CN118302491A

CN118302491A - Method for producing carbon black from low-yield raw materials and products made therefrom

Info

Publication number: CN118302491A
Application number: CN202280077751.6A
Authority: CN
Inventors: D·M·马修; G·D·莫瑟; T·F·克拉克; T·E·麦克尔韦恩; D·S·克罗克; A·戈潘; F·H·朗夫; W·M·波蒂厄斯
Original assignee: Cabot Corp
Current assignee: Cabot Corp
Priority date: 2021-09-30
Filing date: 2022-09-29
Publication date: 2024-07-05

Abstract

Methods of producing carbon black from low yield carbon black feedstock are described. The low-yielding feedstock is used in combination with conventional carbon black feedstock to produce carbon black via a furnace process. Carbon blacks produced from these carbon black feedstocks are further described. The advantages achieved with the method are further described.

Description

Method for producing carbon black from low-yield raw materials and products made therefrom

The present invention relates to a method of producing carbon black produced from an alternative (alternative) carbon black-yielding feedstock, which in many cases may comprise gaseous and/or low-yielding feedstock. The invention further relates to carbon blacks formed from alternative carbon black yielding feedstock including gaseous and/or low yield carbon black feedstock.

Carbon black has been used to alter mechanical, electrical, and optical properties in compositions. Carbon black and other fillers have been used as pigments, fillers and/or reinforcing agents in the compounding and preparation of compositions used in rubber, plastic, paper or textile applications. The nature of the carbon black or other filler is an important factor in determining the various performance characteristics of these compositions. An important use of elastomeric compositions relates to the manufacture of tires, and additional ingredients are often added to impart specific properties to the finished product or components thereof. Carbon blacks have been used to alter functional properties, conductivity, rheology, surface properties, viscosity, appearance, and other properties in elastomeric compositions and other types of compositions.

The conventional and most common process for the industrial production of carbon black is the furnace process. In this process, a first liquid carbonaceous feedstock, such as decant oil (decant oil ), is injected into a fuel-lean hot or combusting gas stream. Some pyrolysis of the feedstock to produce carbon black and byproducts (mainly hydrogen); the remainder is oxidized to produce CO, CO ₂, and H ₂ O. Conventional or traditional feedstocks are decant oils, slurry oils, coker oils, coal tar derivatives, or heavy liquid residues from ethylene cracker processes. These carbon black feedstocks are both heavy (specific gravity > 1.02), have an H: C atomic ratio of up to 1.23, are rich in aromatics (mineral office association index (Bureau of Mines Correlation Index) (BMCI). Gtoreq.100), and are liquid at room temperature and pressure (room temperature and pressure) (e.g., 25 ℃ at 1 atm). They are typically derived from fossil fuels.

The furnace black process (furnace black process) differs from the channel black process (channel black process) and the thermal black process (thermal black process), both of which use natural gas as a feedstock. The channel black process utilizes thousands of small natural gas diffusion flames to produce small amounts of carbon black. Carbon black is collected on a water-cooled metal trough (channel) or drum. The channel black process has an extremely low yield of about 0.05kg C/kg feed, which results in its abandonment in the middle of the 20 th century. The thermal black process produces a special class of very low structure carbon black by feeding natural gas through preheated bricks. Carrying out endothermic pyrolysis on natural gas on the hot bricks to obtain carbon black; however, these bricks cool rapidly and must be periodically reheated by combustion of byproduct hydrogen and natural gas. The thermal carbon black process produces only a very low structure and relatively low yield grade of popular (niche) carbon black; it cannot make the vast majority of carbon black surface area and structure required for reinforcement of tires, plastics or industrial rubber compounds.

The use of gaseous, renewable, recycled and/or sustainable low-yield feedstock in existing carbon black furnace processes would be economically useful and environmentally beneficial. These feedstocks will not necessarily be fossil fuel based. Examples of these include ethylene, which may be cracked from ethane or produced from bioethanol. Another example is natural gas, which may be fossil fuel based or generated from landfill sites or decay of organic matter. Further examples include vegetable oils, oils derived from pyrolysis of recycled tires, plastics, municipal waste, or biomass, or natural gas produced from landfill sites.

Unfortunately, these low yield carbon black feedstock generally give poor yields, low surface area and/or low structure compared to traditionally used furnace carbon black feedstock. The performance of these materials in furnace processes may be so poor that it is not possible to use them to make the structures required for most ASTM grades. The maximally achievable structure of the feedstock at a given surface area helps define the sizing capability of the feedstock.

