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

Abstract

The present invention relates, in part, to a process for preparing carbon black using at least a feedstock additive that is strontium, barium, or a combination thereof, or includes strontium, barium, or a combination thereof. Optional additional feedstock additives may be used in combination with strontium and / or barium. The invention further relates to carbon black produced by one or more methods of the invention. The invention also relates to a carbon black having a nitrogen BET surface area (N2SA) of from 800 m2 / g to 2,500 m2 / g and a concentration (ppm) of a Group IIA element of less than or equal to # imgabs0 # in the carbon black wherein the additive is strontium, barium or a combination thereof or comprises strontium, barium or a combination thereof. In addition, formulations, articles, and devices containing the carbon black are disclosed.

Description

Summary of the Invention

[0001] The present invention relates to carbon black and methods for preparing the same. More particularly, the present invention relates to carbon blacks having or including strontium and / or barium additives. Furthermore, the present invention relates to carbon blacks (e.g., etching carbon blacks) containing strontium and / or barium and optionally one or more other additives.

[0002] The present invention is based, in part, on the presently recognized need to develop a class of carbon blacks that can be produced using lower 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 react stoichiometrically with all fuel streams added to the entire reactor. By reducing the OAC while still producing the same or substantially the same carbon black (based on parameters such as nitrogen surface area and / or COAN), safer operation of the process for producing carbon black can be achieved and / or more environmentally friendly operation of the process for producing carbon black can be achieved and / or more reactor-friendly operation of the process for producing carbon black can be achieved.

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

[0004] Accordingly, the present invention provides a means of achieving and / or solving the above-mentioned problems and achieving the objectives and advantages described herein.

[0005] More specifically, one feature of the present invention is to provide a carbon black having a specific surface area using a high OAC but with less feedstock additives.

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

[0007] Another feature of the present invention is to provide a carbon black having a specified surface area but produced using a lower OAC for a given feedstock addition; using less feedstock additive for a given OAC; or using both a lower OAC and less feedstock additive.

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

[0009] Another feature of the present invention is to provide such 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 a lower OAC to achieve the same or similar effect in the carbon black produced, and / or, producing a lower ash content.

[0010] Another feature of the present invention is to provide a method for producing carbon black that utilizes certain feedstock additives and certain OACs and a reactor configuration based on the desired surface area and OAC to obtain a carbon black that is useful for one or more end uses, such as reinforcement regions and / or polymer conductive formulations.

[0011] Additional features and advantages of the present invention will be explained in part in the following description, and in part will be apparent from the description, or may be learned through practice of the present invention. The purposes and other advantages of the present invention will be realized and obtained through the elements and combinations particularly pointed out in the specification and appended claims.

[0012] To achieve these and other advantages, and in accordance with the purposes 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 feedstock additive with at least one carbon black feedstock to form a feedstock mixture. In the method, the feedstock additive is or includes strontium or barium or a combination thereof. Other optional one or more feedstock additives may be further utilized. The method also includes supplying the feedstock mixture to at least one feedstock introduction point of the carbon black reactor and combining at least the feedstock mixture with the heated gas stream through at least one introduction point to the carbon black reactor to form a reaction stream in which carbon black is formed. The carbon black formed has a mass fraction of 800 m 2 / g to 2,500m 2 / g nitrogen BET surface area. Then, the method involves recovering the carbon black in the reaction stream. In this method, the method includes operating the carbon black reactor at 28% to 50% total combustion (OAC). In addition, in this method, the carbon black reactor is configured so that N2SA is the nitrogen BET surface area measured as described below. "Additive ppm" is the total ppm amount (ppm by weight) of the metal element added to the feedstock, excluding any residual impurities in the feedstock additives.

[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 supplying at least one carbon black feedstock to at least one feedstock introduction point leading to the carbon black reactor. The method further comprises supplying at least one feedstock additive to at least one introduction point leading to the carbon black reactor. Again, herein, the feedstock additive is or comprises strontium or barium or a combination thereof. Other optional one or more feedstock additives may be further utilized. The method further comprises combining the at least one carbon black feedstock and the at least one feedstock additive with the heated gas stream to form a reaction stream in the carbon black reactor, forming a gas stream having 800 m 2 / g to 2,500m 2 / g of nitrogen BET surface area of ​​carbon black. The method then includes recovering the carbon black in the reaction stream. In this method, as in another method, the method involves operating the carbon black reactor at 28% to 50% total combustion (OAC). In addition, the carbon black reactor is configured such that N2SA is the nitrogen BET surface area measured as described below. "Additive ppm" is the total ppm (ppm by weight) of the metal element added to the feedstock, excluding any residual impurities in the feedstock additives.

[0014] Furthermore, the present invention relates to a device having 800m 2 / g to 2,500m 2 / g nitrogen BET surface area (N2SA) and The carbon black may further optionally have a Group IIA concentration (ppm) of Ash content (%). N2SA is the nitrogen BET surface area measured as described below. The Group IIA concentration is in ppm and is the total ppm of all Group IIA elements present in the carbon black (ppm by weight), and includes at least barium and / or strontium. Ash content (%) is measured according to ASTM D1506.

[0015] Unless otherwise indicated, 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 application, illustrate some embodiments of the present invention and, together with the description, serve to explain the principles of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1A and 1Bis a graph showing nitrogen BET surface area as a function of OAC for examples of carbon blacks of the present invention (using Sr (open symbols), Ba (closed symbols), or Sr-Ca blends (stippled triangles) as feed additives) and comparative carbon blacks (using only Ca as a feed additive, stippled circles and diamonds) at different concentrations in the feed (squares - 250 ppm, triangles - 700 ppm, circles - 1000 ppm, diamonds - 1500 ppm). Figure 1A and 1B Further shown are a series of equation lines (striped symbols: squares - 250 ppm, triangles - 700 ppm, circles - 1000 ppm, diamonds - 1500 ppm) that distinguish the inventive furnace operating conditions and resulting nitrogen surface areas from those of the comparative carbon black.

[0019] Figure 2 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 is a graph showing the concentration of Group IIA elements relative to nitrogen BET surface area for examples of carbon blacks of the present invention (produced with Sr or Ba raw material additives, closed symbols) and comparative carbon blacks (produced with only Ca raw material additives, open symbols). Figure 3 Further shown are equation lines that distinguish the properties of the carbon blacks of the present invention from the comparative carbon blacks.

[0021] Figure 4 is a graph showing ash (wt %) as a function of nitrogen BET surface area for examples of inventive carbon blacks (produced with Sr or Ba raw material additives, closed symbols) and comparative carbon blacks (produced with only Ca raw material additives, open symbols). Figure 4 Further shown are equation lines that distinguish the properties of the carbon blacks of the present invention from the comparative carbon blacks. DETAILED DESCRIPTION

[0022] Novel and unique methods for producing carbon black using one or more of certain raw material additives are provided. Further provided are carbon blacks produced by one or more of these methods. The produced carbon blacks include one or more unique properties or relationships.

[0023] The nitrogen BET surface area was measured according to ASTM standard D6556, wherein the sample was degassed at 300°C for 1 hour under a nitrogen flow and the nitrogen BET surface area was measured at 0.05-0.1 P / P o The measurement is carried out in a range of nitrogen partial pressures.

[0024] With respect to the process of the present invention, the process involves utilizing a feedstock additive that is or includes strontium, or that is or includes barium, or that is or includes a combination of strontium and barium (which can be introduced as a pre-blended mixture or can be introduced separately). Additional, but optional, other feedstock additives (e.g., calcium) may be used.

[0025] In more detail, in one method of the present invention, the method for producing carbon black comprises, consists of, or includes the following steps: introducing a heated gas stream into a carbon black reactor.

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

[0027] The method comprises, consists of, or includes the step of supplying a feedstock mixture to at least one feedstock introduction point of a carbon black reactor.

[0028] The method comprises, consists of, or includes the steps of: combining at least a feedstock mixture with a heated gas stream through at least one introduction point to a carbon black reactor to form a reaction stream in the carbon black reactor, forming a gas stream having a flow rate of 800 m 2 / g to 2,500m 2 / g of nitrogen surface area of ​​carbon black.

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

[0030] The method comprises, consists of, or includes the steps of operating the carbon black reactor at an overall combustion (OAC) of 28% to 50% (e.g., 33.5% to 46.5%), and configuring the carbon black reactor such that wherein the additive comprises strontium, barium, or both, e.g., 50-1500 ppm of strontium, barium, or both, as a fraction relative to the total amount of the feedstock. N2SA is the nitrogen BET surface area as measured above. "Additive ppm" is the total ppm (ppm by weight) of the metal element added to the feedstock, excluding any residual impurities in the feedstock additive.

[0031] In another approach, a process 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 the step of supplying at least one carbon black feedstock to at least one feedstock introduction point to a carbon black reactor.

[0033] The method comprises, consists of, or includes the following steps: supplying at least one feedstock additive (e.g., separately from the carbon black feedstock) to at least one introduction point to the carbon black reactor. As previously described, the at least one feedstock additive is, comprises, or contains 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, may be located at the same, approximately the same, or different locations, or may overlap at one or more points if desired.

[0035] The method comprises, consists of, or includes the steps of: combining at least one carbon black feedstock and at least one feedstock additive with a heated gas stream to form a reaction stream in a carbon black reactor, wherein a carbon black feedstock having a mass of 800 m 2 / g to 2,500m 2 The nitrogen surface area is measured as described above.

