 1% to 25% lower. And, these amounts of OAC can be used in the 800m 2 / g~2,500m 2 / g, or 900m 2 / g~2,400m 2 / g, or 1000m 2 / g~2,300m 2 / g, or 1100m 2 / g~2,300m 2 / g, or any other N2SA value or range provided herein.

[0043] As a further example, in this method, the OAC may be 33% to 47% and the N2SA may be 900m 2 / g~2,400m 2 / g.

[0044] As another example, OAC can be 33.5% to 46.5% and N2SA can be 850m 2 / g~2,400m 2 / g.

[0045] As another example, the OAC can be 33.5% to 46.5% and the N2SA is 1000m 2 / g~2,400m 2 / g.

[0046] OAC can be controlled in a number of ways. For example, OAC can be controlled, at least in part, by controlling the amount of feedstock introduced into the carbon black reactor. Other methods of controlling OAC include, but are not limited to, controlling the amount and composition of the heated gas introduced into the carbon black reactor and / or varying the composition of the feedstock (such as the hydrogen to carbon mass ratio).

[0047] In the process of the present invention, the process may include injecting oxygen downstream of the feedstock introduction point and upstream of the quench. The molar ratio of downstream oxygen to the amount of oxidant stream added to the combustion zone of the carbon black reactor may be from 0 to about 1:4, or from about 0.1:4 to about 1:4, or from about 0.2:4 to 0.9:4, or from about 0.3:4 to about 0.8:4, etc. Referring to Figure 2, for example, the molar ratio of downstream oxygen to the amount of oxidant stream 14 added to combustion zone 1 may be as described above.

[0048] The at least one feedstock introduction point may be one or more. If there are two or more, at least one feedstock introduction point may be downstream of at least one other feedstock introduction point.

[0049] Generally, a carbon black reactor includes or comprises a combustion zone, a transition zone, and a reaction zone. For example, a carbon black reactor can include or comprise a combustion zone, a transition zone, a conical inlet section, a stepped inlet section, a reaction zone, and a quench zone. Examples of suitable reactors include, but are not limited to, those described in U.S. Patent Nos. 3,922,335, 4,383,973, 5,190,739, 5,877,250, 5,904,762, 6,153,684, 6,156,837, 6,403,695, 6,485,693, 7,829,057, 8,871,173, 10,829,642, 6,926,877, 6,156,837, 5,190,739, and 5,877,251, the entire contents of all of which are incorporated herein by reference. Any one of these reactors can be used to produce the carbon black of the present invention, implementing and including the operating parameters and components described herein.

[0050] In the method of forming carbon black, at least one feedstock additive is utilized as indicated, which is or includes strontium or barium or a combination thereof.

[0051] Generally, the feedstock additive can be a substance that is a solid, a solution, a dispersion, a gas, or any combination thereof. For purposes of the present invention, the substance can be the metal (or metal ion) itself, a compound containing one or more of these elements (including a salt containing one or more of these elements), or the like. Exemplary Sr and / or Ba metal salts include both organic and inorganic salts, such as salts with either chloride, acetate, or formate, or a combination of two or more such salts. The form of the feedstock additive can, for example, introduce Sr and / or Ba metal or metal ions into the ongoing reaction to form the carbon black product.

[0052] The feedstock additive may preferably be in the form of an aqueous liquid containing at least a dissolved strontium salt and / or barium salt. Nevertheless, the amount of additive added to the feedstock is described herein as the amount of elemental metal relative to the amount of feedstock to which the additive is added, and excludes residual impurities, including elemental metal, typically present in feedstock additive formulations. Thus, the amount of additive does not take into account the aqueous liquid, the counterions of the metal salt, or any metal impurities in the feedstock additive.

[0053] The amount of feed additive provided to one or more feed introduction points or introduction points (e.g., feed additive introduction points) can be in an amount of 50 ppm to 1500 ppm or more (based on elemental metal in ionic or neutral form, excluding residual impurities), based on ppm levels (ppm by weight) of elemental metal, excluding residual impurities, added to the feed before any reaction occurs in the carbon black reactor or before thermal decomposition occurs. The amounts are: 60ppm~1500ppm, 75ppm~1500ppm, 100ppm~1500ppm, 125~1500ppm, 150ppm~1500ppm, 175ppm~1500ppm, 200ppm~1500ppm, 250ppm~1450ppm, 250ppm~1400ppm, 250ppm~1350ppm, 250ppm~1300ppm, 250ppm~1200ppm, 250ppm~1100ppm, 250ppm~1000ppm, 250ppm~900ppm, 250ppm~800ppm, 250ppm~700ppm, 250ppm~600ppm strontium, 250 ppm to 500 ppm, 250 ppm to 400 ppm, 300 ppm to 1500 ppm, 350 ppm to 1500 ppm, 400 ppm to 1500 ppm, 450 ppm to 1500 ppm, 500 ppm to 1500 ppm, 550 ppm to 1500 ppm, 600 ppm to 1500 ppm, 650 ppm to 1500 ppm, 700 ppm to 1500 ppm, 750 ppm to 1500 ppm, 800 ppm to 1500 ppm, and any amount above or below any of these ranges, or any combination of one endpoint of one range with the other endpoint of the other range. These amounts can apply to the feedstock additive as a whole, or to the strontium, barium, or both in the feedstock.

[0054] With particular reference to the feedstock additive amounts described above, use of usable amounts above 1500 ppm tends not to provide additional benefits compared to amounts below 1500 ppm. Furthermore, amounts above 1500 ppm may generally result in undesirably high ash content in the resulting carbon black formed. Therefore, it has been found that the amount of feedstock additive utilized in the process of the present invention is preferably between 50 ppm and 1500 ppm, more preferably between 250 ppm and 1500 ppm.

[0055] Optionally, and preferably, strontium and / or barium are present in the at least one feedstock additive at a maximum weight percentage (based on the total weight of the feedstock additive) compared to any metallic element that may optionally be present in the feedstock additive.

[0056] Optionally, the feedstock additive can be strontium and at least one other metallic element (other than barium, e.g., calcium) to form a total amount of metallic elements. In one such embodiment, strontium can be present, for example, at 30% to 99% by weight (or based on the total weight of the feedstock additive) of the total amount of metallic elements present, excluding residual impurities (e.g., 33% to 99% by weight, 35% to 99% by weight, 40% to 99% by weight, 45% to 99% by weight, 50% to 99% by weight, 55% to 99% by weight, 60% to 99% by weight, 70% to 99% by weight, 80% to 99% by weight, 85% to 99% by weight, 90% to 99% by weight, 95% to 99% by weight).

[0057] Optionally, the feedstock additive can be barium and at least one other metallic element (other than strontium, e.g., calcium) to form a total amount of metallic elements. In one such embodiment, barium can be present, for example, at 30% to 99% by weight (or based on the total weight of the feedstock additive) of the total amount of metallic elements present, excluding residual impurities (e.g., 33% to 99% by weight, 35% to 99% by weight, 40% to 99% by weight, 45% to 99% by weight, 50% to 99% by weight, 55% to 99% by weight, 60% to 99% by weight, 70% to 99% by weight, 80% to 99% by weight, 85% to 99% by weight, 90% to 99% by weight, 95% to 99% by weight).

[0058] The amount of raw material additive utilized in the process of the present invention may alternatively be characterized as utilizing a sufficient amount such that the resulting carbon black formed has from about 100 ppm to about 7,000 ppm or more of the elements strontium or barium, or both. The strontium and / or barium (and optionally other additives) may be uniformly dispersed throughout the carbon black.This amount is 100ppm~7,000ppm, 100ppm~6,500ppm, 100ppm~6,000ppm, 100ppm~5,500ppm, 100ppm~5,000ppm, 100ppm~4,500ppm, 100ppm~4,000ppm, 100ppm~3,500ppm, 100ppm~3,000ppm, 100ppm~2,500ppm, 100ppm~2,000ppm, 100ppm~1,500ppm, 100ppm~1,000ppm, 100ppm~500ppm, 150ppm~7,000ppm, 200ppm~7,000ppm, 250ppm~7,000ppm, 300ppm~7,000ppm, 350ppm~7,000ppm, 400ppm~7,000ppm, 450ppm~7,000ppm, 50 0ppm~7,000ppm, 550ppm~7,000ppm, 600ppm~7,000ppm, 650ppm~7,000ppm, 700ppm~7,000ppm, 750ppm~7,000ppm, 800ppm~7,000ppm, 850p pm~7,000ppm, 900ppm~7,000ppm, 950ppm~7,000ppm, 1,000ppm~7,000ppm, 1,000ppm~6,500ppm, 1000ppm~6,000ppm, 1,000ppm~5,500ppm , 1,000~5,000ppm, 1,000ppm~4,500ppm, 1,000ppm~4,000ppm, 1,000ppm~3,500ppm, 1,000ppm~3,000ppm, 1,000ppm~2,500ppm, 1,000ppm It can be 2,000 ppm, 1,000 to 1,500 ppm, 1,500 ppm to 7,000 ppm, 2,000 ppm to 7,000 ppm, 2,500 ppm to 7,000 ppm, 3,000 ppm to 7,000 ppm, 3,500 ppm to 7,000 ppm, 4,000 ppm to 7,000 ppm, 4,500 ppm to 7,000 ppm, 5,000 ppm to 7,000 ppm, 5,500 ppm to 7,000 ppm, 6,000 ppm to 7,000 ppm, or 6,500 ppm to 7,000 ppm.