Accordingly, there is a need in the industry to provide the following solutions: which is capable of using (allowing use of) large amounts of low-yield carbon black-forming feedstock in existing carbon black furnace processes (e.g., wherein at least a majority of the total feedstock used is low-yield carbon black feedstock) and still produce carbon black comparable to carbon black formed from conventional furnace carbon black feedstock (e.g., producing carbon black with acceptable yields and/or having high surface area and/or high structure). It uses existing furnace methods to use these low-yield feedstocks rather than developing, designing, and constructing new processes to use them, saving significant capital and development resources.

All patents and publications mentioned in their entirety are incorporated herein by reference.

Disclosure of Invention

It is a feature of the present invention to provide a method for preparing or producing carbon black from a feedstock comprising a low yield carbon black feedstock.

It is another feature of the present invention to provide a method of preparing or producing carbon black from a feedstock comprising a gaseous carbon black feedstock.

It is another feature of the present invention to provide carbon blacks made from raw materials including low-yielding carbon black raw materials.

It is another feature of the present invention to provide carbon blacks made from a feedstock comprising gaseous carbon black feedstock.

It is a further feature to provide a process utilizing a carbon black feedstock wherein at least a majority or more of the total amount of feedstock is a low yield carbon black feedstock.

It is a further feature to provide a method of producing carbon black from a low yield carbon black feedstock such that the resulting carbon black has an acceptable (e.g., good) yield, an acceptable (e.g., high) surface area, and/or an acceptable structure (e.g., high structure).

To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates in part to a method for producing carbon black. The method includes the steps of introducing a heated gas stream into a carbon black reactor (e.g., a furnace carbon black reactor), and combining at least one first carbon black feedstock with the heated gas stream to form a reaction stream. The method further includes the step of combining at least one low-yielding carbon black feedstock downstream with the reaction stream present to form carbon black. The method further includes recovering the carbon black in the reaction stream. In this process, the at least one low yield carbon black feedstock preferably comprises a majority or at least 60 wt% (based on total weight) of the total feedstock. The first carbon black feedstock is preferably liquid at the temperature and pressure within the chamber (e.g., 25 degrees celsius at 1 atm).

Furthermore, the present invention relates in part to carbon black, wherein at least a majority of the feedstock used to form the carbon black is a low yield carbon black feedstock.

The present invention further relates to products and/or articles such as, but not limited to, elastomeric compounds formed from any one or more of the carbon blacks of the present invention.

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 present invention as claimed.

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate various features of the application and together with the description, serve to explain the principles of the application.

Drawings

Fig. 1 is a graph showing the H: C (hydrogen atom to carbon atom) atomic ratio of a conventional carbon black raw material, compared with a low-yield raw material partially used in the present invention.

Fig. 2 is a graph showing the specific gravity of a conventional carbon black raw material compared to a low-yield raw material partially used in the present invention.

Fig. 3 is a graph showing BMCI values of conventional raw materials compared to low-yield raw materials partially used in the present invention.

FIG. 4A is a cross-sectional view of one example of a reactor suitable for use in preparing the carbon black of the present invention.

FIG. 4B is a cross-sectional view of another example of a reactor suitable for use in preparing the carbon black of the present invention.

FIG. 5 is a cross-sectional view of yet another example of a reactor suitable for use in preparing the carbon black of the present invention.

Fig. 6A and 6B show in side view an exemplary injector used in some comparative examples.

Fig. 7 and 8 are graphs plotting dimensionless (dimensionless ) yields and STSA (in m ²/g) for some examples of the invention and comparative examples. The numerical labels refer to the example numbers in tables 6-9.

Fig. 9 and 10 are graphs plotting OAN and STSA (in m ²/g) for some embodiments of the invention and comparative examples. Common numerical labels are referred to the example numbers in tables 6-9. The "N" number labels on the open diamond points indicate the data for the indicated ASTM grade carbon black; for example, the point "N330" represents the typical surface area and structure of N330 grade carbon black.

Fig. 11, 12 and 13 are graphs plotting OAN and STSA (in m ²/g) for some embodiments of the invention and comparative examples. Common numerical labels refer to the example numbers in tables 10, 13 and 15.

FIG. 14 is a graph plotting the achievable yield for a given surface area for the examples and comparative examples of the invention. The common numerical labels refer to the example numbers in table 15.

Detailed Description

The present invention relates to a process for producing carbon black using a low yield carbon black feedstock as defined and described herein. The invention also relates to carbon blacks produced by one or more of these methods. Using the methods of the present invention, at least a substantial portion of the total carbon black feedstock utilized can be one or more low yield carbon black feedstock. Using the process of the present invention, not only can large amounts of low-yielding carbon black feedstock be used, but there is no sacrifice in the quality of the carbon black produced. Thus, the process of the present invention utilizes carbon black feedstock that is more desirable for environmental and/or other reasons, and still produces carbon black comparable to carbon black produced using conventional carbon black feedstock used in furnace carbon black processes.