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

[0037] The method comprises, consists of, or includes the steps of operating the carbon black reactor at 28% to 50% overall combustion (OAC), and configuring the carbon black reactor such that wherein 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" is the total ppm (ppm by weight) of the metal element added to the feedstock, excluding any residual impurities in the feedstock additives, relative to the total amount of the feedstock.

[0038] Unless otherwise stated, any detail or option described herein can be used in any method of the invention.

[0039] With respect to the nitrogen surface area (i.e., nitrogen BET surface area or N2SA) that can be achieved using the methods of the present invention, the N2SA can be 800 m 2 / g to 2,500m 2 / g, for example 900m 2 / g to 2,400m 2 / g, or 850m 2 / g to 2,400m 2 / g, or 825m 2 / g to 2,500m 2 / g, or 850m 2 / g to 2,500m 2 / g, or 875m 2 / g to 2,500m 2 / g, or 900m 2 / g to 2,500m 2 / g, or 925m 2 / g to 2,500m 2 / g, or 950m 2 / g to 2,500m 2 / g, or 1,000m 2 / g to 2,500m 2 / g, or 1,100m 2 / g to 2,500m 2 / g, or 1,200m 2 / g to 2,500m 2 / g, or 1,250m 2 / g to 2,500m 2 / g, or 1,300m 2 / g to 2,500m 2 / g, or 800m 2 / g to 2,450m 2 / g, or 800m 2 / g to 2,400m 2 / g, or 800m 2 / g to 2,350m 2 / g, or 800m 2 / g to 2,300m 2 / g, or 800m 2 / g to 2,250m 2 / g, or 800m 2 / g to 2,200m 2 / g, or 800m 2 / g to 2,150m 2 / g, or 800m 2 / g to 2,100m 2 / g, or 800m 2 / g to 2,050m 2 / g, or 800m 2 / g to 2,000m 2 / g, or 800m 2 / g to 1,950m 2 / g, or 800m 2 / g to 1,900m 2 / g, or 800m 2 / g to 1,800m 2 / g, or 800m 2 / g to 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 a second range.

[0040] In the process of the present invention, the carbon black reactor is configured to or operates at 28% to 50% total combustion (OAC). The OAC can be 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. 5% 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 or 28% to 38%, or 28% to 36%, or 28% to 34%, or 28% to 32%, or other OACs above or below any of these ranges, or any combination of one endpoint of one range with the other endpoint of a second range.

[0041] As indicated, the carbon black reactor is configured so that [Equation 1]. The carbon black reactor can be configured so that .

[0042] Referring to Equation 1, OAC may be at least 1% less than the value obtained from Equation 1, or may be at least 2%, 3%, 5%, 7%, 10%, 15%, 20%, or 25%, such as 1% to 25%, less than the value obtained from Equation 1. Moreover, these amounts of OAC may be compared to 800 m 2 / g to 2,500m2 / g, or 900m 2 / g to 2,400m 2 / g, or 1000m 2 / g to 2,300m 2 / g, or 1100m 2 / g to 2,300m 2 / g of N2SA or any other N2SA value or range provided herein.

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

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

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

[0046] OAC can be controlled in a variety 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 ways to control OAC include, but are not limited to, controlling the amount and composition of heated gas introduced into the carbon black reactor and / or varying the composition of the feedstock (e.g., the mass ratio of hydrogen to carbon).

[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 the downstream oxygen to the amount of the oxidant stream added to the combustion zone of the carbon black reactor may 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. Figure 2 , for example, the molar ratio of downstream oxygen to the amount of oxidant stream 14 added to the combustion zone 1 can be as described above.

[0048] With respect to at least one feedstock introduction point(s), this may be one or two or more feedstock introduction points. When there are two or more, at least one feedstock introduction point may be downstream of at least one other feedstock introduction point.

[0049] Typically, the carbon black reactor includes or comprises combustion zone, transition zone and reaction zone.For example, the carbon black reactor may include or comprise combustion zone, transition zone, tapered inlet section, stepped inlet section, reaction zone and quench zone.The example of suitable reactor includes but is not limited to those described in US3922335, US4383973, US5190739, US5877250, US5904762, US6153684, US6156837, US6403695, US6485693, US7829057, US8871173, US10829642, US6926877, US6156837, US5190739 and US5877251, all of which are incorporated herein by reference.Any one of these reactors can be used for implementing and including operating parameters as herein described and assembly (component) to prepare carbon black of the present invention.

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

[0051] Typically, the feedstock additive can be a substance that is a solid, solution, dispersion, gas, or any combination thereof. For the purposes of the present invention, the substance can be a metal (or metal ion) itself, a compound containing one or more of these elements, including salts containing one or more of these elements, etc. Exemplary Sr and / or Ba metal salts include both organic and inorganic salts, for example, salts with any one of 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 an ongoing reaction to form a carbon black product.

[0052] The feedstock additive may preferably be in the form of an aqueous liquid containing at least a strontium salt and / or a barium salt dissolved therein. 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 does not include residual impurities (including elemental metal) typically present in feedstock additive formulations. Thus, the amount of additive does not take into account any metallic impurities in the aqueous liquid, the counterions of the metal salt, or the feedstock additive.

[0053] The amount of feedstock additive supplied to one or more feedstock introduction points or introduction points (e.g., feedstock additive introduction points) can be in an amount of 50 ppm to 1500 ppm or more (based on the elemental metal, in ionic or neutral form, excluding residual impurities), and this amount is based on the ppm level (weight ppm) of the elemental metal (excluding residual impurities) added to the feedstock before any reaction or pyrolysis occurs in the carbon black reactor. The amount can be from 60 ppm to 1500 ppm, from 75 ppm to 1500 ppm, from 100 ppm to 1500 ppm, from 125 to 1500 ppm, from 150 ppm to 1500 ppm, from 175 ppm to 1500 ppm, from 200 ppm to 1500 ppm, from 250 ppm to 1450 ppm, from 250 ppm to 1400 ppm, from 250 ppm to 1350 ppm, from 250 ppm to 1300 ppm, from 250 ppm to 1200 ppm, from 250 ppm to 1100 ppm, from 250 ppm to 1000 ppm, from 250 ppm to 900 ppm, from 250 ppm to 800 ppm, from 250 ppm to 700 ppm, from 250 ppm to 800 ppm. ppm, 50 ppm to 600 ppm, 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 the recited ranges, or any combination of one endpoint of one range with the other endpoint of a second range. These amounts can apply to the total feedstock additive or to the strontium, barium, or both in the feedstock.

[0054] With respect to the amounts of raw material additives specifically described immediately above, amounts greater than 1500 ppm that can be used tend not to provide any additional benefit compared to amounts of 1500 ppm or less. Furthermore, amounts greater than 1500 ppm can often provide the resulting carbon black with an undesirably higher ash content. Thus, using the process of the present invention, it has been found that the amount of raw material additive used is preferably between 50 ppm and 1500 ppm, and more preferably between 250 ppm and 1500 ppm.

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

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

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

[0058] The amount of feedstock additive used in the process of the present invention can alternatively be characterized as using a sufficient amount so that the resulting carbon black formed has from about 100 ppm to about 7,000 ppm or more of elemental strontium or barium or both. The strontium and / or barium (and optional other additives) can be uniformly dispersed throughout the carbon black.The amount can be from 100 ppm to 7,000 ppm, from 100 ppm to 6,500 ppm, from 100 ppm to 6,000 ppm, from 100 ppm to 5,500 ppm, from 100 ppm to 5,000 ppm, from 100 ppm to 4,500 ppm, from 100 ppm to 4,000 ppm, from 100 ppm to 3,500 ppm, from 100 ppm to 3,000 ppm, from 100 ppm to 2,500 ppm, from 100 ppm to 2,000 ppm, from 100 ppm to 1,500 ppm, from 100 ppm to 1,000 ppm, from 100 ppm to 500 ppm , 150ppm to 7,000ppm, 200ppm to 7,000ppm, 250ppm to 7,000ppm, 300ppm to 7,000ppm, 350ppm to 7,000ppm, 400ppm to 7,000ppm, 450ppm to 7,000ppm, 500ppm to 7,000ppm, 550ppm to 7,000ppm, 600ppm to 7,000ppm, 650ppm to 7,000ppm, 700ppm to 7,000ppm, 750ppm to 7,000ppm, 800ppm to 7,000ppm, 850ppm to 7,000ppm, 0ppm to 7,000ppm, 900ppm to 7,000ppm, 950ppm to 7,000ppm, 1,000ppm to 7,000ppm, 1,000ppm to 6,500ppm, 1000ppm to 6,000ppm, 1,000ppm to 5,500ppm, 1,000ppm to 5,000ppm, 1,000ppm to 4,500ppm, 1,000ppm to 4,000ppm, 1,000ppm to 3,500ppm, 1,000ppm to 3,000ppm, 1,000ppm to 2,500ppm, 1,000ppm to 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, 6,500 ppm to 7,000 ppm.

[0059] With respect to the amount of feedstock additive used in the process of the present invention to form a resulting carbon black having from about 100 ppm to about 7,000 ppm of strontium and / or barium present as specifically described immediately above, amounts of additives greater than 7,000 ppm in the resulting carbon black can 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 can generally be accompanied by an undesirably higher ash content in the carbon black.

[0060] The other metal element in the raw material additive may be or include calcium.

[0061] The other metallic elements in the feedstock additives may be or include Group IA elements and / or calcium, which may be introduced at any point. Any optional feedstock additives (e.g., calcium) may be introduced at the same or different times and / or at the same or different locations, and / or combined with the Sr and / or Ba additives prior to introduction into the reactor.