[0059] In the present process, particularly with respect to the amount of raw material additives used to form the resulting carbon black having from about 100 ppm to about 7,000 ppm of strontium and / or barium present, as explained above, amounts of additive greater than 7,000 ppm in the formed carbon black may be achieved, but tend not to provide any additional benefit compared to amounts of 7,000 ppm or less in the carbon black. Furthermore, amounts greater than 7,000 ppm in the carbon black may generally result in an undesirably high ash content in the carbon black.

[0060] The other metallic element in the feedstock additive may be or may include calcium.

[0061] The other metal elements in the feedstock additives may be or include Group IA elements and / or calcium, which may be introduced at any time. Optional feedstock additives such as calcium may be introduced at the same time or at a different time and / or at the same or a different location prior to introduction into the reactor, and / or may be combined with the Sr and / or Ba additives.

[0062] The amount of Group IA element and / or calcium can be less than 500 ppm based on the total feedstock. This amount is based on the ppm level of the metal element added to the feedstock, excluding residual impurities and excluding any counterions or solvents that are part of the feedstock additive before any reaction occurs in the carbon black reactor or before thermal decomposition occurs. This amount can be less than 450 ppm, less than 400 ppm, less than 350 ppm, less than 300 ppm, less than 250 ppm, less than 200 ppm, less than 150 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm, less than 15 ppm, less than 10 ppm, less than 1 ppm, 1 ppm to 499 ppm, 10 ppm to 450 ppm, 25 ppm to 425 ppm, 50 ppm to 475 ppm, 75 ppm to 450 ppm, or 100 ppm to 400 ppm. These amounts can apply to the total amount of Group IA element (if used) and calcium (if used), or these amounts can apply individually to calcium or individually to one or more Group IA elements.

[0063] For example, Group IA elements may be introduced at any one time in an amount less than 10 ppm based on the total feedstock, and calcium may also be introduced at any one time in an amount less than 10 ppm based on the total feedstock.

[0064] As another example, no Group IA elements are introduced at any time and less than 500 ppm of calcium is introduced at any time.

[0065] As indicated, the use of Group IA elements and / or calcium is optional, and thus, optionally, Group IA elements are not incorporated or are not present. Optionally, calcium is not incorporated or is not present. Optionally, less than 50 ppm calcium is present.

[0066] Optionally, no potassium additive is introduced and no potassium is present in the formed carbon black.

[0067] Optionally, 100 ppm or less of potassium additive is introduced in the process of the present invention. The formed carbon black may also contain 100 ppm or less of elemental potassium in the formed carbon black. The amount of potassium additive present or introduced in the process of the present invention may be 90 ppm or less, 80 ppm or less, 70 ppm or less, 60 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, 15 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, or 1 ppm or less. The amount of potassium additive may be 0.1 ppm to 100 ppm, or 0.5 ppm to 100 ppm, or 1 ppm to 100 ppm.

[0068] The amount of potassium present in the formed carbon black can be 100 ppm or less, 90 ppm or less, 80 ppm or less, 70 ppm or less, 60 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, 15 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, or 1 ppm or less, or from 1 ppm to 100 ppm, or from 5 ppm to 20 ppm, or from 1 ppm to 50 ppm (based on the total weight of the carbon black).

[0069] Optionally, no sodium additive is introduced and no sodium is present in the formed carbon black. Optionally, the amount of sodium additive introduced or present in the carbon black in the present method can be 100 ppm or less, 50 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, 1 ppm or less, or 0.1 ppm or less. The amount of sodium present in the formed carbon black can be 100 ppm or less, 90 ppm or less, 80 ppm or less, 70 ppm or less, 60 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, or 1 ppm or less, or 1 ppm to 100 ppm, or 5 ppm to 100 ppm, or 1 ppm to 50 ppm (based on the total weight of the carbon black).

[0070] Examples of Group IA elements include lithium, sodium, potassium, rubidium, cesium, or francium, or any combination of two or more thereof. These elements may be contained in a feedstock additive that is a solid, a solution, a dispersion, a gas, or any combination thereof. For purposes of the present invention, a substance may be the metal (or metal ion) itself, a compound containing one or more of these elements (including a salt containing one or more of these elements), or the like. Exemplary Group IA metal salts include both organic and inorganic salts, such as, for example, salts of sodium and / or potassium with either chloride, acetate, or formate, or a combination of two or more such salts.

[0071] With respect to the feedstock additives, whether strontium and / or barium are used alone or together with other metallic elements such as calcium, the materials can be added together, separately, sequentially, or at different reaction locations. For example, the materials can be added at any time before full quenching, such as before introducing the carbon black yielding feedstock into zones 1 or 2 (of FIG. 2), during the introduction of the carbon black yielding feedstock into zone 3, after introducing the carbon black yielding feedstock into zones 4-10, or at any step before full quenching. More than one introduction point for the feedstock additives can be used.

[0072] The feed additives can be added in any manner, including any conventional means. In other words, the feed additives can be added in the same manner as the carbon black-yielding feedstock is introduced. The material can be added as a gas, liquid, or solid, or any combination thereof. The feed additives can be added at one or several points, as shown at point 12 in FIG. 2, and can be added in a single stream or multiple streams. The feed additives can also, or alternatively, be mixed with the feedstock, fuel, and / or oxidant before and / or during their introduction, such as in one or more of feed streams 7, 13, and 14 shown in FIG. 2, or at other reactor locations. The feed additives can be introduced at different points within the reactor (not shown) and / or through separate injectors and / or lances.

[0073] As previously mentioned, the present method has the advantage of utilizing strontium and / or barium as a feed additive instead of calcium alone. For example, in the present method, the method can form carbon black having a surface area and structure, and the carbon black reactor is operated at a desired OAC (%), due at least in part to the temperature of the heated gas stream and the reaction stream, to form carbon black (having a surface area and structure) with a reduction in OAC (%) of at least 4% compared to an otherwise identical method using only calcium (without strontium or barium) as a feed additive. A "reduction in OAC (%) of at least 4%" can mean at least 5%, at least 6%, or at least 7%, e.g., a 4% to 10% reduction in OAC (%), or a 5% to 8% reduction, or a 4% to 6% reduction in OAC (%), meaning that the OAC value as a percentage is reduced by a specified percentage in the present method (i.e., subtract the difference in OAC values, divide by the OAC value of a method using only calcium, and multiply by 100).

[0074] Although reference is made to a method of forming carbon black, this process can be considered a furnace carbon black or a furnace carbon black process for forming furnace black.

[0075] 2 shows an exemplary section of one type of carbon black reactor that can be used to produce the carbon blacks of the present invention, taking into account the process conditions and ingredients and additives described herein. The process conditions and reactor configuration for producing the carbon blacks of the present invention can include the following features:

[0076] Generally, the following process conditions and equipment configurations 1) and, optionally, one or more or all of 2) to 4) can be used to produce the carbon black of the present invention. At least 1) is always used, and preferably 2), or 3), or 4), or 2) to 3), or 3) to 4), or 2) to 4). The process conditions and equipment configurations are as follows: 1) Specified amounts of strontium and / or barium elements or their ions (e.g., Sr / Sr 2+ , Ba / Ba 2+ ) by introduction (e.g., injection). 2) Optionally inject water and oxygen downstream of the point of introduction of the carbon black-yielding feedstock but upstream of the quench to raise the temperature and create a humid environment. 3) Calcium is optionally introduced or added into the reactor to etch the carbon black within the reactor. 4) Potassium or other Group IA elements or their ions of the periodic table (e.g., Na / Na + , K / K + , Cs / Cs + ) is optionally introduced (e.g., injected).

[0077] In one embodiment, the carbon black of the present invention is produced in a furnace carbon black reactor, for example, as shown in Figure 2, having a combustion zone 1 with a converging diameter zone 2, a transition zone 3, a conical inlet section 4, a stepped inlet section 5, and a reaction zone 6. The diameter of combustion zone 1 is designated D-1 up to the point where converging diameter zone 2 begins, the diameter of zone 3 is designated D-2, the inlet and outlet diameters of conical zone 4 are designated D-3 and D-4, respectively, the diameters of stepped inlet zone 5 are designated D-5, D-6, and D-7, and the diameters of reaction zone 6 are designated D-8 and D-9. The lengths of combustion zone 1 are designated L-1 up to the point where converging diameter zone 2 begins, L-2 the length of the converging diameter zone, L-3 the length of the transition zone, L-4 the length of the conical section (zone 4), and L-5, L-6, and L-7 the lengths of the stages in the reactor inlet section (zone 5). The length of reaction zone 6 is designated L-8 and L-9.

[0078] To produce carbon black, hot combustion gases (also referred to as a heated gas stream) are generated in combustion zone 1 by contacting a liquid or gaseous fuel 13 with a suitable oxidant stream 14, such as air, oxygen, or a mixture of air and oxygen. When oxygen is added to the oxidant stream (referred to herein as "enriched oxygen"), the oxygen is added to enrich the oxygen content of the air to a level of about 21% to about 35%. Suitable fuels for contacting the oxidant stream in combustion zone 1 to produce hot combustion gases include any readily combustible gas, vapor, or liquid stream, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene. Generally, fuels are enriched in carbon-containing components, particularly hydrocarbons. By way of example, the volumetric ratio of air to natural gas utilized to produce the carbon black of the present invention can be from about 5:1 to about 100:1. The oxidant stream can be preheated to facilitate the production of hot combustion gases.