The method for producing the carbon black of the present invention comprises, consists essentially of, consists of, or comprises the following: introducing the heated gas stream into a carbon black reactor (e.g., a furnace carbon black reactor); combining at least one first carbon black feedstock with the heated gas stream to form a reaction stream; at least one low yield carbon black feedstock is combined downstream with the reaction stream present to form carbon black, and the carbon black in the reaction stream is recovered. In the process, preferably, the at least one low yielding carbon black feedstock comprises a majority of the total feedstock, and more preferably comprises at least 60 wt% of the total feedstock.

For the purposes of the present invention, a "low yielding carbon black feedstock" is a carbon black feedstock having at least one of the following properties:

1) A mineral office association index (BMCI) <100 (which provides an indication of low aromatic content of the liquid feed) (e.g., a BMCI of less than 99, less than 95, less than 90, less than 85, less than 80, less than 75, less than 70, such as a BMCI of 50 to 99, or 60 to 99, or 70 to 99, or 50 to 95, or 50 to 90), and/or

2) Carbonaceous material that is gaseous at the temperature (e.g., 25 degrees celsius) and pressure (1 atm) within the chamber, and/or

3) An H to C atomic ratio of greater than 1.23 (e.g., an H to C atomic ratio of 1.24 or greater, 1.25 or greater, 1.26 or greater, 1.27 or greater, 1.28 or greater, 1.29 or greater, 1.30 or greater, 1.35 or greater, 1.40 or greater, 1.45 or greater, 1.50 or greater, such as 1.235 to 1.5, or 1.235 to 1.45, or 1.235 to 1.4, or 1.235 to 1.35, or 1.235 to 1.3, or 1.235 to 1.29, or 1.235 to 1.28, or 1.235 to 1.27, or 1.24 to 1.5, or 1.25 to 1.5, or 1.26 to 1.5, or 1.27 to 1.5, or 1.28 to 1.5, or 1.29 to 1.5, or 1.3 to 1.5), and/or

4) A specific gravity of at most 1.02 (e.g., at most 1.015, at most 1.01, at most 1.005, at most 1.01, at most 1.00, at most 0.99, at most 0.95, such as 0.80 to 1.019, or 0.80 to 1.015, or 0.80 to 1.01, or 0.80 to 1.005, or 0.80 to 1.00, or 0.80 to 0.95, or 0.80 to 0.9, or 0.80 to 1.015, or 0.90 to 1.01, or 0.90 to 1.005, or 1.005 to 1.015).

The low yield carbon black feedstock may have only BMCI properties. The low yield carbon black feedstock may have only atomic H: C properties. The low yield carbon black feedstock may have only specific gravity properties. The low yield carbon black feedstock may have only gaseous properties.

The low yield carbon black feedstock can have BMCI properties and atomic H: C properties.

The low yield carbon black feedstock can have BMCI properties and specific gravity properties.

The low yield carbon black feedstock can have BMCI properties and gas properties.

The low yield carbon black feedstock can have BMCI properties, atomic H: C properties, and specific gravity properties.

The low yield carbon black feedstock can have BMCI properties, atomic H: C properties, and gas properties.

The low yield carbon black feedstock can have BMCI properties, atomic H: C properties, specific gravity properties, and gas properties.

The low yield carbon black feedstock can have atomic H: C properties and specific gravity properties.

The low yield carbon black feedstock can have atomic H: C properties and gaseous properties.

The low yield carbon black feedstock can have atomic H: C properties, specific gravity properties, and gas properties.

The low yield carbon black feedstock can have specific gravity properties and gas properties.

The low yield carbon black feedstock can be a feedstock derived from sources that are considered sustainable, biological, and/or recycled. For example, the low yield carbon black feedstock may be or include ethylene, a gas at room temperature and pressure. Ethylene may be produced from ethanol of biological origin, such as from corn fermentation or fermentation of other plant material. Another example of a low yield carbon black feedstock is natural gas.

For the purposes of the present invention, a low yield carbon black feedstock may be a feedstock that is not derived from fossil fuel based gasoline production, or coal cracking, or cracking to produce olefins. Thus, a low yield carbon black feedstock is a feedstock other than coal tar liquid, oil refinery liquid, or ethylene cracker residue.