[0062] The amount of the Group IA elements and / or calcium can be an amount less than 500ppm based on the total feedstock amount. This amount is based on the ppm level of the metallic element added to the feedstock before any reaction or pyrolysis occurs in the carbon black reactor, excluding residual impurities, and not taking into account any counterions or solvents as part of a feedstock additive. This amount can be less than 450ppm, less than 400ppm, less than 350ppm, less than 300ppm, less than 250ppm, less than 200ppm, less than 150ppm, less than 100ppm, less than 50ppm, less than 25ppm, less than 15ppm, less than 10ppm, less than 1ppm, 1ppm to 499ppm, 10ppm to 450ppm, 25ppm to 425ppm, 50ppm to 475ppm, 75ppm to 450ppm, 100ppm to 400ppm. These amounts can be applied to the total combined amount of the Group IA elements (if used) and calcium (if used), or these amounts can be applied individually to calcium and individually to one or more Group IA elements.

[0063] For example, the Group IA element may be introduced at any point in an amount of less than 10 ppm based on the total raw material amount, and calcium may also be introduced at any point in an amount of less than 10 ppm based on the total raw material amount.

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

[0065] As indicated, the use of Group IA elements and / or calcium is optional, and thus, as an option, no Group IA elements are introduced or present. As an option, no calcium is introduced or present. As an option, less than 50 ppm of calcium is present.

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

[0067] As an option, 100 ppm or less of a potassium additive is introduced into the method of the present invention. Also, the carbon black formed may contain 100 ppm or less of elemental potassium in the formed carbon black. The amount of the potassium additive present or introduced into the method 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 the potassium additive may be from 0.1 ppm to 100 ppm, or from 0.5 ppm to 100 ppm, or from 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] As an option, no sodium additive is introduced and no sodium is present in the carbon black formed. As an option, the amount of sodium additive introduced in the process or present in the carbon black can be 100 ppm or less, 50 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, or 1 ppm or less, or 0.1 ppm or less. The amount of sodium present in the carbon black formed 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 from 1 ppm to 100 ppm, or from 5 ppm to 100 ppm, or from 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 of these. These elements may be included in a feed additive that may be a solid, solution, dispersion, gas, or any combination thereof. For purposes of the present invention, the substance may be the metal (or metal ion) itself, a compound containing one or more of these elements, including salts containing one or more of these elements, etc. Exemplary Group IA metal salts include both organic and inorganic salts, for example, salts having any one of chloride, acetate, or formate (such as sodium and / or potassium salts), or a combination of two or more such salts.

[0071] Regarding feedstock additives, whether strontium and / or barium are used alone or in combination with other metallic elements (e.g., calcium), the substances may be added together, separately, sequentially, or at different reaction locations. For example, the substances may be added at any point prior to complete quenching, including, for example, at ( Figure 2 The feedstock additive may be introduced before the carbon black-producing feedstock is introduced in zone 1 or 2; during the introduction of the carbon black-producing feedstock in zone 3; after the introduction of the carbon black-producing feedstock in zones 4-10; or at any step prior to complete quenching. More than one feedstock additive introduction point may be used.

[0072] The feedstock additives may be added in any manner, including any conventional means. In other words, the feedstock additives may be added in the same manner as the feedstocks used to produce the carbon black. The substances may be added as gases, liquids, or solids, or any combination thereof. The feedstock additives may be added at one point or at several points, such as Figure 2 The feed additives may also or alternatively be introduced into the feed, fuel and / or oxidant (e.g., Figure 2 The feedstock additives may be mixed with the feedstock, fuel, and / or oxidant before and / or during the reactor operation (e.g., one or more of the feed streams 7, 13, and 14 shown in FIG. 1 ), or at other reactor locations. The feedstock additives may be introduced at various points in the reactor and / or through separate injectors and / or lances (not shown).

[0073] As previously mentioned, the use of strontium and / or barium as a feedstock additive instead of calcium itself is advantageous for the methods of the present invention. For example, in the methods of the present invention, the method can form a carbon black having surface area and structure, and wherein the carbon black reactor is operated at a desired OAC (%), at least in part due to the temperature of the heated gas stream and the reaction stream, and the OAC (%) is at least 4% lower than that of an otherwise identical process using only the same amount of calcium (instead of strontium or barium) as a feedstock additive to form the carbon black (having surface area and structure). "At least 4% lower" in terms of OAC (%) can mean at least 5%, at least 6%, at least 7% lower in terms of OAC (%), e.g., 4% to 10% lower, or 5% to 8% lower, or 4% to 6% lower, meaning that the OAC value, expressed as a percentage, is lower by a certain percentage (i.e., the difference in OAC value minus the difference, divided by the OAC value of the process using only calcium, and multiplied by 100).

[0074] Although reference is made to a method of forming carbon black, the process may be considered to be a furnace carbon black process that forms furnace carbon black or furnace black.

[0075] Figure 2 An illustrative portion of one type of carbon black reactor that can be used to produce the carbon black of the present invention, taking into account the process conditions and components and additives described herein, is shown. The process conditions and reactor arrangement for producing the carbon black of the present invention can include the following features.

[0076] In general, to prepare the carbon black of the present invention, one or more or all of the following process conditions and equipment arrangements 1) and optionally 2) to 4) may be used. At least 1) is always used, and preferably used together with 2), or 3), or 4), or 2) to 3), or 3) to 4), or 2) to 4). The process conditions and equipment arrangements are as follows:

[0077] 1) Introducing (e.g., implanting) the indicated amounts of strontium and / or barium elements or ions thereof (e.g., Sr / Sr 2+ 、Ba / Ba 2+ ).

[0078] 2) Optionally injecting water and oxygen downstream of the point of introduction of the carbon black generating feedstock but upstream of the quench to increase the temperature and provide a humid environment.

[0079] 3) Optionally, calcium is introduced or added to the reactor to etch the carbon black therein.

[0080] 4) optionally introducing (e.g., injecting) a certain amount of potassium or other Group IA elements of the periodic table or their ions (e.g., Na / Na + , K / K + 、Cs / Cs + ).

[0081] In one aspect, the carbon black of the present invention is produced, for example, in a furnace carbon black reactor, such as Figure 2 As shown, the furnace carbon black reactor has a combustion zone 1 (which has a converging diameter zone 2), a transition zone 3, a tapered inlet section 4, a stepped inlet section 5, and a reaction zone 6. The diameter of combustion zone 1 (up to the point where converging diameter zone 2 begins) is shown as D-1; the diameter of zone 3 is shown as D-2; the inlet and outlet diameters of tapered zone 4 are shown as D-3 and D-4, respectively; the diameters of stepped inlet zone 5 are shown as D-5, D-6, and D-7; and the diameter of reaction zone 6 is shown as D-8 and D-9. The length of combustion zone 1 (up to the point where converging diameter zone 2 begins) is shown as L-1; the length of the converging diameter zone is shown as L-2; the length of the transition zone is shown as L-3; the length of the tapered section (zone 4) is shown as L-4; and the lengths of the steps in the reactor inlet section (zone 5) are shown as L-5, L-6, and L-7. The lengths of reaction zone 6 are L-8 and L-9.

[0082] To produce carbon black, hot combustion gases (also referred to as heated gas streams) are produced in a combustion zone 1 by contacting a liquid or gaseous fuel 13 with a suitable oxidant stream 14 (e.g., air, oxygen, a mixture of air and oxygen, etc.). When oxygen is added to the oxidant stream (referred to herein as "enrichment oxygen"), the oxygen is added to enrich the oxygen content of the air to a level of about 21% to about 35%. Among the fuels suitable for contacting the oxidant stream in the combustion zone 1 to produce hot combustion gases are any readily combustible gas, vapor, or liquid stream, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene. Typically, the fuel has a high content of carbonaceous components, particularly hydrocarbons. As an example, the volume ratio of air to natural gas used to produce the carbon black of the present invention can be from about 5:1 to about 100:1. In order to promote the generation of hot combustion gases, the oxidant stream can be preheated.

[0083] The hot combustion gas stream (or heated gas stream) flows downstream from zones 1 and 2 into zones 3, 4, 5 and 6. The hot combustion gas stream is in the direction of Figure 2Indicated by the "F" arrow in the figure. The raw material for producing carbon black (also called carbon black raw material) can be introduced at point 7 (located in zone 3). The hydrocarbon raw materials for producing carbon black that are suitable for use as readily volatile hydrocarbons under reaction conditions herein are: unsaturated hydrocarbons such as acetylene; olefins such as ethylene, propylene, butene; aromatic compounds such as benzene, toluene and xylene; certain saturated hydrocarbons; and other hydrocarbons such as kerosene, naphthalene, terpenes, ethylene tar, aromatic cycle stock, etc. Raw material additives can be introduced at point 7 or other points in zone 3 or other zones. The raw material additives can be pre-combined with the raw material for producing carbon black or added to the reactor separately.

[0084] As an option, a feedstock with a lower sulfur content can be used. Based on the total carbon black-producing feedstock used in the entire process, the sulfur level can be, for example, 0 to about 5 weight percent, or 0 to about 1 weight percent, or 0 to about 0.5 weight percent, or 0 to about 0.1 weight percent. These sulfur level ranges and amounts can also be applied to any individual carbon black-producing feedstock stream.

[0085] Typically, the raw materials for producing carbon black (alone or in combination with raw material additives) are injected at point 7 in the form of multiple streams (not shown), which penetrate into the inner area of ​​the hot combustion gas flow to ensure high-speed mixing and shearing of the raw materials for producing carbon black by the hot combustion gases, thereby causing the raw materials to be quickly and completely decomposed and converted into carbon black.