[0079] The hot combustion gas stream (or heated gas stream) flows downstream from zones 1 and 2 to zones 3, 4, 5, and 6. The direction of the hot combustion gas flow is indicated by the "F" arrow in FIG. 2. A carbon black-yielding feedstock (also referred to as carbon black feedstock) can be introduced at point 7 (located in zone 3). Suitable carbon black-yielding hydrocarbon feedstocks readily volatilizable under reaction conditions for use herein include unsaturated hydrocarbons such as acetylene; olefins such as ethylene, propylene, and butylene; aromatics such as benzene, toluene, and xylene; certain saturated hydrocarbons; and other hydrocarbons such as kerosene, naphthalene, terpenes, ethylene tar, and aromatic cycle stock. Feedstock additives can be introduced at point 7 or at other points within zone 3 or other zones. The feedstock additives can be precombined with the carbon black-yielding feedstock or added separately to the reactor.

[0080] Optionally, a feedstock with a lower sulfur content can be used. The sulfur level can be, for example, from 0 to about 5 weight percent, or from 0 to about 1 weight percent, or from 0 to about 0.5 weight percent, or from 0 to about 0.1 weight percent, based on the total amount of carbon black yielding feedstock used in the entire process. These sulfur level ranges and amounts can also apply to any individual carbon black yielding feedstock stream.

[0081] Generally, the carbon black yielding feedstock (alone or in combination with feedstock additives) is injected at point 7 in the form of multiple streams (not shown) that penetrate the inner region of the hot combustion gas stream to ensure high speed mixing and shearing of the carbon black yielding feedstock by the hot combustion gases, thereby rapidly and completely decomposing and converting the feedstock to carbon black.

[0082] A mixture of carbon black-yielding feedstock (including feedstock additives) and hot combustion gases (also referred to as the reaction stream) flows downstream through zone 3 to zones 4, 5, and 6. Water can be injected into zone 6 at point 8 within the reactor. Without being bound by theory, this water may vaporize to steam, increasing the concentration of gaseous species capable of oxidizing carbon and, consequently, the rate of oxidative attack on the carbon black surface. This can result in the production of etched or porous carbon black. The weight ratio of injected water to carbon black-yielding feedstock is typically 0 to about 1:1, or about 0.1:1 to about 1:1, or about 0.2:1 to about 0.5:1, or about 0.3:1 to about 0.7:1, or about 0.4:1 to about 0.8:1, etc. This water (referred to herein as "intermediate water") is distinct from the quench water located at point 10, the purpose of which is to quench the reaction. In Figure 2, "A" is the distance from the beginning of zone 4 to intermediate water point 8, which varies depending on the location of intermediate water injection. Oxygen gas (referred to herein as "intermediate oxygen") can be added to zone 6 at point 9. Without being bound by theory, the oxygen reacts with combustible species, such as carbon monoxide and hydrogen, in the gas to increase the temperature of the system, thereby increasing the rate of oxidative attack on the carbon black surface, resulting in etched or porous carbon black with a higher surface area than carbon black not treated with oxygen gas. The molar ratio of intermediate oxygen to the amount of air added to zone 1 can be 0 to about 1:4, or about 0.1:4 to about 1:4, or about 0.2:4 to 0.9:4, or about 0.3:4 to about 0.8:4, etc. In Figure 2, "B" is the distance from the beginning of zone 4 to intermediate oxygen point 9, which varies depending on the location of intermediate oxygen injection.As an example, water and oxygen can be injected downstream of the carbon black yielding feedstock introduction point and upstream of the quench and are effective to increase the temperature in the reactor by at least about 5%, or at least about 10%, or at least about 15%, or at least about 20%, and / or increase the moisture content by at least about 5%, or at least about 10%, or at least about 15%, or at least about 20%, compared to the temperature and moisture content in the reactor without the water and oxygen injection and all other conditions remaining the same.

[0083] As shown, the feed additives may be introduced into the reactor by themselves and / or in a precombined state at one or more various points in the reactor (with reference to FIG. 2, these points may be or include points 3, 4, 5, 8, 6, and / or 9).

[0084] A reactor quench 11, located at point 10, is utilized to inject a quench fluid, which may be water, to stop further formation of carbon black. Point 10 may be determined by any method known in the art for selecting a quench location to stop pyrolysis. In Figure 2, "Q" is the distance from the beginning of Zone 4 to quench point 10 and varies depending on the location of the quench. As an example, for these carbon blacks, maximizing Q maximizes the time available for etching and creates a high surface area.

[0085] After quenching the mixture of hot combustion gases and carbon black-yielding feedstock, the cooled gases are passed downstream to any conventional cooling and separation equipment, thereby recovering the carbon black. Separation of the carbon black from the gas stream is readily accomplished by conventional equipment, such as a settler, cyclone separator, or bag filter. This separation can be followed by pelletization, for example, using a wet pelletizer.

[0086] As indicated, the present invention further relates to novel carbon blacks (e.g., furnace carbon blacks). In particular, the present invention relates to 800m 2 / g~2,500m2 For carbon black having a nitrogen BET surface area (N2SA) of 1 / g, the concentration of Group IIA elements in the carbon black can be less than or equal to 4.3*N2SA-2150 [Equation 2]. The concentration (ppm) of Group IIA elements in the carbon black can be an amount less than 4.3*N2SA-2150. This amount can be characterized as a certain percentage lower than 4.3*N2SA-2150, e.g., at least 1% lower, at least 5% lower, at least 10% lower, at least 15% lower, or at least 20% lower, e.g., 1% to 50% lower, preferably up to 75% lower than 4.3*N2SA-2150. Preferably, the Group IIA elements include at least strontium, barium, or a combination thereof. As noted above, the metal elements in the carbon black can further include Group IA and / or additional Group IIA elements in addition to strontium, barium, or both. The ash content (wt%) of the carbon black can be less than or equal to 0.0012*N2SA-0.24 [Equation 3]. The ash content (wt%) of the carbon black can be less than 0.0012*N2SA-0.24.

[0087] Referring to Equation 3, the ash content (wt%) can be at least 1% lower than the value obtained from Equation 3, or can be at least 2%, 3%, 5%, 7%, 10%, 15%, 20%, or 25% lower than the value obtained from Equation 3, for example, 1% to 25% lower.

[0088] The Group IIA and Group IA elements in the carbon black are the result of a "feedstock additive" comprising metallic elements including or consisting essentially of strontium and / or barium, and the descriptions and parameters set forth above for this feedstock additive are equally applicable to the Group IIA and Group IA elements contained in the carbon black product.

[0089] The carbon black of the present invention has a viscosity of 800 m 2 / g~2,500m 2 / g, e.g., 900m 2 / g~2,400m 2 / g, or 850m 2 / g~2,400m 2 / g, or 825m 2 / g~2,500m 2 / g, or 850m 2 / g~2,500m 2 / g, or 875m 2 / g~2,500m 2 / g, or 900m 2 / g~2,500m 2 / g, or 925m 2 / g~2,500m 2 / g, or 950m 2 / g~2,500m 2 / g, or 1,000m 2 / g~2,500m 2 / g, or 1,100m 2 / g~2,500m 2 / g, or 1,200m 2 / g~2,500m 2 / g, or 1,250m 2 / g~2,500m 2 / g, or 1,300m 2 / g~2,500m 2 / g, or 800m 2 / g~2,450m 2 / g, or 800m 2 / g~2,400m 2 / g, or 800m 2 / g~2,350m 2 / g, or 800m 2 / g~2,300m 2 / g, or 800m 2 / g~2,250m 2 / g, or 800m 2 / g~2,200m 2 / g, or 800m 2 / g~2,150m 2 / g, or 800m 2 / g~2,100m 2 / g, or 800m 2 / g~2,050m 2 / g, or 800m 2 / g~2,000m 2 / g, or 800m 2 / g~1,950m 2 / g, or 800m 2 / g~1,900m 2 / g, or 800m 2 / g~1,800m 2 / g, or 800m 2 / g to 1,700 m / g, or any N2SA below or above any of these ranges, or any range defined by any combination of one endpoint of one range with the other endpoint of the other range. N2SA is the nitrogen BET surface area measured as above.

[0090] Optionally, the concentration (ppm) of the Group IIA element in the carbon black can be 100 to 7000 ppm (by weight based on the total mass of the carbon black). For example, the concentration of the Group IIA element can be 200 ppm to 6500 ppm, 300 ppm to 6000 ppm, 400 ppm to 5000 ppm, 500 ppm to 4000 ppm, 600 ppm to 7000 ppm, or 800 ppm to 6500 ppm, or any range defined by any combination of one endpoint of one range with the other endpoint of the other range.

[0091] Optionally, the concentration (ppm) of strontium and / or barium in the carbon black can be 100 to 7000 ppm (by weight, based on the total mass of the carbon black). For example, the concentration of Group IIA elements can be 200 ppm to 6500 ppm, 300 ppm to 6000 ppm, 400 ppm to 5000 ppm, 500 ppm to 4000 ppm, 600 ppm to 7000 ppm, or 800 ppm to 6500 ppm, or any range defined by any combination of one endpoint of one range with the other endpoint of the other range.