Other examples of low-yielding liquid carbon black feedstock may include, but are not limited to, the following: tire pyrolysis oil, plastic pyrolysis oil, recycled oil, algae oil, plant derived oil, oil derived from pyrolysis of municipal solid waste, oil derived from pyrolysis or decay of biomass (e.g., animals or vegetables) or agricultural waste, oil derived from processing of pulp or paper production byproducts, and/or additional oil derived primarily from biological materials, or any combination thereof. Exemplary low-yield feedstocks include, but are not limited to, vegetable or other plant-derived oils, bioethanol of biological origin, plant or animal produced waxes or resins, oils made from animal fats, algae oils, oils made from pyrolysis of sewage sludge or agricultural waste, by-product liquids from processing of biogenic (biogenic) materials, liquids produced by hydrothermal liquefaction of biological materials, crude tall oil, tall oil rosin, tall oil pitch, or tall oil fatty acids, oils produced from recycled materials, oils derived from pyrolysis of low quality, off-grade or scrapped (end-of-life) tires, oils derived from pyrolysis of waste or recycled plastic or rubber products, oils derived from pyrolysis of municipal solid waste, or oils derived from pyrolysis of biomass, or any combination thereof. These liquid feedstocks have an H to C atomic ratio of greater than 1.23, or a specific gravity of up to 1.02, or a BMCI value of less than 100. The H to C atomic ratio can be measured according to ASTM D5291; specific gravity can be measured by ASTM D4052; BMCI may be measured according to Smith,H.M.(1940).Correlation Index To Aid In Interpreting Crude-Oil Analyses Technical Paper 610.Washington,DC,U.S.Department of the Interior,Bureau of Mines; the sulfur content may be measured according to the IP-336 or ISO 8754 standards. Flash points can be measured according to ISO 2719. Specific examples of liquid low-yielding carbon black feedstock are presented in table 1 below:

Examples of raw materials	Bolder 350 tire pyrolysis oil	DELTA ENERGY DE-Solv tire pyrolysis oil	Soybean oil	Corn oil	Peanut oil
						Atomic H: C	1.32	1.5	1.87	1.87	1.87
Specific gravity	1.00	0.94	0.93	0.92	0.91
						BMCI	94	62.5	56	54	50
Sulfur content (wt.%)	1.08	1.03	0	0	0
						Flash point (. Degree. C.)	68	32	>110	321	315

TABLE 1

FIG. 1 is a graph showing the H to C atomic ratio of a conventional high yield carbon black feedstock compared to a Tire Pyrolysis Oil (TPO), a vegetable oil (Veg. Oil), and two gas phase feedstocks (natural gas and ethylene) (gases). For conventional feedstocks, about 1000 representative collections of coal tar liquids, decant oils, and ECRs, H: C, were plotted for use as carbon black feedstock for furnace carbon black processes between 2016 and 2021. The range of H: C values can be compared to the three low yielding carbon black feedstock groups. It is clear that the conventional feedstock has a low H: C value of 1.23 or less (dashed line in the figure). The low yielding carbon black feedstock in FIG. 1 all have H: C values > 1.23.

Fig. 2 is a graph showing an example of specific gravity of a conventional high-yield raw material compared with a Tire Pyrolysis Oil (TPO) and a vegetable oil (veg.oil). For conventional feedstocks, the specific gravity of a collection of about 1000 representative coal tar liquids, decant oils, and ECRs used as carbon black feedstock for furnace carbon black processes between 2016 and 2021 were plotted. The specific gravity range was compared to two low yield carbon black feedstock groups. It is clear that conventional raw materials generally have a specific gravity (broken line in the drawing) of more than 1.02, whereas low-yield carbon black raw materials have a specific gravity of 1.02 or less.

Fig. 3 is a graph showing an example of BMCI values of a conventional high-yield raw material compared with Tire Pyrolysis Oil (TPO) and vegetable oil (veg.oil). For conventional carbon black feedstock, BMCI values for a collection of about 1000 representative coal tar liquids, decant oils, and ECRs used as feedstock for a furnace carbon black process between 2016 and 2021 were plotted. Their BMCI values were compared to two low-yielding feedstock groups. Almost all conventional feedstocks have BMCI values of >110, and all examples shown herein have BMCI values greater than or equal to 100 (dashed lines). In contrast, TPO and vegetable oil groups have BMCI values of less than 100.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: renewable feedstock, biologically derived or bio-based feedstock, and/or other byproducts of the refining process, or any combination thereof.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: vegetable or other plant derived oils (e.g., corn oil and/or corn distillate oil).

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: ethanol of biological origin (fermentation products from corn fermentation or other plant, vegetable or fruit sources).

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: waxes and resins produced by plants or animals, such as lanolin or shellac (lac).

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: an oil made from animal fat.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: algae oil.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: an oil produced by pyrolysis of sewage sludge or agricultural waste.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: byproduct liquids from the processing of biogenic materials.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: a liquid produced by the hydrothermal liquefaction of biological material.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: crude tall oil, tall oil rosin, tall oil pitch, or tall oil fatty acid (e.g., from a papermaking process).