[0086] A mixture of carbon black producing feedstock (with feedstock additives) and hot combustion gases (also referred to as a reaction stream) flows downstream through zone 3 into zones 4, 5, and 6. Water can be injected into zone 6 at point 8 in the reactor. Without being bound by any particular theory, this water can evaporate into steam, which increases the concentration of gaseous species that can oxidize the carbon, resulting in an increased oxidative erosion rate of the carbon black surface. This can result in etched or porous carbon black. The weight ratio of the water injected to the amount of carbon black producing 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 different from the quench water located at point 10, the purpose of which is to stop the reaction. At Figure 2In , "A" is the distance from the start of zone 4 to the intermediate water point 8, and will vary depending on the location of the intermediate water injection. Oxygen (referred to herein as "intermediate oxygen") can be added to zone 6 at point 9. Without being bound by any particular theory, oxygen can react with combustible species in the gas (such as carbon monoxide and hydrogen) to increase the temperature of the system, thereby increasing the oxidative corrosion rate of the carbon black surface, resulting in etched or porous carbon black (which has a higher surface area than carbon black that has not been treated with oxygen). 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 Where "B" is the distance from the start of zone 4 to the intermediate oxygen point 9 and can vary depending on the location of the intermediate oxygen injection. For example, water and oxygen can be injected downstream of the point of introduction of the carbon black-producing feedstock and upstream of the quench to effectively 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%, relative to the temperature and moisture content in the reactor without the water and oxygen injection and all other conditions being the same.

[0087] As indicated, the feed additives may be introduced into the reactor as such and / or pre-combined at one or more different points in the reactor (see Figure 2 , these points may be or include points 3, 4, 5, 8, 6 and / or 9).

[0088] The quench 11 of the reactor at point 10 injects a quench fluid (which may be water) and serves to stop further formation of carbon black. Point 10 may be determined in any manner known in the art for selecting a quench location to stop pyrolysis. Figure 2 In FIG, “Q” is the distance from the start of zone 4 to the quench point 10 and will vary depending on the location of the quench. For these carbon blacks, as an example, Q can be maximized to maximize the time available for etching to create a high surface area.

[0089] After the mixture of hot combustion gases and carbon black-producing raw materials is quenched, the cooled gases are passed downstream to any conventional cooling and separation device, whereupon the carbon black is recovered. Separation of the carbon black from the gas stream can be readily accomplished using conventional equipment such as precipitators, cyclones, or bag filters. This separation can be followed by granulation using, for example, a wet granulator.

[0090] As indicated, the present invention further relates to novel carbon blacks (e.g., furnace blacks). In particular, the present invention relates to novel carbon blacks having a nitrogen BET surface area (N2SA) of 800 m 2 / g to 2,500m 2 / g of carbon black, and the concentration of the Group IIA element in the carbon black may be less than or equal to [Equation 2] The concentration (ppm) of the Group IIA element in carbon black can be less than The amount can be characterized as a ratio A lower percentage, for example, At least 1% lower, at least 5% lower, at least 10% lower, at least 15% lower, or at least 20% lower, for example, 1% to 50% lower, preferably up to 75% lower. Preferably, the Group IIA elements include at least strontium, barium, or a combination thereof. As described above, the metal elements in the carbon black may include, in addition to strontium, barium, or both, elements of Group IA and / or additional Group IIA. The ash content (wt%) in the carbon black may be equal to or less than [Equation 3] The ash content (weight %) in carbon black can be less than .

[0091] Referring to Equation 3, the ash content (weight %) can be at least 1% lower than the value obtained from Equation 3, or, can be at least 2% lower, 3% lower, 5% lower, 7% lower, 10% lower, 15% lower, 20% lower, or 25% lower than the value obtained from Equation 3, for example, 1% to 25% lower.

[0092] The Group IIA and Group IA elements in carbon black are the result of a "raw material additive" that includes metal elements, which includes strontium and / or barium or is essentially composed of strontium and / or barium, and the descriptions and parameters mentioned above for the raw material additive can also be applied here to the Group IIA and Group IA elements contained in the carbon black product.

[0093] The N2SA of the carbon black of the present invention can be 800m 2 / g to 2,500m 2 / g, for example 900m 2 / g to 2,400m 2 / g, or 850m 2 / g to 2,400m 2 / g, or 825m 2 / g to 2,500m 2 / g, or 850m 2 / g to 2,500m 2 / g, or 875m 2 / g to 2,500m 2 / g, or 900m 2 / g to 2,500m 2 / g, or 925m 2 / g to 2,500m 2 / g, or 950m 2 / g to 2,500m 2 / g, or 1,000m 2 / g to 2,500m 2 / g, or 1,100m 2 / g to 2,500m 2 / g, or 1,200m 2 / g to 2,500m 2 / g, or 1,250m 2 / g to 2,500m 2 / g, or 1,300m 2 / g to 2,500m 2 / g, or 800m 2 / g to 2,450m 2 / g, or 800m 2 / g to 2,400m 2 / g, or 800m 2 / g to 2,350m 2 / g, or 800m 2 / g to 2,300m 2 / g, or 800m 2 / g to 2,250m 2 / g, or 800m 2 / g to 2,200m 2 / g, or 800m 2 / g to 2,150m 2 / g, or 800m 2 / g to 2,100m 2 / g, or 800m 2 / g to 2,050m 2 / g, or 800m 2 / g to 2,000m 2 / g, or 800m 2 / g to 1,950m 2 / g, or 800m 2 / g to 1,900m 2 / g, or 800m 2 / g to 1,800m 2 / g, or 800m 2 / g to 1,700m 2 / 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 a second range. N2SA is the nitrogen BET surface area measured as described above.

[0094] Alternatively, the concentration (ppm) of the Group IIA element in the carbon black can be from 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 from 200 ppm to 6500 ppm, from 300 ppm to 6000 ppm, from 400 ppm to 5000 ppm, from 500 ppm to 4000 ppm, from 600 ppm to 7000 ppm, or from 800 ppm to 6500 ppm, or any range defined by any combination of one endpoint of one range and the other endpoint of a second range.

[0095] Alternatively, the concentration (ppm) of strontium and / or barium in the carbon black can be from 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 from 200 to 6500 ppm, from 300 to 6000 ppm, from 400 to 5000 ppm, from 500 to 4000 ppm, from 600 to 7000 ppm, or from 800 to 6500 ppm, or any range defined by any combination of one endpoint of one range with the other endpoint of a second range.

[0096] As a result of the above-mentioned raw material additives, the carbon black may include only strontium or barium or a combination thereof.

[0097] As a result of using the above-mentioned raw material additives, the carbon black may include only Group IIA elements (which include at least strontium and / or barium).

[0098] The total weight of the Group IIA elements present can be at least 30 weight percent strontium, based on the total weight of the Group IIA elements, or at least 35 weight percent strontium, based on the total weight of the Group IIA elements, or at least 40 weight percent strontium, or at least 50 weight percent strontium, or at least 60 weight percent strontium, or at least 70 weight percent strontium, or at least 80 weight percent strontium, or at least 99 weight percent strontium, based on the total weight of the Group IIA elements.

[0099] The total weight of the Group IIA elements present can be at least 30 weight percent barium based on the total weight of the Group IIA elements, or at least 35 weight percent barium based on the total weight of the additive, or at least 40 weight percent barium, or at least 50 weight percent barium, or at least 60 weight percent barium, or at least 70 weight percent barium, or at least 80 weight percent barium, or at least 99 weight percent barium based on the total weight of the Group IIA elements.

[0100] If present together (strontium and barium), the total weight of the Group IIA elements present can be at least 30 weight percent strontium / barium based on the total weight of the Group IIA elements, or at least 35 weight percent strontium / barium based on the total weight of the Group IIA elements, or at least 40 weight percent strontium / barium, or at least 50 weight percent strontium / barium, or at least 60 weight percent strontium / barium, or at least 70 weight percent strontium / barium, or at least 80 weight percent strontium / barium, or at least 99 weight percent strontium / barium based on the total weight of the Group IIA elements.

[0101] The total weight of the Group IIA elements present may be at least 30 weight percent strontium or barium or a combination thereof, and 70 weight percent or less may be one or more other additives, such as, but not limited to, calcium. The weight ratio of the Group IIA element (A) being strontium, barium or a combination thereof to the other additive (e.g., Ca) (B) may be in 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, 60:40 to 50:50, 99:1 to 51:49, 99:1 to 55:45, 99:1 to 60:40, 99:1 to 65:35, 95:1 to 55:45, 95:1 to 60:40, 95:1 to 65:35, 30:70 to 99:1, 35:65 to 99:1, 40:60 to 99:1, 45:55 to 99:1, and other amounts within or outside of these ranges as specified.

[0102] As an option, the carbon black has less than 0.1 wt%, 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 calcium.

[0103] As an option, the carbon black has less than 0.1 wt%, 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 potassium and / or sodium.

[0104] As an option, the carbon black has less than 0.1 wt%, 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 of Group IA elements.

[0105] A simplified description of a carbon black particle is an aggregate of many particulates, which are referred to as primary particles ("primaries"). The size of the primaries in the carbon black particle can vary, but the production of carbon black having primaries as small as at least about 8 nm in size (diameter) is feasible, for example, using a process as described herein. The number of primaries in the aggregate can also vary, for example, from about one to about tens or possibly hundreds, thus resulting in a carbon black particle size of up to about 500 nm. The number of primaries and their arrangement in the carbon black particle determines not only the size of the carbon black particle, but also the structure of the carbon black.