[0092] As a result of the above-mentioned raw material additives, the carbon black may contain only strontium or barium, or a combination thereof.

[0093] As a result of using the above-mentioned raw material additives, the carbon black may contain only Group IIA elements, including at least strontium and / or barium.

[0094] The total weight of Group IIA elements present can be at least 30% by weight strontium, based on the total weight of the Group IIA elements, or at least 35% by weight strontium, or at least 40% by weight strontium, or at least 50% by weight strontium, or at least 60% by weight strontium, or at least 70% by weight strontium, or at least 80% by weight strontium, based on the total weight of the Group IIA elements, or at least 99% by weight strontium, based on the total weight of the Group IIA elements.

[0095] The total weight of Group IIA elements present can be at least 30% by weight barium based on the total weight of the Group IIA elements, or at least 35% by weight barium based on the total weight of the additive, or at least 40% by weight barium, or at least 50% by weight barium, or at least 60% by weight barium, or at least 70% by weight barium, or at least 80% by weight barium, or at least 99% by weight barium based on the total weight of the Group IIA elements.

[0096] When present together (strontium and barium), the total weight of the Group IIA elements present can be at least 30% by weight strontium / barium based on the total weight of the Group IIA elements, or at least 35% by weight strontium / barium based on the total weight of the Group IIA elements, or at least 40% by weight strontium / barium, or at least 50% by weight strontium / barium, or at least 60% by weight strontium / barium, or at least 70% by weight strontium / barium, or at least 80% by weight strontium / barium, or at least 99% by weight strontium / barium based on the total weight of the Group IIA elements.

[0097] The total weight of the Group IIA element present can be at least 30 wt.% strontium or barium or a combination thereof, and up to 70 wt.% can be one or more other additives, such as, but not limited to, calcium. The weight ratio of the Group IIA element (A), which is strontium, barium, or a combination thereof, to the other additive (B), such as Ca, can be a weight ratio A:B of 99:1 to 30:70, such as 98:2 to 50:50, 95:5 to 50:50, 90:10 to 50:50, 80:20 to 50:50, 70:30 to 50:50, 60:10 to 50:50, 70:30 to 50:50, 80:10 to 50:50, 80:20 to 50:50, 80:30 to 50:50, 80:40 to 50:50, 80:5 ... :40~50:50, 99:1~51:49, 99:1~55:45, 99:1~60:40, 99:1~65:35, 95:1~55:45, 95:1~60:40, 95:1~65:35, 30:70~99:1, 35:65~99:1, 40:60~99:1, 45:55~99:1, and other amounts within or outside these specified ranges.

[0098] Optionally, the carbon black has less than 0.1 wt. % calcium, or less than 500 ppm, or less than 250 ppm, or less than 100 ppm, or less than 50 ppm, or less than 25 ppm, or less than 5 ppm, or less than 1 ppm, or 0 ppm.

[0099] Optionally, the carbon black has less than 0.1 wt. % potassium and / or sodium, or less than 500 ppm, or less than 250 ppm, or less than 100 ppm, or less than 50 ppm, or less than 25 ppm, or less than 5 ppm, or less than 1 ppm, or 0 ppm.

[0100] Optionally, the carbon black has less than 0.1 wt. % Group IA elements, or less than 500 ppm, or less than 250 ppm, or less than 100 ppm, or less than 50 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 0 ppm.

[0101] Simply described, carbon black particles are aggregates of many small particles called primary particles ("primaries"). The size of the primary particles in a carbon black particle can vary, but the processes exemplified herein, for example, are capable of producing carbon black having primary particles with a size (diameter) of at least about 8 nm. The number of primary particles in an aggregate can also vary, for example, from about one to about several tens, or even several hundred, resulting in carbon black particles with a size of up to about 500 nm. The number of primary particles in a carbon black particle and their arrangement determine not only the size of the carbon black particle but also the structure of the carbon black.

[0102] The average primary particle size, as determined by ASTM D3849-04 (incorporated herein by reference in its entirety), can be, for example, less than about 100 nm, or less than about 75 nm, or less than about 50 nm, or less than about 30 nm, or less than about 20 nm, or less than about 10 nm. Carbon black aggregates can be, for example, collections of primary carbon black particles that are fused at contact points and cannot be easily separated by shear. The average aggregate size of carbon black can be extracted from TEM image analysis using the imaging techniques described in ASTM D3849-04 (incorporated herein by reference in its entirety). Carbon black can have an average aggregate size of, for example, less than about 500 nm, or less than about 400 nm, or less than about 300 nm, or less than about 200 nm, or less than about 100 nm.

[0103] The average primary particle size and / or average aggregate particle size that the carbon black of the present invention can have is not limited, but the carbon black can have one or more of the following properties: a) an average primary particle size of about 8 nm to about 100 nm, or about 8 nm to about 50 nm, or about 9 nm to about 40 nm, or about 9 nm to about 30 nm, or about 10 nm to about 20 nm, or about 10 to about 15 nm; b) an average aggregate particle size of about 8 nm to about 500 nm, or about 20 nm to about 400 nm, or about 30 to about 300 nm, or about 50 nm to about 250 nm, or about 75 nm to about 200 nm, or about 100 nm to about 175 nm, or about 125 nm to about 150 nm, or about 50 nm to about 70 nm, or about 55 nm to about 65 nm, or about 58 nm to about 62 nm. For example, the carbon black of the present invention may have an average primary particle size of about 8 nm to about 100 nm and an average carbon black particle size of about 8 nm to about 500 nm.

[0104] The carbon black of the present invention can be prepared by simultaneously adjusting, for example, the burner natural gas rate, the enriched oxygen rate, the feedstock feed rate, the type of feedstock, the feedstock additive element concentration in the feedstock, the optional Group IA element concentration in the feedstock, the intermediate water rate and location, and the intermediate oxygen rate and location to achieve the desired properties. Selection of the specific reactor configuration described herein can also be important in achieving the desired properties. The surface area of ​​the carbon black can be increased, for example, by increasing the burner natural gas rate, increasing the enriched oxygen rate, decreasing the feedstock feed rate, increasing the feedstock additive element concentration, increasing the Sr and / or Ba concentration in the feedstock additive (e.g., from 30 / 70 Sr / Ca to 90 / 10 Sr / Ca), and / or increasing the intermediate water rate while simultaneously increasing the intermediate oxygen rate. The exact level of each variable required to produce carbon black with the desired properties can depend on the reactor configuration and the various injection methods into the reactor.

[0105] The carbon black products of the present invention can be in powder or finely divided form. The carbon black products of the present invention can also be pelletized, agglomerated, or mixed with any other substance, such as particles, liquids, solids, polymers, or other materials.

[0106] Typical feed additives used in carbon black production are calcium or potassium, or sodium, or combinations thereof. The use of strontium and / or barium as feed additives has not been considered an option that offers particular advantages in carbon black production, especially compared to calcium. Therefore, it was quite unexpected to discover that the use of strontium alone, barium alone, and / or a combination of strontium and barium, or strontium and / or barium with certain amounts of calcium, did not produce comparable results, and in fact, produced significantly and unexpectedly superior results in some areas.

[0107] As described above and / or shown in the examples, the present invention can provide the following unique and unexpected properties and / or advantages, particularly compared to the use of standard calcium additives alone as a raw material additive during carbon black production: 1) The same or nearly the same N2SA carbon black can be formed using fewer ppm Sr (relative to Ca) ("nearly the same" means within 10% or within 5%). The ppm% Sr (relative to Ca) can be reduced by at least 25%, at least 50%, at least 60%, at least 75%, or at least 80% (relative to Ca). 2) Higher N2SA carbon black can be formed using fewer ppm Sr (relative to Ca). The % increase in N2SA can be at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% (compared to Ca, but at a lower ppm amount), and the ppm % of Sr (compared to Ca) can be reduced by at least 25%, at least 50%, at least 60%, at least 75%, or at least 80% (compared to Ca). 3) The same or nearly the same N2SA carbon black can be formed with a lower OAC (compared to Ca). The % reduction in OAC (the difference in OAC under different operating conditions) can be at least 1%, at least 2%, at least 3%, at least 4%, or at least 5%, and it is understood that each OAC % is important in the carbon black industry. Therefore, a reduction in OAC of 2% or more is very important. 4) A higher N2SA carbon black can be formed with a lower OAC (compared to Ca). It is understood that the % reduction in OAC can be at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, and each OAC % is significant, and the % increase in N2SA can be at least a 10% increase, at least a 20% increase, at least a 30% increase, at least a 40% increase, or at least a 50% increase (compared to Ca at the lower ppm amounts).A-1: The above-mentioned unique and unexpected properties and / or advantages 1), 2), 3), and 4) are particularly more pronounced when the OAC used to produce the carbon black is 32% or more, 32.5% or more, 33% or more, 33.5% or more, 34% or more, for example, 32%, 32.5%, 33%, or 33.5% to 44%, 45%, 46%, 46.5%, 47%, or 48%. A-2: The above-mentioned unique and unexpected properties and / or advantages 1), 2), 3), and 4) are particularly more pronounced when the N2SA is 800m. 2 / g or more, or 900m 2 / g or more, or 1000m 2 / g or more, e.g., 800m 2 / g~2500m 2 / g, or 900m 2 / g~2500m 2 / g, or 1000m 2 / g~2500m 2 / g. A-3: The above unique and unexpected properties and / or advantages 1), 2), 3), and 4) are particularly more pronounced when the ppm amount of Sr is at least 250 ppm, at least 300 ppm, at least 350 ppm, at least 400 ppm, at least 500 ppm, at least 600 ppm, or less than 1000 ppm, or less than 900 ppm, or less than 800 ppm, or less than 700 ppm, for example, 200 ppm to 1000 ppm. References to ppm amount are based on ppm (by mass) of the additive in the raw material.