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: renewable raw materials such as oil produced from recycled materials.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: oil derived from pyrolysis of low quality, off-spec or scrapped tires.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: oils derived from pyrolysis of waste or recycled plastics.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: an oil derived from pyrolysis of municipal solid waste.

Other examples of low yield carbon black feedstock may include, but are not limited to, the following: oils (bio-oils) derived from pyrolysis of biomass such as animals or plants (e.g., vegetables).

As noted above, in the present invention, at least a majority (in weight%) of the total feedstock utilized in some processes of the present invention is one or more low yield carbon black feedstock. Preferably, the amount is at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, for example 51 wt% to 95 wt%, or 60 wt% to 95 wt%, or 65 wt% to 95 wt%, or 70 wt% to 95 wt%, or 75 wt% to 95 wt%, or 60 wt% to 90 wt%, or 60 wt% to 85 wt%, or 60 wt% to 80 wt%, or 60 wt% to 75 wt%, based on the total weight percentage of all raw materials used.

For the purposes of the present invention, a "first carbon black feedstock" or "high yield carbon black feedstock" is a feedstock that is not a low yield carbon black feedstock as defined herein. The first carbon black feedstock can be considered or referred to as a carbon black feedstock conventionally used in furnace carbon black processes ("conventional" carbon black feedstock). As discussed further herein, as an option, the first carbon black feedstock may be a feedstock blend containing a small amount of a low yield carbon black feedstock.

The first carbon black feedstock is typically from the family of decant or slurry oils, coal tar or coal tar distillate fractions, or ethylene or phenol cracker residues. Their defining characteristics with respect to carbon black production in a typical furnace process are discussed further below.

The first carbon black feedstock had all three of the following properties:

1) At least 100 BMCIs (e.g., at least 101, at least 102, at least 103, at least 104, at least 105, at least 110, at least 115, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, such as 100 to 180, 101 to 180, 102 to 180, 103 to 180, 104 to 180, 105 to 180, 110 to 180, 115 to 180, 120 to 180, 130 to 180, 140 to 180, 150 to 180, 160 to 180, 100 to 175, 100 to 170, 100 to 165, 110 to 175, 115 to 175, 120 to 175, 125 to 170, 130 to 170),

2) A specific gravity of greater than 1.02 (e.g., greater than 1.025, greater than 1.03, greater than 1.035, greater than 1.04, greater than 1.05, such as 1.021 to 1.3, or 1.025 to 1.3, or 1.03 to 1.3, or 1.05 to 1.3, or 1.07 to 1.25),

3) At most 1.23 (e.g., at most 1.22, at most 1.21, at most 1.2, at most 1.15, at most 1.1, at most 1.05, at most 1, at most 0.9, at most 0.8, such as 1.225 to 0.7, 1.225 to 0.8, 1.225 to 0.9, 1.225 to 1, 1.225 to 1.1, 1.22 to 0.7, 1.21 to 0.7, 1.2 to 0.7).

As an option, the first carbon black feedstock may also be liquid at the temperature and pressure within the chamber (e.g., 25 degrees celsius and 1 atm). Although liquid, the first carbon black feedstock may be asphalt or similar material having a very high viscosity and need not exhibit significant flow.

Examples of the first carbon black feedstock are given in table 2 below and include coal tar, liquids distilled from coal tar, decant or slurry oils obtained from catalytic cracking, and resids from ethylene cracking. As shown in table 2, these feedstocks have H: C of up to 1.23, and specific gravities greater than 1.02, and BMCI values of at least 100.

TABLE 2

The first carbon black feedstock may also comprise a fraction derived from refined or distilled tire pyrolysis oil. Tire pyrolysis may be accomplished by any method known to those skilled in the art. Exemplary methods include, but are not limited to, those found in US8350105 and US20180320082, the entire contents of both of which are incorporated herein by reference. Distillation of the oil obtained may also be accomplished by any method known to those skilled in the art. Exemplary methods include, but are not limited to, those found in US9920262, WO2019236214, the contents of which are incorporated herein by reference. The tire pyrolysis oil can be distilled to provide at least one fraction useful as a first carbon black feedstock and at least one fraction that is a low yield carbon black feedstock. In practice, distillation may produce a light fraction that may be more economically used in other unit processes of the carbon black production process, for example, as fuel for a dryer for carbon black or for a heater for preheating one or both of the first carbon black feedstock or the second carbon black feedstock, as disclosed in US20130039841, the contents of which are incorporated herein by reference. Thus, integration of the distillation process with the carbon black reactor may make recycling of the carbon black-filled tires economically and environmentally beneficial.