[0106] The average primary particle size is determined by ASTM D3849-04, the entire contents of which are incorporated herein by reference, and 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. The carbon black aggregate can be, for example, a collection of primary carbon black particles that are fused at the contact point and cannot be easily separated by shearing. The average aggregate size of the carbon black can be extracted from TEM image analysis using the imaging technique described in ASTM D3849-04, the entire contents of which are incorporated herein by reference. The carbon black can have, for example, an average aggregate size of 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.

[0107] The carbon black of the present invention may have, but is not limited to, an average primary particle size and / or an average aggregate particle size, and may have one or more of the following properties:

[0108] 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;

[0109] b) an average aggregate particle size of from about 8 nm to about 500 nm, or from about 20 nm to about 400 nm, or from about 30 to about 300 nm, or from about 50 nm to about 250 nm, or from about 75 nm to about 200 nm, or from about 100 nm to about 175 nm, or from about 125 nm to about 150 nm, or from about 50 nm to about 70 nm, or from about 55 nm to about 65 nm, or from about 58 nm to about 62 nm. For example, the carbon black of the present invention can have an average size of primaries of from about 8 nm to about 100 nm and an average size of carbon black particles of from about 8 nm to about 500 nm.

[0110] The carbon black of the present invention can be prepared, for example, by simultaneously adjusting the rate of burner natural gas, the rate of oxygen enrichment, the rate of raw material, the type of raw material, the concentration of the raw material additive element in the raw material, the concentration of the optional Group IA element in the raw material, the rate and position of intermediate water, and the rate and position of intermediate oxygen to obtain the desired properties. The selection of the specific reactor geometry described herein can also be important for achieving the desired properties. The surface area of ​​the carbon black can be increased, for example, by increasing the rate of burner natural gas, increasing the rate of oxygen enrichment, reducing the rate of raw material, increasing the concentration of the raw material additive element, increasing the concentration of Sr and / or Ba in the raw material additive (for example, changing from 30 / 70 Sr / Ca to 90 / 10 Sr / Ca), and / or increasing the rate of intermediate water while increasing the rate of intermediate oxygen. The exact level of each variable required to produce a carbon black with the desired properties can depend on the geometry of the reactor and the method of injecting each species into the reactor.

[0111] The carbon black product of the present invention may be in powder form or finely divided form. The carbon black of the present invention may also be, for example, pelletized, agglomerated or mixed with any other substance (eg, particles, liquids, solids, polymers or other materials).

[0112] Typical raw material additives for carbon black production are calcium or potassium or sodium or a combination thereof. The use of strontium and / or barium as raw material additives was not considered an option with any particular benefit to carbon black manufacturing, especially compared to calcium. Therefore, it was quite unexpected to find that the use of strontium alone, barium alone, and / or a combination of strontium and barium, or strontium and / or barium with a certain amount of calcium did not produce comparable results, but in fact, it produced significantly and unexpectedly superior results in several areas.

[0113] As described above and / or as shown in the examples, the present invention can provide the following unique and unexpected properties and / or advantages, particularly when compared to the use of standard calcium additives alone as feedstock additives during carbon black manufacturing: 1) carbon blacks having the same or approximately the same N2SA (where "approximately the same" means not more than 10% or not more than 5%) can be formed using fewer ppm of Sr (compared to Ca). The percentage of ppm of Sr (compared to Ca) can be at least 25% lower, at least 50% lower, at least 60% lower, at least 75% lower, or at least 80% lower (compared to Ca); and 2) carbon blacks having higher N2SA can be formed using fewer ppm of Sr (compared to Ca). The higher percentage in terms of N2SA can be at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, or at least 50% higher (compared to Ca, but at a lower ppm amount), and the percentage in ppm of Sr (compared to Ca) can be at least 25% lower, at least 50% lower, at least 60% lower, at least 75% lower, at least 80% lower (compared to Ca); 3) the same or substantially the same N2SA carbon black can be formed at a lower OAC (compared to Ca). The lower percentage of OAC (as a difference in OAC for different operating conditions) can be at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, and it should be understood that each OAC% is significant in the carbon black industry. Therefore, a 2% or more reduction in OAC is quite significant; 4) a higher N2SA carbon black can be formed at a lower OAC (compared to Ca). The lower percentage of OAC can be at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, and it will be understood that each OAC % is significant and that the higher percentage in terms of N2SA can be at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, or at least 50% higher (compared to the lower ppm amount of Ca). A-1: ​​The unique and unexpected properties and / or advantages 1), 2), 3), and 4) described above are particularly significant when the OAC used to prepare the carbon black is 32% and above, 32.5% and above, 33% and above, 33.5% and above, 34% and above (e.g., from 32% or 32.5% or 33% or 33.5% to 44%, 45%, 46%, 46.5%, 47%, or 48%). A-2: When the N2SA is 800 m 2 / g or higher, or 900m 2 / g or higher, or 1000m 2 / g or higher (e.g. 800m 2 / g to 2500m 2 / g, or 900m 2 / g to 2500m 2 / g, or 1000m 2 / g to 2500m2 The above-mentioned unique and unexpected properties and / or advantages 1), 2), 3), and 4) are particularly pronounced when the amount of Sr in the raw materials is less than 100 ppm, less than 300 ppm, less than 350 ppm, less than 400 ppm, less than 500 ppm, less than 600 ppm, or less than 1000 ppm, less than 900 ppm, less than 800 ppm, or less than 700 ppm (e.g., from 200 ppm to 1000 ppm). The ppm amounts mentioned are relative to the ppm (by mass) of the additive in the raw materials.

[0114] The unique and unexpected properties and / or advantages 1), 2), 3) and 4) described above, as well as A-1 to A-3, also apply when the additive is Ba (compared to Ca).

[0115] In Figure 1, Figure 3 and Figure 4 The above-mentioned unique and unexpected properties and / or advantages are further illustrated in FIG.

[0116] C-1: Unique and unexpected properties and / or advantages are also seen when 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, wherein Sr is present in an amount of 30:70 (Sr:Ca) to 99:1 (Sr:Ca) by weight, a carbon black with a higher N2SA can be produced at the same additive loading (compared to 100% Ca at the same ppm loading). The amount of Sr:Ca can be from 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, or 90:10 to 99:1 (Sr:Ca). When the N2SA is 800 m 2 / g or higher, or 825m 2 / g or higher, or 850m 2 / g or higher, or 1000m 2 / g or higher (e.g. 800m 2 / g to 2500m 2 / g, or 850m 2 / g to 2500m 2 / g, or 1000m 2 / g to 2500m 2These unique and unexpected properties and / or advantages of the Sr:Ca blends / mixtures / combinations are particularly pronounced when the total additive amount (total amount of Sr and Ca) 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 ppm, 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 the feedstock refer to the ppm of metal element relative to the amount of feedstock to which the metal element is added (by mass), excluding any residual impurities in the delivery vehicle (typically an aqueous salt solution), and not taking into account counterions of the metal salt or aqueous carrier added to the feedstock.

[0117] The unique and unexpected properties and / or advantages C-1 described above also apply when the additive is Ba instead of a combination of Sr and Ca.

[0118] pass Figure 1A-1B 、 Figure 3 and Figure 4 The unique and unexpected properties and / or advantages described above are further illustrated in part in C-1. As explained in the Examples section below, and as can be seen in the data, when Sr or Ba are used as feed additives, lower OACs can produce carbon blacks with specified N2SAs.

[0119] In addition, if Figure 3 As shown, the data below the line are all examples using Sr or Ba as the raw material additive, and the data above the line are all examples using Ca as the raw material additive, and it can be seen that when Sr or Ba is used, a much lower Group IIA element concentration (ppm) is achieved relative to the specified N2SA carbon black, thereby allowing lower ash formation on the carbon black.

[0120] In addition, if Figure 4 As shown, the data below the line are all examples where Sr or Ba is used as a raw material additive, and the data above the line are all examples where Ca is used as the only raw material additive, and it can be seen that when Sr or Ba is used, a much lower ash content (weight %) is achieved relative to the specified N2SA carbon black.

[0121] The carbon black of the present invention can be post-treated after leaving the reactor, such as Figure 2As shown, for example, by water washing or pickling, heat treatment and / or chemical molecular treatment. Post-treatment can be a simple water (hot or cold) washing procedure or pickling procedure or heat treatment. The temperature of the heat treatment can be such that some graphitization of carbon black can be caused. Alternatively, the temperature can be such that it does not cause any additional graphitization, for example, below about 1100 ° C, such as in J. Chem. Soc., Faraday Trans. I, 82, 2915-2928 (1986) of DH Everett et al. The heat treatment can be carried out, for example, in an inert atmosphere, such as argon or nitrogen. Alternatively, or in addition, carbon black can be heat treated as described in US11352536 and / or US20130295462 to change surface characteristics (such as Raman crystallite size, crystallinity, or water spreading pressure), the entire contents of which are incorporated herein by reference.