[0108] The above unique and unexpected properties and / or advantages 1), 2), 3), and 4) and A-1 through A-3 equally apply when the additive is Ba (compared to Ca).

[0109] The above-described unique and unexpected properties and / or advantages are further illustrated in FIGS.

[0110] Unique and unexpected properties and / or advantages are also observed when C-1:Sr is used in combination with Ca (e.g., both are used as additives during the carbon black process). More specifically, by using a blend or combination of Sr and Ca, where Sr is present in a weight percent amount of 30:70 (Sr:Ca) to 99:1 (Sr:Ca), higher N2SA carbon black can be produced at the same additive loading (compared to 100% Ca at the same ppm loading). The Sr:Ca amount can be 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, or from 90:10 to 99:1 (Sr:Ca). These unique and unexpected properties and / or advantages of Sr:Ca blends / mixtures / combinations are observed when N2SA is used at 800m 2 / g or more, or 825m 2 / g or more, or 850m 2 / g or more, or 1000m 2 / g or more, e.g., 800m 2 / g~2500m 2 / g, or 850m 2 / g~2500m 2 / g, or 1000m 2 / g~2500m 2 / g. The unique and unexpected properties and / or advantages of the Sr:Ca blend / mixture / combination are particularly pronounced when the total amount of additive (Sr and Ca combined) is at least 250 ppm, at least 300 ppm, at least 350 ppm, at least 400 ppm, at least 500 ppm, at least 600 ppm, at least 700 ppm, at least 800 ppm, at least 900 ppm, at least 1000, at least 1100 ppm, at least 1200 ppm, at least 1300 ppm, at least 1400 ppm, at least 1500 ppm, e.g., 250 ppm to 1500 ppm. References to ppm amounts in a feedstock are based on ppm (by mass) of elemental metal relative to the amount of feedstock added, excluding residual impurities in the delivery vehicle (typically an aqueous salt solution) and not taking into account counterions of metal salts or aqueous carriers added to the feedstock.

[0111] The above unique and unexpected properties and / or advantages C-1 also apply equally when the additive is Ba instead of Sr in combination with Ca.

[0112] The above-described unique and unexpected properties and / or advantages C-1 are further illustrated in part by Figures 1A-1B, 3, and 4. As explained in the Examples section below, and as can be seen from the data, it was possible to produce carbon blacks having a given N2SA with reduced OAC when Sr or Ba were used as feedstock additives.

[0113] Furthermore, as shown in FIG. 3, all data below the line are examples in which Sr or Ba was used as a feedstock additive, and all data above the line are examples in which Ca was used as a feedstock additive. As can be seen from the figure, the use of Sr or Ba significantly reduced the Group IIA element concentration (ppm) per specified N2SA carbon black, resulting in less ash formation on the carbon black.

[0114] Furthermore, as shown in FIG. 4, all data below the line are examples where Sr or Ba was used as a feedstock additive, and all data above the line are examples where Ca was used as the only feedstock additive. As can be seen from the figure, the use of Sr or Ba significantly reduced the ash content (wt %) per designated N2SA carbon black.

[0115] The carbon black of the present invention can be post-treated after exiting the reactor, as shown in FIG. 2, by, for example, water or acid washing, heat treatment, and / or chemical molecular treatment. The post-treatment can be a simple water (hot or cold) wash, or an acid washing procedure or heat treatment. The temperature of the heat treatment can be such that it results in some degree of graphitization of the carbon black. Alternatively, the temperature can be such that it does not result in additional graphitization, for example, below about 1100°C. This is shown, for example, in D.H.E. Verett, et al., J. Chem. Soc., Faraday Trans. I, 82, 2915-2928 (1986). The heat treatment can be carried out in an inert atmosphere, for example, argon or nitrogen. Alternatively or additionally, the carbon black can be heat treated as described in U.S. Pat. No. 1,352,536 and / or U.S. Patent Application Publication No. 20130295462, the entire contents of both of which are incorporated herein by reference, to alter surface properties such as Raman crystallite size, crystallinity, or water diffusion pressure.

[0116] The carbon black of the present invention may have one or more chemical groups, such as organic groups, attached to its surface (e.g., chemically bonded, adsorbed, coated, or otherwise present). For example, the carbon black may have attached at least one organic group comprising an aromatic group and / or an alkyl group. The aromatic group or alkyl group may be directly attached to the carbon black (e.g., a carbon atom of the aromatic group or alkyl group is bonded (e.g., attached) to the carbon black). Exemplary chemical groups, and methods for attaching these groups to conventional carbon black, are described in the following U.S. patents and publications, all of which are incorporated herein by reference in their entireties: U.S. Patent Nos. 5,851,280, 5,837,045, 5,803,959, 5,672,198, 5,571,311, 5,630,868, 5,707,432, 5,554,739, 5,689,016, 5,713,988, and WO 96 / 18688, WO 97 / 47697, and WO 97 / 47699. The organic groups that can be attached onto the carbon black can be electron donor and / or electron acceptor groups. Alternatively, the organic groups that can be attached to the carbon black can contain electron donor and / or electron acceptor groups. Yet another possibility is that the electron donor and / or electron acceptor groups can associate with the carbon black surface as counterions. The organic groups attached to the carbon black can be simple small molecules, oligomers, or polymers. Examples of such electron donor and electron acceptor groups include, but are not limited to, substituted or unsubstituted quinones; organometallic groups such as substituted or unsubstituted metallocenes (e.g., ferrocene); substituted or unsubstituted thiophenes, furans, pyrroles, or carbazoles; substituted or unsubstituted tetrathiafulvalenes; and / or substituted or unsubstituted aromatic amines, such as triphenylamine. Examples of polymeric electron donor and acceptor groups include, but are not limited to, polythiophenes, polyacetylenes, polyphenylene vinylenes, polyanilines, and polyvinyl carbazoles.

[0117] The organic groups that can be attached to the carbon black can be at least one or more ionic or ionizable groups, or both. Ionic or ionizable functional groups that form anions or anionic groups include, for example, acidic groups or salts of acidic groups. Examples of organic groups that are anionic in nature include -C6H4-COO - X + ;-C6H4-SO3-X + ;-C6H4-(PO3) 2- 2X + ;-C6H2-(COO - X + )3;-C6H3-(COO - X + )2;-(CH2)2-(COO - X + );-C6H4-(CH2)2-(COO - X + ), but are not limited to, X + Na + , H + , K. + , NH4 + , Li + , Ca 2+ , Mg 2+ As will be appreciated by those skilled in the art, X is any cation such as + may be formed in situ as part of the manufacturing process or may be associated with aromatic or alkyl groups via typical salt or ion exchange processes. Amines represent examples of ionizable functional groups that form cations or cationic groups. Quaternary ammonium, phosphonium, and sulfonium groups also represent examples of cationic groups. Examples of organic groups that are cationic in nature include -CHN(CH). + Y - , -C6H4COCH2N(CH3)3 + Y - , -C6H4(NC5H5) + Y - , -(C5H4N)C2H5 + Y - , -(C3H5N2) + Y - (imidazole)-C7H7N2)+ Y - (indazole), -C6H4COCH2(NC5H5) + Y - , -(C5H4N)CH3 + Y - , and -C6H4CH2N(CH3)3 + Y - These include, but are not limited to, Y - is any halide or anion, e.g., RSO3 - , SO4 2- , PO4 3- , NO3 - , OH3 - , CH3COO - or a combination thereof, where R is an alkyl group or an aromatic group. As will be appreciated by those skilled in the art, Y - may be formed in situ as part of the manufacturing process or may be associated with aromatic or alkyl groups via typical salt or ion exchange processes.

[0118] Any physically acceptable level of treatment of chemical groups (e.g., organic groups) with carbon black is generally acceptable. The treatment level of chemical groups (e.g., organic groups) on carbon black is expressed in μmol / m of carbon. 2 For example, about 0.1 to about 10 μmol / m 2 It could be more than that.

[0119] The carbon black of the present invention may have one type of chemical group (e.g., organic group) attached to its surface, or two or more types of chemical groups attached. In other words, double- or multi-treated modified carbon blacks can be used. Also, mixtures of modified carbon blacks with different chemical groups attached can be used.

[0120] The carbon black of the present invention can be used, for example, in capacitors, e.g., electrochemical capacitors, batteries, or other energy storage devices. The carbon black can be, for example, part of an electrode. The electrode can be in direct contact with a current collector, which is generally a metal (e.g., strip, rod, etc.), such as aluminum, aluminum with a thin conductive carbon coating, etched aluminum, and aluminum with a thin AlN coating, although other configurations are contemplated.