Alternatively, in the method of the present invention, the first carbon black raw material may be used in an amount of 49 wt% or less, 45 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, for example, 5 wt% to 49 wt%, or 5 wt% to 45 wt%, or 10 wt% to 40 wt%, or 10 wt% to 35 wt%, or 10 wt% to 30 wt%, based on the total amount of raw materials (in wt%) utilized.

The first carbon black feedstock can be a liquid at room temperature (e.g., 25 ℃) and atmospheric (atmosphere) (e.g., 1 atm) conditions. By "aromatic-rich" is meant that the feedstock has substantial amounts of aromatic compounds present. For example, the plurality of aromatic compounds is a BMCI in which the total weight percent of aromatic compounds present is at least 20 weight percent, or has at least 100, or both. The first carbon black feedstock can be heated such that the feedstock is in the form of steam and thus can become or in practice be used as aromatic-rich steam.

With respect to the method steps of the present invention, the method includes forming a heated gas stream or introducing a heated gas stream into a carbon black reactor (e.g., a furnace carbon black reactor).

The "heated gas stream" may be a stream of hot gas or hot combustion gas. The heated gas stream may be generated by contacting the solid, liquid, and/or gaseous fuel with a suitable oxidant stream such as, but not limited to, air, oxygen, a mixture of air and oxygen, and the like. Alternatively, the preheated oxidant stream may be passed without the addition of liquid or gaseous fuel. Examples of fuels suitable for use in contacting the oxidant stream to produce the hot gas include any readily combustible gas, steam or liquid stream, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene. In general, it is preferred to use fuels having a high content of carbonaceous components and in particular hydrocarbons. The equivalence ratio (defined below) of the mixture of fuel and oxidant mixed to form the hot gas may be from 10 (very fuel rich) to about 0.1 (very fuel lean), or the minimum value that the use of a given burner or oxidizer still allows the hot gas to be produced. As described, to facilitate the generation of hot gases, the oxidant stream may be preheated. Basically, the heated gas stream is generated by igniting or combusting a fuel and/or an oxidant. For the heated gas stream, a temperature of, for example, about 1000 degrees celsius to about 3500 degrees celsius may be obtained.

The carbon black reactor is preferably a furnace carbon black reactor. More preferably, the carbon black reactor is a version of a furnace reactor known as a staged (staged) carbon black reactor (e.g., a multi-stage carbon black reactor or a multi-stage reactor). By "staged" is meant that the feedstock is introduced or injected at more than one axial location along the long axis of the furnace.

For the purposes of this process, as well as other processes described herein, a multi-stage carbon black reactor may be used, such as those described in U.S. Pat. No.4,383,973, U.S. Pat. No.7,829,057, U.S. Pat. No.5,190,739, U.S. Pat. No.5,877,251, U.S. Pat. No.6,153,684, or U.S. Pat. No.6,403,695, all of which are incorporated herein by reference in their entirety.

The general process of forming carbon black and obtaining a suitable hot gas to form carbon black by a carbon black reactor, such as a multistage reactor, is further described in the above-referenced patents, which are incorporated herein by reference and may be employed in the present invention with the variations described herein.

Fig. 4A and 4B show cross-sectional views of a carbon black reactor (50 in fig. 4A and 80 in fig. 4B) that may be used. In fig. 4A, hot combustion gases are produced in a combustion zone or chamber 1 by contacting fuel 9 in the form of a liquid or gaseous fuel stream with an oxidant stream 5, such as air, oxygen, or a mixture of air and oxygen (also known in the art as "oxygen-enriched air"). The fuel may be any readily combustible gas, vapor, or liquid stream, such as hydrocarbons (e.g., methane, natural gas, acetylene), hydrogen, alcohols, kerosene, fuel mixtures, and the like. In many cases, the fuel selected has a high content of carbonaceous components.

Various gaseous or liquid fuels, such as hydrocarbons, may be used as combustion fuels. The equivalence ratio is the ratio of the fuel to the amount of stoichiometric oxidant required to completely combust the fuel. Typical values for the equivalence ratio in the combustion zone are in the range of 1.2 to 0.2. To facilitate the generation of hot combustion gases, the oxidant stream may be preheated.

In the present invention, the combustion step may consume the combustion fuel completely or almost completely. Oxygen, fuel selection, burner design, injection speed, mixing conditions and/or mode, fuel to air, oxygen enriched air or pure oxygen ratio, temperature, and/or other factors may be adjusted or optimized.

The hot combustion gas stream flows downstream from zones 1 and 2 into zones 3 and 4. The carbon black feedstock is introduced at one or more suitable locations relative to the other reactor components and feeds. Zone 2 of the combustion chamber may be the location where one or more carbon black feedstock is introduced. In fig. 4A, injector 10 and/or injector 6 may be used to introduce carbon black feedstock into the reactor. For example, the injector 10 may introduce or inject a first carbon black feedstock into the reactor. Alternatively, the first carbon black feedstock may also be introduced into the chamber using an axial tube or lance (lance) (shown as tube or lance 63 in fig. 4B). As a further alternative, the first carbon black feedstock may be injected or introduced simultaneously by a variety of methods. The lance or any other injector exposed to the reactor or combustion chamber may need to be cooled or protected from overheating in the combustion chamber by methods known in the art.