[0122] Carbon black of the present invention can have one or more chemical groups, for example, be connected to its surperficial organic group (for example, chemical connection, adsorption, covering or otherwise exist).For example, carbon black can have at least one organic group that comprises aromatic group and / or alkyl that is connected.Aromatic group or alkyl can be directly connected to carbon black (for example, the carbon atom of aromatic group or alkyl is connected (for example, bonding) to 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 entirety: 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, WO96 / 18688, WO97 / 47697, and WO97 / 47699. The organic group that can be attached to the carbon black can be an electron donor and / or electron acceptor group. Alternatively, the organic group that can be attached to the carbon black can include an electron donor and / or electron acceptor group. Another possibility is that the electron donor and / or electron acceptor group can associate with the carbon black surface as a counterion. The organic groups attached to the carbon black can be simple small molecules, oligomers, or polymers. Examples of such electron donor and 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 / 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, polyphenylenevinylenes, polyanilines, and polyvinylcarbazoles.

[0123] The organic group that can be attached to the carbon black can be at least one or more ionic groups or ionizable groups or both. Ionic functional groups 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, but are not limited to: 、 、 、 、 、 、 , where X + is any cation, such as Na + 、H + , K + NH4 + 、Li + , Ca 2+ Mg 2+ As those skilled in the art will recognize, X + It can be formed in situ as part of the manufacturing process, or it can be associated with an aromatic group or an alkyl group through a typical salt swap or ion-exchange process. Amines represent examples of ionizable functional groups that form cations or cationic groups. Onium groups and sulfonium groups also represent examples of cationic groups. Examples of organic groups that are cationic in nature include, but are not limited to: 、 、 、 、 、 、 、 and , where Y - Any halide or anion, such as RSO3 - 、SO4 2- PO4 3- 、NO3 - OH3 - 、CH3COO - etc.; or a combination thereof, wherein R is an alkyl or aromatic group. As will be appreciated by those skilled in the art, Y - It can be formed in situ as part of the manufacturing process, or it can be associated with aromatic or alkyl groups through typical salt swap or ion-exchange processes.

[0124] Any physically permissible treatment level for chemical groups (e.g., organic groups) on carbon black is generally permitted. The treatment level for chemical groups (e.g., organic groups) on carbon black (which can be expressed in μmol / m 2 carbon) can be, for example, about 0.1 to about 10 μmol / m 2 or higher.

[0125] The carbon black of the present invention can have one type of chemical group (e.g., organic group) connected to its surface or more than one type of chemical group connected to its surface. In other words, a double or multiple treated modified carbon black can be used. In addition, a mixture of modified carbon blacks having different chemical groups connected thereto can be used.

[0126] The carbon black of the present invention can be used, for example, in capacitors, such as 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 typically a metal (e.g., a strip, a rod, etc.), such as aluminum, aluminum with a thin conductive carbon cover, etched aluminum, and aluminum with a thin AlN cover, although other configurations are also contemplated.

[0127] For example, the carbon black of the present invention can be used as part of a battery paste. For lead-acid batteries, the battery paste can include lead oxide and carbon black particles, as well as one or more other components of the expander formulation commonly used in the negative plates of lead-acid batteries, such as barium sulfate and / or lignin sulfonate or other organic materials. In addition, the paste will contain a sufficient amount of sulfuric acid to produce the desired consistency in the paste. To produce battery plates, the components of the paste are added to a commercial paste mixer, mixed to the desired consistency and then applied to a conductive lead alloy structure called a grid. Typically, the pasted grid is then cured in a heated chamber containing air with high relative humidity. This curing process produces the necessary chemical and physical structures required for performance in the battery and subsequent processing. After curing, the plate is dried using any suitable means. The resulting plate containing the negative active material is then suitable for use in lead-acid batteries.

[0128] For use in electrochemical capacitors, the carbon black of the present invention can be formulated into electrodes by combining it with materials such as activated carbon (or other large porous particles) and polymers such as polymeric binders, such as fluorinated polymers, such as poly(vinylidene fluoride-co-chlorotrifluoroethylene) copolymers or similar polymers.

[0129] In the present invention, carbon black is, for example, conductive carbon black. Therefore, it can be used to enhance the conductivity of the electrode paste of a lithium ion battery. The positive electrode of a lithium ion battery typically includes a conductive substrate that carries a mixture (e.g., a mixture applied as a paste), the mixture having at least an electroactive material, a binder, and a conductivity additive (which may include the carbon black of the present invention), and optional graphite and / or other conductivity additives typically used for lithium ion batteries. The electroactive material (e.g., lithium transition metal oxide) is capable of receiving and releasing lithium ions. The binder (e.g., polyvinylidene fluoride) is used to provide mechanical integrity and stability to the electrode. Typically, since the electroactive material and the binder are poorly conductive or insulating, conductivity additives (e.g., graphite and carbon black) are added to enhance the conductivity of the electrode. The electrode is formed by depositing the paste onto a conductive substrate (e.g., an aluminum current collector) and then 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” (Yuping Wu, CRC Press, (2015)).

[0130] Electrodes comprising carbon black and optionally other components can be formed, for example, by coating a current collector with a liquid dispersion comprising these components as a dispersion formulation. Exemplary liquids include, but are not limited to, organic-based solvents, such as ketone-based solvents such as methyl ethyl ketone or methyl isobutyl ketone, and aqueous solvents. Other examples are water and N-methylpyrrolidone (NMP).

[0131] Generally, any dispersion formulation containing the carbon black of the present invention and the dispersion preparation and processing can be used as part of electrode manufacturing. The dispersion formulation can include several components: carbon black, binder, dispersant, rheology modifier, solvent, etc. The dispersion formulation can be, for example, in the form of a slurry. The temperature can be controlled at 15°C to 45°C or other ranges during dispersion mixing. Mixing can be carried out via a high shear process, etc., wherein the mixing device can be a rotor stator, a horizontal mill, a sonic horn, a sonic bath, a cowl blade, etc. Any viscosity of the dispersion can be achieved by selecting the appropriate mass content of the particles in the dispersion, and the viscosity is selected based on the application method of the dispersion. Examples of coating methods include, for example, extrusion lamination, doctor blade method, gravure coating method, reverse-coat method, applicator coating method, and screen printing method.

[0132] The carbon black of the present invention can also be used in various other energy storage devices, including, for example, as a conductivity additive for electrodes in batteries, as a catalyst support in fuel cells, and in hybrid energy storage devices, which are devices that combine battery electrodes and EDLC electrodes in one cell (also known as asymmetric supercapacitors or hybrid batteries / supercapacitors). For example, hybrid lead-carbon energy storage devices use a lead-acid battery positive electrode and a supercapacitor negative electrode, as described in, for example, U.S. Patent Nos. 6,466,429, 6,628,504, 6,706,079, 7,006,346, and 7,110,242.

[0133] Alternatively, or in addition, the carbon black of the present invention (with or without any of the above-mentioned modifications) can also be compounded with thermoplastics to form a masterbatch or compound. Such a compound can be prepared in any manner known to those of ordinary skill in the art for preparing resin compositions. Typically, the components are admixed with the desired resin at or above the softening point of the resin in a conventional mixing apparatus (such as a twin-rotor mixer, a co-kneader, a twin-screw kneader, a Farrell continuous mixer (FCM), a long continuous mixer with axial discharge (LCM-AX), etc.). The masterbatch or other thermoplastic composition can include any amount of carbon black (e.g., up to 25% carbon black) and can also include 0-2% by weight of an antioxidant (e.g., in an amount of 0-2% by weight), and / or a processing aid (e.g., in an amount of 0-50% by weight) (e.g., metal stearates, organic stearates, and fluoroelastomers). Other additives such as UV stabilizers, slip stabilizers, lubricants, optical brighteners, antifog and antistatic agents, fillers, pigments, thermal conductivity additives and / or electrical conductivity additives may also be incorporated into the masterbatch or compound. The masterbatch may be combined with additional thermoplastics and optional additives and formed into any product by any method including, but not limited to, injection molding, compression molding, extrusion molding from sheet, film forming, and blow molding. Exemplary polymers that may be combined with carbon black include, but are not limited to, 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 E PDM styrene (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.

[0134] The present invention includes the following aspects / embodiments / features in any order and / or in any combination:

[0135] 1. A method for producing carbon black, comprising:

[0136] introducing a heated gas stream into a carbon black reactor;

[0137] 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 comprises strontium or barium or a combination thereof;

[0138] supplying the feed mixture to at least one feed introduction point of the carbon black reactor,

[0139] At least the feedstock mixture is combined with the heated gas stream through the at least one introduction point to the carbon black reactor to form a reaction stream in the carbon black reactor, wherein a gas having a flow rate of 800 m / s is formed in the reaction stream. 2 / g to 2,500m 2 / g of nitrogen surface area (N2SA) of carbon black; and

[0140] Recovering the carbon black in the reaction stream, wherein the method further comprises operating the carbon black reactor at 28% to 50% total combustion (OAC), and configuring the carbon black reactor so that the , and wherein N2SA is the nitrogen BET surface area, and "additive ppm" is the total ppm amount (ppm by weight) of metallic elements added to the feedstock excluding residual impurities in the feedstock additives.

[0141] 2. A process for producing carbon black comprising:

[0142] introducing a heated gas stream into a carbon black reactor;

[0143] supplying at least one carbon black feedstock to at least one feedstock introduction point to a carbon black reactor;

[0144] supplying at least one feed additive to at least one introduction point to a carbon black reactor, wherein the at least one feed additive comprises strontium or barium or a combination thereof;

[0145] The at least one carbon black feedstock and the at least one feedstock additive are combined with the heated gas stream to form a reaction stream in the carbon black reactor, wherein a carbon black feedstock having a flow rate of 800 m 2 / g to 2,500m 2 / g of nitrogen surface area (N2SA) of carbon black; and

[0146] Recovering the carbon black in the reaction stream, wherein the method further comprises operating the carbon black reactor at 28% to 50% overall combustion (OAC), and configuring the carbon black reactor so that the , and wherein N2SA is the nitrogen BET surface area, and "additive ppm" is the total ppm amount (ppm by weight) of metallic elements added to the feedstock excluding residual impurities in the feedstock additives.