[0121] For example, the carbon black of the present invention can be used as part of a battery paste. In the case of lead-acid batteries, the battery paste may contain one or more lead oxide and carbon black particles, along with other ingredients of expandable formulations typically used in negative lead-acid battery plates (e.g., barium sulfate and / or lignosulfonate or other organic materials). Additionally, the paste contains a sufficient amount of sulfuric acid to produce the desired consistency in the paste. To produce a battery plate, the paste components are added to a commercially available paste mixer, mixed to the desired consistency, and then applied to a conductive lead alloy structure known as a grid. Typically, the pasted grid is then cured in a heated chamber containing air with high relative humidity. This curing process creates the chemical and physical structure necessary for subsequent battery handling and performance. After curing, the plate is dried using any suitable means. The resulting plate contains negative active material and is suitable for use in lead-acid batteries.

[0122] For use in electrochemical capacitors, the carbon blacks of the present invention can be formulated into electrodes by combining them with materials such as activated carbon (or other large porous particles) and polymers (such as polymeric binders, e.g., fluorinated polymers such as poly(vinylidene fluoride-co-chlorotrifluoroethylene) copolymers or similar polymers).

[0123] In the present invention, the carbon black is, for example, conductive carbon black. Therefore, it can be used to enhance the conductivity of electrode pastes for lithium-ion batteries. The positive electrode of a lithium-ion battery typically includes a conductive substrate supporting a mixture (e.g., applied as a paste) having at least an electroactive material, a binder, and a conductive additive. The conductive additive may include the carbon black of the present invention, and optionally includes graphite and / or other conductive additives typically used in lithium-ion batteries. The electroactive material, such as a lithium transition metal oxide, can accept and release lithium ions. A binder, such as polyvinylidene fluoride, is used to provide mechanical integrity and stability to the electrode. Typically, the electroactive material and binder have poor electrical conductivity or are insulating, so conductive additives (e.g., graphite and carbon black) are added to enhance the conductivity of the electrode. The electrode is formed by depositing the paste on a conductive substrate (e.g., an aluminum current collector) and subsequently removing the solvent. The formed electrodes can be incorporated into lithium ion batteries according to methods known in the art, for example, as described in "Lithium Ion Batteries Fundamentals and Applications," by Yuping Wu, CRC press, (2015).

[0124] Electrodes containing carbon black and optionally other components can be formed, for example, by coating a current collector with a liquid dispersion containing these components in a dispersed formulation. Exemplary liquids include, but are not limited to, organic solvents, such as ketone-based solvents like methyl ethyl ketone or methyl isobutyl ketone, and aqueous solvents. Other examples are water and N-methylpyrrolidone (NMP).

[0125] Generally, any dispersion formulation containing the carbon black of the present invention, as well as the preparation and processing of the dispersion, can be used as part of electrode manufacturing. The dispersion formulation can include multiple components, such as carbon black, binder, dispersant, rheology modifier, and solvent. The dispersion formulation can be, for example, in the form of a slurry. The temperature during dispersion mixing can be controlled between 15 and 45°C or other ranges. Mixing can be performed by a high-shear process, and the mixing device can be a rotor-stator, horizontal mill, sonic horn, sonic bath, cowl blade, or the like. Any viscosity of the dispersion can be achieved by selecting the appropriate mass content of particles in the dispersion, and this viscosity is selected based on the application method of the dispersion. Coating methods include, for example, extrusion lamination, doctor blade, gravure coating, reverse coating, applicator coating, and screen printing.

[0126] The carbon blacks of the present invention can also be used in a variety of other energy storage devices, including, for example, as conductive additives in battery electrodes, as catalyst supports in fuel cells, and in hybrid energy storage devices that combine battery electrodes and EDLC electrodes into one cell (also known as asymmetric supercapacitors or hybrid battery / supercapacitors). For example, hybrid lead-carbon energy storage devices employ a lead acid battery positive electrode and a supercapacitor negative electrode, as described, for example, in U.S. Patent Nos. 6,466,429, 6,628,504, 6,706,079, 7,006,346, and 7,110,242.

[0127] Alternatively or additionally, the carbon black of the present invention, with or without any of the modifications described above, can be blended with a thermoplastic material to form a masterbatch or compound. Such compounds can be prepared by any method known to those skilled in the art for preparing resin compositions. Typically, the components are blended with the desired resin at or above the resin's softening point in conventional mixing equipment, such as a two-rotor mixer, co-kneader, twin-screw kneader, Farrell continuous mixer (FCM), or long axial discharge continuous mixer (LCM-AX). The masterbatch or other thermoplastic composition can contain any amount of carbon black, e.g., up to 25% carbon black, and can also contain 0-2 wt.% antioxidants, e.g., antioxidants in amounts of 0-2 wt.%, and / or processing aids, e.g., metal stearates, organic stearates, and fluoroelastomers, in amounts of 0-50 wt.%. Other additives such as UV stabilizers, slip stabilizers, lubricants, optical brighteners, anti-fog and anti-static agents, fillers, pigments, thermally conductive additives, and / or electrically conductive additives can also be incorporated into the masterbatch or compound. The masterbatch can be combined with additional thermoplastics and optional additives and formed into any article of manufacture by any method, including, but not limited to, injection molding, compression molding, extrusion from sheet, film formation, and blow molding.Exemplary polymers that can be combined with carbon black include thermoplastic polyolefins (TPO), polyethylene (PE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), very low density polyethylene (VLDPE), metallocene medium density polyethylene (mLLDPE), polypropylene, copolymers of polypropylene, ethylene propylene rubber (EPR), ethylene propylene diene terpolymer (EPDM), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene EPDM (AES), styrene-butadiene-styrene. (SBS), polyoxymethylene (POM), polyamide (PA), polyvinyl chloride (PVC), tetraethylene hexapropylene vinylidene fluoride polymer (THV), perfluoroalkoxy polymer (PFA), polyhexafluoropropylene (HFP), polyketone (PK), ethylene vinyl alcohol (EVOH), copolyester, polyurethane (PU), thermoplastic polyurethane, polystyrene (PS), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene oxide (PPO) and polyphenylene ether (PPE), and mixtures or blends of any of these.