Further carbon black feedstock, such as low yield carbon black feedstock, may be introduced into the reactor zone 3 by injector 6 at injection point 7. In the present invention, generally, at least a portion, if not all, of the first carbon black feedstock can be injected or introduced prior to introducing the low yield carbon black feedstock into the reactor. Preferably, a majority (> 50%) of the first carbon black feedstock used in the reactor is introduced prior to the introduction of any low yield carbon black feedstock. Zones 3 and 4 are reaction zones and zone 8 is a quenching (quenching, quench) zone. Q represents the length of zone 4 prior to quenching zone 8.

The carbon black feedstock may be injected into the combustion gas stream through one or more nozzles designed to optimally distribute the feedstock into the combustion gas stream. Such nozzles may be single fluid or dual fluid. The two-fluid nozzle may atomize the feedstock using, for example, steam, air, or nitrogen. The single fluid nozzle may be pressure atomized or the feedstock may be injected directly into the gas stream. In the latter case, atomization occurs by the force of the air flow.

The carbon black feedstock may be injected by an axial injection lance, or a central tube may be used, and/or one or more radial lances arranged on the circumference of the reactor in a plane perpendicular to the flow direction. One reactor may contain multiple planes with radial lances along the flow direction. A spray or injection nozzle may be arranged on the head of the spray gun, by means of which nozzle the raw material is mixed into the flow of the heated gas stream.

Fig. 4B shows a cross section of another example of a carbon black reactor in a furnace process that may be used in the present invention. In this example, as in fig. 4A, oxidant stream 51 is combined with combustion fuel 52 in combustion chamber 55.

The hot combusted or partially combusted gas stream produced in chamber 55 flows in direction A to a throat or constriction 64. The first carbon black feedstock is introduced into the furnace carbon black reactor 80 prior to the low yield carbon black feedstock. The first carbon black feedstock may be introduced using an optional center tube 63, or lance, or injector, or lance set 56, or via a lance or injector placed at or near a throat 64 as indicated by 57. The first carbon black feedstock can be introduced at one of these locations, or simultaneously in two of these locations, or simultaneously in all three locations. When more than one location is used, the manner and division of the first feedstock injection may be varied between these locations to alter product properties and process economics. The injector and the combustion chamber itself (or portions thereof) may be cooled as desired by methods known in the art.

In fig. 4B, the length between the optional center tube injector 63 and the middle of the constriction 64 is labeled as length 60. If the center tube is used, the length is preferably 1 to 10 times the narrowest diameter of the first constriction 64. If a center tube is used simultaneously with the injector or lance array 57 for introducing the first carbon black feedstock, the length 60 may be as described above or as small as 0. Adjusting this length may allow for a balance of structural and process economics. The height or diameter 54 of the combustion chamber is shown and is greater than the height or diameter 64, and the height or diameter 64 may be at least 20%, at least 30%, at least 40%, at least 50% less than the height or diameter 54.

After the first carbon black feedstock is introduced, a hot gas stream mixed with the feedstock enters the first reaction chamber 58. The purpose of this chamber is to provide a residence time such that the pyrolysis reaction to produce carbon black can complete the induction time and optionally begin to produce a population of seed particles (SEED PARTICLE pulses) for subsequent structure growth, as taught in U.S. patent No.7,829,057. The length of the chamber 66 may typically be 1 to 20 times the narrowest diameter of the first constriction 64.

At the end of the first reaction chamber 58, a low yield carbon black feedstock may be introduced. It may be introduced using an injector or array of injectors 59 located in or near the second constriction 65. Alternatively, the lance may be introduced substantially upstream of the constriction 65, but within the chamber 58.

After the introduction of the low-yield carbon black raw material, the mixture flows into the second reaction chamber 61. The cooled spray of liquid or vapor 62 is then used to quench it, as is known in the art. The length from the injection point 59 of the low yielding carbon black feedstock to the quench location 62 is labeled 67 in fig. 4B. The length is set to provide a residence time that controls some product properties, as is known in the oven process art.

An alternative arrangement would be to introduce a first carbon black feedstock at locations 63 and/or 56 and then a low yield carbon black feedstock at locations 57 and/or 59, if two locations are used, then both could be introduced simultaneously. This can provide a beneficial tradeoff between carbon black structural ability and yield or process economics. In all of the above embodiments, at least a portion and preferably a majority (> 50%) of the first carbon black feedstock used, e.g., all of the first carbon black feedstock, is introduced prior to and upstream of the low yielding carbon black feedstock.