[0147] 3. The method of any preceding or subsequent embodiment / feature / aspect, wherein the N2SA is 900 m 2 / g to 2,400m 2 / g.

[0148] 4. The method of any preceding or subsequent embodiment / feature / aspect, wherein .

[0149] 5. The method of any preceding or subsequent embodiment / feature / aspect, wherein the N2SA is 850 m 2 / g to 2,400m 2 / g.

[0150] 6. The method of any preceding or following embodiment / feature / aspect, wherein the OAC is 33.5% to 46.5%.

[0151] 7. The method of any preceding or following embodiment / feature / aspect, wherein the OAC is 33.5% to 46.5% and the N2SA is 900 m 2 / g to 2,400m 2 / g.

[0152] 8. The method of any preceding or following embodiment / feature / aspect, wherein the OAC is 33.5% to 46.5% and the N2SA is 850 m 2 / g to 2,400m 2 / g.

[0153] 9. The method of any preceding or following embodiment / feature / aspect, wherein the OAC is 33.5% to 46.5% and the N2SA is 1000 m 2 / g to 2,400m 2 / g.

[0154] 10. The method of any preceding or following embodiment / feature / aspect, wherein the method further comprises injecting oxygen downstream of the feedstock introduction point and upstream of quenching.

[0155] 11. The method of any preceding or following embodiment / feature / aspect, wherein the at least one feedstock introduction point is two or more feedstock introduction points, wherein at least one feedstock introduction point is downstream from at least one other feedstock introduction point.

[0156] 12. The method of any preceding or following embodiment / feature / aspect, wherein the carbon black reactor comprises a combustion zone, a transition zone, and a reaction zone.

[0157] 13. The method of any preceding or following embodiment / feature / aspect, wherein the carbon black reactor comprises a combustion zone, a transition zone, a tapered inlet section, a stepped inlet section, a reaction zone, and a quench zone.

[0158] 14. The method of any preceding or following embodiment / feature / aspect, wherein the method is operated by controlling at least the amount of feedstock introduced such that the overall combustion (OAC) is between 33.5% and 46.5%.

[0159] 15. The method of any preceding or following embodiment / feature / aspect, wherein the Group IA element and / or calcium is introduced at any point in an amount less than 500 ppm as a fraction relative to the total amount of feedstock.

[0160] 16. The method of any preceding or following embodiment / feature / aspect, wherein the Group IA element and / or calcium is introduced at any point in an amount less than 100 ppm as a fraction relative to the total amount of feedstock.

[0161] 17. The method of any preceding or following embodiment / feature / aspect, wherein the Group IA element and / or calcium is introduced at any point in an amount less than 10 ppm as a fraction relative to the total amount of feedstock.

[0162] 18. The method of any preceding or subsequent embodiment / feature / aspect, wherein the Group IA element is introduced at any point in an amount of less than 10 ppm based on the total feedstock amount, and calcium is introduced at any point in an amount of less than 10 ppm as a fraction relative to the total feedstock amount.

[0163] 19. The method of any preceding or following embodiment / feature / aspect, wherein no Group IA elements are introduced at any point, and wherein calcium is not introduced at any point.

[0164] 20. The method of any preceding or following embodiment / feature / aspect, wherein the at least one feedstock additive is an aqueous liquid having a strontium salt and / or a barium salt dissolved therein.

[0165] 21. The method of any preceding or following embodiment / feature / aspect, wherein strontium and / or barium is present in the at least one feedstock additive in a largest weight percentage compared to any metal element present in the feedstock additive.

[0166] 22. The method of any preceding or subsequent embodiment / feature / aspect, wherein the feedstock additive comprises the strontium and at least one other metallic element to form a total amount of metallic elements, wherein the strontium comprises 30 wt% to 99 wt% of the total amount of metallic elements present.

[0167] 23. The method of any preceding or subsequent embodiment / feature / aspect, wherein the feedstock additive comprises the strontium and at least one other metallic element to form a total amount of metallic elements, wherein the strontium comprises 80 wt% to 99 wt% of the total amount of metallic elements present.

[0168] 24. The method of any preceding or following embodiment / feature / aspect, wherein the at least one other metallic element is calcium.

[0169] 25. The method of any preceding or following embodiment / feature / aspect, wherein the feedstock additive comprises strontium and barium, and wherein the at least one other metallic element is calcium.

[0170] 26. The method of any preceding or following embodiment / feature / aspect, wherein the feedstock additive is in an amount of 50 ppm to 1500 ppm of elemental metal as a fraction relative to the total feedstock.

[0171] 27. The method of any preceding or following embodiment / feature / aspect, 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 element strontium, barium, or both present in the carbon black.

[0172] 28. The method of any preceding or following embodiment / feature / aspect, wherein said method forms said carbon black having surface area and structure, and wherein said carbon black reactor is operated at said OAC due at least in part to the temperature of said heated gas stream and said reaction stream, and wherein said OAC at which said carbon black is formed is at least 4% lower than a method utilizing only the same amount of calcium for said feedstock additive but an otherwise identical process.

[0173] 29. Carbon black having 800m 2 / g to 2,500m 2 / g of nitrogen BET surface area (N2SA) and the concentration of the Group IIA element in the carbon black (ppm) is less than or equal to , wherein the Group IIA element comprises at least strontium, barium or a combination thereof.

[0174] 30. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has Ash content (%).

[0175] 31. The carbon black of any preceding or following embodiment / feature / aspect, wherein the N2SA is 900 m 2 / g to 2,400m 2 / g.

[0176] 32. The carbon black of any preceding or following embodiment / feature / aspect, wherein the N2SA is 850 m 2 / g to 2,400m 2 / g.

[0177] 33. The carbon black of any preceding or following embodiment / feature / aspect, wherein said concentration (ppm) of Group IIA elements in said carbon black is less than .

[0178] 34. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 95% strontium, barium, or a combination thereof.

[0179] 35. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 30 wt% strontium, based on the total weight of the Group IIA elements.

[0180] 36. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 50 wt% strontium, based on the total weight of the Group IIA elements.

[0181] 37. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 99 weight percent strontium, based on the total weight of the Group IIA elements.

[0182] 38. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 30 wt% barium, based on the total weight of the Group IIA elements.

[0183] 39. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 50 wt% barium, based on the total weight of the Group IIA elements.

[0184] 40. The carbon black of any preceding or following embodiment / feature / aspect, wherein the Group IIA element is at least 99 wt% barium, based on the total weight of the Group IIA elements.

[0185] 41. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 100 ppm.

[0186] 42. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 50 ppm.

[0187] 43. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 20 ppm.

[0188] 44. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 15 ppm.

[0189] 45. The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a strontium and / or barium concentration of 100 ppm to 7000 ppm.

[0190] 46. ​​The carbon black of any preceding or following embodiment / feature / aspect, wherein the carbon black has a concentration of strontium and / or barium of at least 200 ppm.

[0191] The present invention may include any combination of these various features or embodiments set forth above and / or below in sentences and / or paragraphs.Any combination of features disclosed herein is considered part of the present invention and is not intended to limit the combinable features.

[0192] The present invention will be further illustrated by the following examples, which are intended to be exemplary of the present invention only. Unless otherwise indicated, all amounts, percentages, ratios, etc. used herein are by weight.

[0193] Example

[0194] Example 1:

[0195] Preparation of carbon black

[0196] Using liquid feedstocks having the properties shown in Table 1 and reactor conditions and geometries shown in Table 2, the reactor was Figure 2 Carbon black was produced in a reactor of 100 nm. Natural gas was used as fuel for the combustion reaction. An aqueous solution of strontium or barium or calcium (comparison) or an aqueous solution of strontium and calcium was used as a feed additive and was mixed with the liquid feed before being injected into the reactor in zone 3 (reference Figure 2 Strontium, barium, and calcium were all used as aqueous solutions of metal acetates. The reaction was quenched using water purified by reverse osmosis.

[0197] Table 1: Raw material properties

[0198]

[0199] Table 2: Reactor geometry and fixed operating conditions

[0200]

[0201] nm 3 Refers to standard cubic meters, where "standard" refers to the volume of a gas corrected to 25°C and 1 atm pressure.

[0202] Primary combustion is defined as the percentage of oxygen added to the combustion zone 1 compared to the total amount of oxygen required to react stoichiometrically with the natural gas added to the combustion zone 1 .

[0203] Table 3: Operating conditions for the calcium addition examples

[0204]

[0205] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0206] Table 4: Operating Conditions for Calcium / Strontium Addition Examples

[0207]

[0208] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0209] Table 5: Operating Conditions for Strontium Addition Examples

[0210]

[0211] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0212] Table 6: Operating Conditions for Barium Addition Examples

[0213]

[0214] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0215] Tables 3, 4, 5 and 6 show the surface area (BET surface area measured as described above) and the calcium, strontium and barium contents of the carbon black. The amounts of these Group IIA elements present were determined by inductively coupled plasma as follows. A 5-10 mg sample was 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 sample was then brought to 50 mL using reagent grade water and yttrium as an internal standard and analyzed using an Agilent ICP-OES 5110 spectrometer.