[0128] The present invention includes the following aspects / embodiments / features in any order and / or in any combination. 1. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; combining at least one feedstock additive comprising strontium or barium or a combination thereof with at least one carbon black feedstock to form a feedstock mixture; feeding the feed mixture to at least one feed introduction point of a carbon black reactor; Combining at least the feed mixture through at least one introduction point into the carbon black reactor with a heated gas stream and heating the carbon black reactor at a rate of 800 m 2 / g~2,500m 2 forming a reaction stream in which carbon black having a nitrogen surface area (N2SA) of 1 / g is formed; and recovering the carbon black in the reaction stream, the method further comprising operating the carbon black reactor at an overall actuated combustion (OAC) of 28% to 50%, wherein the carbon black reactor is configured such that the OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area and "additive ppm" is the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive. 2. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; feeding at least one carbon black feedstock to at least one feedstock introduction point into a carbon black reactor; providing at least one feedstock additive comprising strontium or barium or a combination thereof to at least one entry point into a carbon black reactor; The at least one carbon black feedstock and the at least one feedstock additive are combined with a heated gas stream in the carbon black reactor to generate a carbon black mixture of 800 m 2 / g~2,500m 2 forming a reaction stream in which carbon black having a nitrogen surface area (N2SA) of 1 / g is formed; and recovering the carbon black in the reaction stream, the method further comprising operating the carbon black reactor at an overall actuated combustion (OAC) of 28% to 50%, wherein the carbon black reactor is configured such that the OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area and "additive ppm" is the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive. 3. N2SA is 900m 2 / g~2,400m 2 The method according to any one of the above or below embodiments / features / aspects, wherein 4. The method of any one of the above or below embodiments / features / aspects, wherein the OAC<[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5). 5. N2SA is 850m 2 / g~2,400m 2 The method according to any one of the above or below embodiments / features / aspects, wherein 6. The method of any one of the above or below embodiments / features / aspects, wherein the OAC is 33.5% to 46.5%. 7. OAC is 33.5%-46.5% and N2SA is 900m 2 / g~2,400m 2 The method according to any one of the above or below embodiments / features / aspects, wherein 8. OAC is 33.5%-46.5% and N2SA is 850m 2 / g~2,400m 2 The method according to any one of the above or below embodiments / features / aspects, wherein 9. OAC is 33.5%-46.5% and N2SA is 1000m 2 / g~2,400m 2 The method according to any one of the above or below embodiments / features / aspects, wherein 10. The method of any one of the above or below embodiments / features / aspects, wherein the method further comprises injecting oxygen downstream of the feed introduction point and upstream of the quench. 11. The method of any one of the above or below embodiments / features / aspects, wherein the at least one feedstock introduction point is two or more feedstock introduction points, and at least one feedstock introduction point is located downstream of at least one other feedstock introduction point. 12. The method of any one of the above or below embodiments / features / aspects, wherein the carbon black reactor comprises a combustion zone, a transition zone, and a reaction zone. 13. The method of any one of the above or below embodiments / features / aspects, wherein the carbon black reactor comprises a combustion zone, a transition zone, a conical inlet section, a stepped inlet section, a reaction zone, and a quench zone. 14. The method of any one of the above or below embodiments / features / aspects, operated by controlling at least the amount of feedstock introduced such that the overall efficiency of combustion (OAC) is between 33.5% and 46.5%. 15. The method of any one of the above or below embodiments / features / aspects, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 500 ppm as a percentage of the total amount of feedstock. 16. The method of any one of the above or below embodiments / features / aspects, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 100 ppm as a percentage of the total amount of feedstock. 17. The method of any one of the above or below embodiments / features / aspects, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 10 ppm as a percentage of the total amount of feedstock. 18. The method of any one of the above or below embodiments / features / aspects, wherein the Group IA element is introduced at any one time in an amount of less than 10 ppm based on the total amount of feedstock, and wherein calcium is introduced at any one time in an amount of less than 10 ppm as a percentage of the total amount of feedstock. 19. The method of any one of the above or below embodiments / features / aspects, wherein no Group IA element is introduced at any time and no calcium is introduced at any time. 20. The method of any one of the above or below embodiments / features / aspects, wherein the at least one feedstock additive is an aqueous liquid containing dissolved strontium and / or barium salts. 21. The method of any one of the above or below embodiments / features / aspects, wherein strontium and / or barium are present in the at least one feedstock additive in a greatest weight percent relative to any metallic element present in the feedstock additive. 22. The method of any one of the above or below embodiments / features / aspects, wherein the feedstock additive comprises said strontium and at least one other metallic element, forming a total amount of metallic elements, and said strontium comprises 30% to 99% by weight of the total amount of metallic elements present. 23. The method of any one of the above or below embodiments / features / aspects, wherein the feedstock additive comprises said strontium and at least one other metallic element, forming a total amount of metallic elements, and said strontium constitutes 80% to 99% by weight of the total amount of metallic elements present. 24. The method of any one of the above or below embodiments / features / aspects, wherein the at least one other metallic element is calcium. 25. The method of any one of the above or below embodiments / features / aspects, wherein the feedstock additives include strontium and barium, and the at least one other metallic element is calcium. 26. The method of any one of the above or below embodiments / features / aspects, wherein the amount of the feedstock additive is from 50 ppm to 1500 ppm of elemental metal as a percentage of the total amount of feedstock. 27. The method of any one of the above or below embodiments / features / aspects, wherein the amount of the feedstock additive is an amount that results in a carbon black having from 100 ppm to 7,000 ppm of the elements strontium, barium, or both present in the carbon black. 28. The method of any one of the above or below embodiments / features / aspects, wherein a carbon black reactor is operated at the OAC due, at least in part, to the temperature of the heated gas stream and reaction stream, to form the carbon black having a surface area and structure that reduces the OAC by at least 4% compared to an otherwise identical process using only the same amount of calcium as the feedstock additive. 29. 800m 2 / g~2,500m 2 / g, wherein the concentration (ppm) of Group IIA elements in the carbon black is less than or equal to 4.3*N2SA-2150, and the Group IIA elements include at least strontium, barium, or a combination thereof. 30. The carbon black of any one of the above or below embodiments / features / aspects, wherein the carbon black has a % ash content less than or equal to 0.0012*N2SA-0.24. 31. N2SA is 900m 2 / g~2,400m 2 / g 32. N2SA is 850m 2 / g~2,400m 2 / g 33. The carbon black of any one of the above or below embodiments / features / aspects, wherein the concentration (ppm) of Group IIA elements in the carbon black is less than 4.3*N2SA-2150. 34. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 95% strontium, barium, or a combination thereof. 35. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 30 wt.% strontium, based on the total weight of the Group IIA elements. 36. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 50 wt.% strontium, based on the total weight of the Group IIA elements. 37. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 99 wt.% strontium, based on the total weight of the Group IIA elements. 38. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 30 wt.% barium, based on the total weight of the Group IIA elements. 39. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 50 wt.% barium, based on the total weight of the Group IIA elements. 40. The carbon black of any one of the above or below embodiments / features / aspects, wherein the Group IIA element is at least 99 wt.% barium, based on the total weight of the Group IIA elements. 41. The carbon black of any one of the above or below embodiments / features / aspects, having a concentration of Group IA elements in the carbon black of less than 100 ppm. 42. The carbon black of any one of the above or below embodiments / features / aspects, having a concentration of Group IA elements in the carbon black of less than 50 ppm. 43. The carbon black of any one of the above or below embodiments / features / aspects, having a concentration of Group IA elements in the carbon black of less than 20 ppm. 44. The carbon black of any one of the above or below embodiments / features / aspects, having a concentration of Group IA elements in the carbon black of less than 15 ppm. 45. The carbon black of any one of the above or below embodiments / features / aspects, having a strontium and / or barium concentration of 100 to 7000 ppm. 46. ​​The carbon black of any one of the above or below embodiments / features / aspects, having a concentration of strontium and / or barium of at least 200 ppm. The present invention may include any combination of these various features or embodiments described above and / or below in sentences and / or paragraphs. Any combination of features disclosed herein is considered part of the invention, and no limitation is intended with respect to features that can be combined.

[0129] The present invention will be further defined by the following examples, which are intended to be exemplary of the invention only. Unless otherwise specified, all amounts, percentages, ratios, etc. used herein are by weight. [Example]

[0130] Example 1: Preparation of carbon black Carbon black was prepared in a reactor as described above and shown in Figure 2, utilizing a liquid feedstock having the properties listed in Table 1 and the reactor conditions and configuration listed in Table 2. Natural gas was used as fuel for the combustion reaction. Aqueous solutions of strontium, barium, calcium (comparison), or strontium with calcium were used as feed additives and mixed with the liquid feedstock before injection into the reactor in zone 3 (see Figure 2). Strontium, barium, and calcium were all used as aqueous solutions of metal acetates. The reaction was quenched with water purified by reverse osmosis. [Table 1] [Table 2] * nm 3 refers to standard cubic meters, where "standard" refers to the amount of gas corrected to 25°C and 1 atmosphere. **Primary combustion is defined as the percentage of oxygen added to combustion zone 1 compared to the total amount of oxygen required to stoichiometrically react with the natural gas added to combustion zone 1. [Table 3] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor. [Table 4] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor. [Table 5] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor. [Table 6] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor.

[0131] Tables 3, 4, 5, and 6 show the surface area (BET surface area measured as described above) and calcium, strontium, and barium contents of carbon black. The abundances of these Group IIA elements were measured by inductively coupled plasma (ICP) analysis as follows: 5-10 mg samples were ashed using a muffle furnace as described in ASTM D1506. The resulting ash was combined with 2 mL of concentrated HCl, 0.5 mL of concentrated HNO3, and a small amount of reagent-grade water. The samples were then made up to 50 mL with yttrium as an internal standard and reagent-grade water and analyzed using an Agilent ICP-OES Model 5110 spectrometer.

[0132] The results from Tables 3, 4, 5, and 6 are plotted in Figures 1A, 1B, 3, and 4. Figures 1A and 1B are graphs plotting OAC (%) versus nitrogen surface area. Because both OAC and feed additive concentration affect surface area, each additive concentration used in the feed is plotted with a unique symbol: square—250 ppm (Figure 1A), triangle—700 ppm (Figure 1B), circle—1000 ppm (Figure 1A), and diamond—1500 ppm (Figure 1B). The striped symbols represent the curve for each additive concentration, OAC=[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5). From the graph, it can be seen that carbon blacks made with Sr (open symbols), Ba (filled symbols), and Sr-Ca blends (stippled triangles) always satisfy the equation OAC≦[(1350+N2SA-244*ln(additive ppm+1)) / 0.003]^(1 / 3.5) and lie either tangent to or below their corresponding curves (depending on the additive concentration). In contrast, carbon blacks made with Ca only (stippled circles and diamonds) do not satisfy this equation and lie above their corresponding curves (depending on the additive concentration).

[0133] Figure 3 is a graph showing the total concentration of Group IIA elements in carbon black versus surface area. It can be seen that carbon blacks made with Sr or Ba (including Sr-Ca blends) consistently have Group IIA concentrations (ppm) in CB less than 4.3*N2SA-2150, while carbon blacks made with Ca alone have higher amounts of Group IIA elements. This reduction in Group IIA elements correlates with reduced ash levels, potentially improving the conductivity of the carbon black and improving the appearance and processability of thermoplastics containing such carbon blacks. Figure 4 is a graph confirming the reduction in ash levels. It can be seen that carbon blacks made with Sr or Ba (including Sr-Ca blends) consistently have ash concentrations (%) in CB less than 0.0012*N2SA-0.24, while carbon blacks made with Ca alone have higher ash levels.

[0134] Example 2 Carbon black is prepared in a reactor such as that described above and shown in Figure 2, utilizing a liquid feedstock having the properties listed in Table 1 and the reactor conditions and configuration listed in Table 2. Natural gas is used as the fuel for the combustion reaction. Aqueous solutions of strontium or calcium (comparison) and potassium (as potassium acetate) are used as feedstock additives and are mixed with the liquid feedstock before being injected into the reactor in zone 3 (see Figure 2). The reaction is quenched with water purified by reverse osmosis. [Table 7] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor.

[0135] Varying the amount of potassium in the feedstock is expected to have little effect on the surface area of ​​the carbon black, especially compared to the effect of strontium addition.