[0216] The results from Tables 3, 4, 5, and 6 are plotted on Figures 1A-1B , 3 and 4. Figure 1A and 1B is a graph plotting OAC (%) versus nitrogen surface area. Since both OAC and feed additive concentration affect surface area, each additive concentration used in the feed is plotted with its own symbol (square - 250 ppm ( Figure 1A ), triangle -700ppm( Figure 1B ), round -1000ppm( Figure 1A ), rhombus-1500ppm( Figure 1B )). The striped symbols indicate the equation for each additive concentration. As can be seen from the figure, the carbon blacks produced with Sr (open symbols), Ba (filled symbols), and Sr-Ca blends (stippled triangles) consistently satisfy the equation , and are located above or below their corresponding curves (depending on the additive concentration). In contrast, carbon blacks produced with only Ca (stippled circles and diamonds) do not satisfy this equation and are located above their corresponding curves (depending on the additive concentration).

[0217] Figure 3 is a graph showing the total concentration of Group IIA elements in carbon black relative to surface area. As can be seen from the graph, carbon blacks produced using Sr or Ba (including Sr-Ca blends) consistently exhibit less than The carbon blacks produced with Ca have a lower Group IIA concentration (ppm), while the carbon blacks produced with Ca alone have higher amounts of Group IIA elements. This reduction in Group IIA elements is associated with lower ash levels, which can enhance the conductivity of the carbon blacks and improve the appearance and processability of thermoplastics containing such carbon blacks. Figure 4 is a graph demonstrating the reduced ash concentration. As can be seen from the graph, carbon blacks produced using Sr or Ba (including Sr-Ca blends) consistently exhibit less than ash concentration (%), while carbon black produced with Ca alone has a higher ash level.

[0218] Example 2

[0219] Using liquid feedstocks having the properties shown in Table 1 and reactor conditions and geometries shown in Table 2, the reactor was Figure 2 Carbon black was produced in a reactor with a temperature of 100 °C. Natural gas was used as the fuel for the combustion reaction. An aqueous solution of strontium or calcium (comparison) and potassium (as potassium acetate) was used as a feed additive and was mixed with the liquid feed before injection into the reactor in zone 3 (reference Figure 2 The reaction was quenched using water purified by reverse osmosis.

[0220] Table 7: Operating conditions for potassium addition examples

[0221]

[0222] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0223] It is expected that varying the amount of potassium in the feedstock will have a negligible effect on the surface area of ​​the carbon black, especially compared to the effect of strontium addition.

[0224] Example 3

[0225] Using liquid feedstocks having the properties shown in Table 1 and reactor conditions and geometries shown in Table 2, the reactor was Figure 2 Carbon black was produced in a reactor of 100 nm. Natural gas was used as fuel for the combustion reaction. An aqueous solution of strontium acetate and barium acetate was used as a feed additive and was mixed with the liquid feed before being injected into the reactor in zone 3 (refer to Figure 2 The reaction was quenched using water purified by reverse osmosis.

[0226] Table 8: Operating Conditions for Strontium / Barium Blend Addition Examples

[0227]

[0228] Gross combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to react stoichiometrically with all fuel streams added to the entire reactor.

[0229] It is expected that the combined use of strontium and barium at a total burn rate of 36% will result in a carbon black having a surface area satisfying the following equation: .

[0230] The applicant specifically incorporates the full contents of all cited references into the present disclosure. In addition, when the value or parameter of amount, concentration or other is given as a list of range (preferred interval) or upper preferred value and lower preferred value, this should be understood as specifically disclosing all ranges formed by any pairing of any upper range limit or preferred value and any lower range limit or preferred value, and no matter whether scope is disclosed individually. In the case of enumerating numerical ranges in this article, unless otherwise stated, the scope is intended to include all integers and fractions within its endpoints and the range. When limiting the range, the scope of the present invention is not intended to be limited to the specific values ​​cited. It should also be understood that for any scope provided herein, numerical range can be "about (about)" these ranges, and vice versa, when using "about (about)" scope to provide range, these ranges can be exactly the numerical range provided. Any combination of embodiments described herein and / or composition and / or component and / or property can be carried out in this article and is considered to be a part of the present invention.

[0231] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. The specification and examples are intended to be considered exemplary only, with the true scope and spirit of the invention being indicated by the following claims and their equivalents.

Claims

1. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; 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 comprises strontium or barium or a combination thereof; supplying the feed mixture to at least one feed introduction point of the carbon black reactor, At least the feedstock mixture is combined with the heated gas stream through the at least one introduction point to the carbon black reactor to form a reaction stream in the carbon black reactor, wherein a gas having a flow rate of 800 m / s is formed in the reaction stream. 2 / g to 2,500m 2 / g of nitrogen surface area (N2SA) of carbon black; and Recovering the carbon black in the reaction stream, wherein the method further comprises operating the carbon black reactor at 28% to 50% overall combustion (OAC), and configuring the carbon black reactor so that the , and wherein N2SA is the nitrogen BET surface area, and "additive ppm" is the total ppm amount (ppm by weight) of metallic elements added to the feedstock excluding residual impurities in the feedstock additives.

2. A method for producing carbon black, comprising: introducing a heated gas stream into a carbon black reactor; supplying at least one carbon black feedstock to at least one feedstock introduction point to a carbon black reactor; supplying at least one feed additive to at least one introduction point to a carbon black reactor, wherein the at least one feed additive comprises strontium or barium or a combination thereof; The at least one carbon black feedstock and the at least one feedstock additive are combined with the heated gas stream to form a reaction stream in the carbon black reactor, wherein a carbon black feedstock having a flow rate of 800 m 2 / g to 2,500m 2 / g of nitrogen surface area (N2SA) of carbon black; and Recovering the carbon black in the reaction stream, wherein the method further comprises operating the carbon black reactor at 28% to 50% overall combustion (OAC), and configuring the carbon black reactor so that the , and wherein N2SA is the nitrogen BET surface area, and "additive ppm" is the total ppm amount (ppm by weight) of metallic elements added to the feedstock excluding residual impurities in the feedstock additives.

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

4. The method according to claim 1 or 2, wherein .

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

6. The method of claim 1 or 2, wherein the OAC is 33.5% to 46.5%.

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

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

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

10. The process of claim 1 or 2, wherein the process further comprises injecting oxygen downstream of the feedstock introduction point and upstream of quenching.

11. The method of claim 1 or 2, wherein the at least one feedstock introduction point is two or more feedstock introduction points, wherein: At least one feedstock introduction point is downstream from at least one other feedstock introduction point.

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

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

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

15. The method according to claim 1 or 2, wherein the Group IA elements and / or calcium are introduced in an amount of less than 500 ppm at any point as a fraction relative to the total amount of the raw materials.

16. The method according to claim 1 or 2, wherein the Group IA element and / or calcium is introduced in an amount of less than 100 ppm at any point as a fraction relative to the total amount of the raw materials.

17. The method according to claim 1 or 2, wherein the Group IA element and / or calcium is introduced in an amount of less than 10 ppm at any point as a fraction relative to the total amount of the raw materials.

18. The method according to claim 1 or 2, wherein the Group IA element is introduced at any point in an amount of less than 10 ppm based on the total raw material amount, and calcium is introduced at any point in an amount of less than 10 ppm as a fraction relative to the total raw material amount.

19. The method according to claim 1 or 2, wherein no Group IA element is introduced at any point, and calcium is not introduced at any point.

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

21. The method of claim 1 or 2, wherein strontium and / or barium is present in the at least one feedstock additive in the largest weight percentage compared to any metal element present in the feedstock additive.

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

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

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

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

26. The process according to any one of the preceding claims, wherein the amount of the feedstock additive is from 50 ppm to 1500 ppm of elemental metal as a fraction relative to the total amount of feedstock.

27. The method of any one of the preceding claims, 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 process of any one of the preceding claims, wherein the process forms the carbon black having surface area and structure, and wherein the carbon black reactor is operated at the OAC due, at least in part, to the temperature of the heated gas stream and the reaction stream, and wherein the OAC at which the carbon black is formed is at least 4% lower than an otherwise identical process utilizing only the same amount of calcium for the feedstock additive.

29. Carbon black having 800m 2 / g to 2,500m 2 / g of nitrogen BET surface area (N2SA) and the concentration of the Group IIA element in the carbon black (ppm) is less than or equal to , wherein the Group IIA element comprises at least strontium, barium or a combination thereof.

30. The carbon black according to claim 29, wherein the carbon black has Ash content (%).

31. The carbon black according to claim 29, wherein the N2SA is 900 m 2 / g to 2,400m 2 / g.

32. The carbon black of claim 29, wherein the N2SA is 850 m 2 / g to 2,400m 2 / g.

33. The carbon black of claim 29, wherein the concentration (ppm) of the Group IIA element in the carbon black is less than .

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

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

36. The carbon black according to claim 29, wherein The Group IIA element is at least 50 weight percent strontium, based on the total weight of the Group IIA elements.

37. The carbon black according to claim 29, wherein The Group IIA element is at least 99 weight percent strontium, based on the total weight of the Group IIA elements.

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

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

40. The carbon black according to claim 29, 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 claim 29, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 100 ppm.

42. The carbon black of claim 29, wherein the carbon black has a Group IA element concentration in the carbon black of less than 50 ppm.

43. The carbon black of claim 29, wherein the carbon black has a concentration of Group IA elements in the carbon black of less than 20 ppm.

44. The carbon black of claim 29, wherein the carbon black has a Group IA element concentration in the carbon black of less than 15 ppm.

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

46. ​​The carbon black of claim 29, wherein the carbon black has a concentration of strontium and / or barium of at least 200 ppm.

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