[0136] Example 3 Carbon black is prepared in a reactor such as that described above and shown in Figure 2, utilizing a liquid feedstock having the properties listed in Table 1 and the reactor conditions and configuration listed in Table 2. Natural gas is used as the fuel for the combustion reaction. Aqueous solutions of strontium acetate and barium acetate are used as feed additives and are mixed with the liquid feedstock before being injected into the reactor in zone 3 (see Figure 2). The reaction is quenched with water purified by reverse osmosis. [Table 8] *** The overall combustion rate is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all fuel streams added to the entire reactor.

[0137] The combined use of strontium and barium at 36% total burn-up is expected to result in a carbon black with a surface area that satisfies the equation OAC < [(1350 + N2SA-244 * ln(ppm additive + 1)) / 0.003]^(1 / 3.5).

[0138] The applicants specifically incorporate the entire contents of all cited references into this disclosure. Furthermore, when an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pairing of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is described herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. The scope of the invention is not intended to be limited to the specific values ​​recited when defining the range. For any ranges provided herein, it is further understood that numerical ranges may be "about" these ranges, and vice versa, and that when ranges are provided using "about" ranges, these ranges may be the exact numerical ranges provided. Any combination of the embodiments, and / or ingredients, and / or components, and / or properties described herein can be made herein and are considered part of the invention.

[0139] Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims

1. 1. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; combining at least one feedstock additive comprising strontium or barium or a combination thereof with at least one carbon black feedstock to form a feedstock mixture; feeding the feed mixture to at least one feed introduction point of the carbon black reactor; 2. Combining at least the feed mixture through the at least one introduction point into the carbon black reactor with the heated gas stream to form a carbon black reactor having a flow rate of 800 m ２ / g~2,500m ２ forming a reaction stream in which carbon black having a nitrogen surface area (N2SA) of 1 / g is formed; recovering the carbon black in the reaction stream, the method further comprising operating the carbon black reactor at an overall acid combustion (OAC) of 28% to 50%, wherein the carbon black reactor is configured such that the OAC≦[(1350+N2SA−244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area and "additive ppm" is the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive.

2. 1. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; feeding at least one carbon black feedstock to at least one feed point into said carbon black reactor; providing at least one feedstock additive comprising strontium or barium or a combination thereof to at least one entry point into said carbon black reactor; The at least one carbon black feedstock and the at least one feedstock additive are combined with the heated gas stream in the carbon black reactor to form a mixture of 800 m ２ / g~2,500m ２ forming a reaction stream in which carbon black having a nitrogen surface area (N2SA) of 1 / g is formed; recovering the carbon black in the reaction stream, the method further comprising operating the carbon black reactor at an overall acid combustion (OAC) of 28% to 50%, wherein the carbon black reactor is configured such that the OAC≦[(1350+N2SA−244*ln(additive ppm+1)) / 0.003]^(1 / 3.5), where N2SA is the nitrogen BET surface area and "additive ppm" is the total ppm (ppm by weight) of metal elements added to the feedstock, excluding residual impurities in the feedstock additive.

3. The N2SA is 900m ２ / g~2,400m ２ The method according to claim 1 or 2, wherein the saturation is 0.05 to 0.15 g.

4. 3. The method of claim 1 or 2, wherein the OAC<[(1350+N2SA-244*ln(ppm additive+1)) / 0.003]^(1 / 3.5).

5. The N2SA is 850m ２ / g~2,400m ２ The method according to claim 1 or 2, wherein the saturation is 0.05 to 0.15 g.

6. 3. The method of claim 1, wherein the OAC is between 33.5% and 46.5%.

7. The OAC is 33.5% to 46.5% and the N2SA is 900m ２ / g~2,400m ２ The method according to claim 1 or 2, wherein the saturation is 0.05 to 0.15 g.

8. The OAC is 33.5% to 46.5% and the N2SA is 850m ２ / g~2,400m ２ The method according to claim 1 or 2, wherein the saturation is 0.05 to 0.15 g.

9. The OAC is 33.5% to 46.5% and the N2SA is 1000m ２ / g~2,400m ２ The method according to claim 1 or 2, wherein the saturation is 0.05 to 0.15 g.

10. 3. The method of claim 1 or 2, further comprising injecting oxygen downstream of the feed introduction point and upstream of the quench.

11. 3. The method of claim 1, wherein the at least one feedstock introduction point is two or more feedstock introduction points, and at least one feedstock introduction point is located downstream of at least one other feedstock introduction point.

12. 3. The method of claim 1 or 2, wherein the carbon black reactor comprises a combustion zone, a transition zone, and a reaction zone.

13. 3. The method of claim 1 or 2, wherein the carbon black reactor comprises a combustion zone, a transition zone, a conical inlet section, a stepped inlet section, a reaction zone, and a quench zone.

14. 3. The method of claim 1 or 2, wherein the method is operated by controlling at least the amount of feedstock introduced so that the overall efficiency of combustion (OAC) is between 33.5% and 46.5%.

15. 3. The method of claim 1 or 2, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 500 ppm relative to the total amount of feedstock.

16. 3. The method of claim 1 or 2, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 100 ppm relative to the total amount of feedstock.

17. 3. The method of claim 1 or 2, wherein the Group IA element and / or calcium is introduced at any one time in an amount of less than 10 ppm relative to the total amount of feedstock.

18. 3. The method of claim 1 or 2, wherein the Group IA element is introduced at any one time in an amount of less than 10 ppm based on the total amount of feedstock, and the calcium is introduced at any one time in an amount of less than 10 ppm as a percentage of the total amount of feedstock.

19. 3. The method of claim 1 or 2, wherein no Group IA elements are introduced at any time and no calcium is introduced at any time.

20. 3. The method of claim 1 or 2, wherein the at least one feedstock additive is an aqueous liquid containing dissolved strontium and / or barium salts.

21. 3. The method of claim 1 or 2, wherein strontium and / or barium are present in the at least one feedstock additive in a maximum weight percent compared to any metallic element present in the feedstock additive.

22. 3. The method of claim 1 or 2, wherein the feedstock additive comprises the strontium and at least one other metallic element, forming a total amount of metallic elements, and the strontium comprises 30% to 99% by weight of the total amount of the metallic elements present.

23. 3. The method of claim 1 or 2, wherein the feedstock additives comprise the strontium and at least one other metallic element, forming a total amount of metallic elements, and the strontium comprises 80% to 99% by weight of the total amount of metallic elements present.

24. 22. The method of claim 20 or 21, wherein the at least one other metallic element is calcium.

25. 22. The method of claim 20 or 21, wherein the feedstock additives include strontium and barium, and the at least one other metallic element is calcium.

26. 26. The method of any one of claims 1 to 25, wherein the amount of the feedstock additive is from 50 ppm to 1500 ppm of elemental metal as a percentage of the total amount of feedstock.

27. 27. The method of any one of claims 1 to 26, wherein the amount of the feedstock additive is an amount that results in the carbon black having from 100 ppm to 7,000 ppm of the elements strontium, barium, or both present in the carbon black.

28. 28. The method of any one of claims 1 to 27, wherein the carbon black reactor is operated at an OAC due, at least in part, to the temperature of the heating gas stream and the reaction stream, to form the carbon black with at least 4% less OAC compared to an otherwise identical process using only the same amount of calcium as the feedstock additive.

29. 800m ２ / g~2,500m ２ / g nitrogen BET surface area (N2SA), wherein the concentration (ppm) of Group IIA elements in said carbon black is less than or equal to 4.3*N2SA-2150, and said Group IIA elements include at least strontium, barium, or a combination thereof.

30. 30. The carbon black of claim 29, having a percent ash content less than or equal to 0.0012*N2SA-0.

24.

31. The N2SA is 900m ２ / g~2,400m ２ / g.

32. The N2SA is 850m ２ / g~2,400m ２ / g.

33. 30. The carbon black of claim 29, wherein the concentration (ppm) of Group IIA elements in the carbon black is less than 4.3*N2SA-2150.

34. 30. The carbon black of claim 29, wherein the Group IIA element is at least 95% strontium, barium, or a combination thereof.

35. 30. The carbon black of claim 29, wherein said Group IIA element is at least 30 wt.% strontium, based on the total weight of said Group IIA elements.

36. 30. The carbon black of claim 29, wherein said Group IIA element is at least 50 wt.% strontium, based on the total weight of said Group IIA elements.

37. 30. The carbon black of claim 29, wherein said Group IIA element is at least 99 wt.% strontium, based on the total weight of said Group IIA elements.

38. 30. The carbon black of claim 29, wherein said Group IIA element is at least 30 wt.% barium, based on the total weight of said Group IIA elements.

39. 30. The carbon black of claim 29, wherein said Group IIA element is at least 50% by weight barium, based on the total weight of said Group IIA elements.

40. 30. The carbon black of claim 29, wherein said Group IIA element is at least 99% by weight barium, based on the total weight of said Group IIA elements.

41. 30. The carbon black of claim 29, having a concentration of Group IA elements in said carbon black of less than 100 ppm.

42. 30. The carbon black of claim 29, having a concentration of Group IA elements in said carbon black of less than 50 ppm.

43. 30. The carbon black of claim 29, having a concentration of Group IA elements in said carbon black of less than 20 ppm.

44. 30. The carbon black of claim 29, having a concentration of Group IA elements in said carbon black of less than 15 ppm.

45. 30. The carbon black of claim 29, having a concentration of strontium and / or barium from 100 to 7000 ppm.

46. 30. The carbon black of claim 29 having a concentration of strontium and / or barium of at least 200 ppm.

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