In yet another example of the present invention, the first carbon black feedstock can be a blend of a low yielding carbon black feedstock and a high yielding carbon black feedstock that meets the BMCI, specific gravity, and H: C parameters described above, provided that the blend meets the BMCI, specific gravity, and H: C parameters described above for the first carbon black feedstock. The blend may contain greater than 50 wt.% high yield carbon black feedstock (e.g., 50.5 wt.% to 99.5 wt.%, such as 60 wt.% to 99 wt.% high yield carbon black feedstock) by mass.

Similarly, the low-yielding carbon black feedstock can optionally be a blend of a high-yielding carbon black feedstock and a non-high-yielding carbon black feedstock that does not meet at least one of the BMCI, H: C, and specific gravity parameters for the first carbon black feedstock, provided that the blend also does not meet at least one of the BMCI, H: C, and specific gravity parameters required for the first carbon black feedstock. The non-high yielding carbon black feedstock can be present in an amount greater than 50% by mass of the total feedstock of the optional blend (e.g., 50.5 wt.% to 99.5 wt.%, such as 60 wt.% to 99 wt.% of the non-high yielding carbon black feedstock). In addition, the total amount of the first carbon black feedstock introduced into the reactor by the sum of all injection sites is less than 50 wt.% based on the total amount of carbon black feedstock used at any site in the reactor. The total amount of low yield carbon black feedstock is greater than 50 wt.% based on the total feedstock.

Optionally, in one method of the invention, the method includes the step of introducing at least one first carbon black feedstock into the carbon black reactor with the heated gas stream to form a reaction stream. The first carbon black feedstock can be one first carbon black feedstock, or a combination of two or more different first carbon black feedstock. When more than one type of feedstock is utilized as the first carbon black feedstock, the multiple first carbon black feedstocks may be blended together and injected through one or more locations as one blended feedstock, or each feedstock may be injected separately into the combustion chamber at the same or different locations.

Optionally, in one method of the invention, the method includes the step of introducing at least one low yield carbon black feedstock into the reaction stream. The low-yield carbon black feedstock can be one low-yield carbon black feedstock, or a combination of two or more different low-yield carbon black feedstock. When more than one type of feedstock is utilized as the low yield carbon black feedstock, the multiple low yield carbon black feedstocks may be blended together and injected through one or more locations as one blended feedstock, or each feedstock may be injected separately into the combustion chamber at the same or different locations.

Generally, any carbon black feedstock utilized in any of the methods of the present invention can be injected into the reactor through a single stream or multiple streams using an injector that penetrates into the interior region of the hot combustion gas stream. The injector may better ensure high mixing and shear rates of the hot combustion gases and carbon black feedstock. This ensures that the feedstock is pyrolyzed and preferably pyrolyzed at a fast rate and/or in high yield to form the carbon black of the present invention.

FIG. 5 shows a specific example of a reactor that can be used to practice the present invention and to prepare examples 1-13 below.

The first carbon black feedstock can be introduced at one location in the reactor or at multiple locations in the reactor. The introduction of the feedstock may be accomplished with a center tube or lance 73 located in the combustion chamber 74 having a maximum diameter D _Chamber in the reactor 90, as shown for example in fig. 5. The central tube may be positioned substantially on the centerline (axial center) of the reactor. The center tube may have an injection head 77 or spray head on the tip. The injector on the tip may have, for example, one or more holes (2, or 3, or 4, or more) around the tip (e.g., a plurality of holes, substantially evenly spaced as shown in fig. 6A, wherein one of the plurality of holes 610 is shown). The injection point may be accomplished through a center tube or may be accomplished using other injection means.

In one embodiment of the invention, the low yield carbon black feedstock may be introduced at one location in the reactor or at multiple locations in the reactor. As noted, in this process of the present invention, one or more locations in the reactor are downstream of the one or more locations where the first carbon black feedstock is injected or introduced. The introduction of the low yield carbon black feedstock can be performed with one or more injectors (e.g., metal tubes located on the reactor wall) that introduce the feedstock into the combustion chamber of the reactor, as shown, for example, in fig. 4A and 4B. The injector may have an injection head or spray head on the tip. The injector on the tip may have, for example, one or more holes (2, or 3, or 4, or more) (a plurality of holes spaced substantially evenly) around the tip.

Alternatively, the introduction of a low yield carbon black feedstock into the reactor and into the reaction stream may be such that the feedstock is introduced perpendicular to the cross flow of the reaction stream through the reactor, as shown, for example, in fig. 4A and 4B. The vertical may be plus or minus 15 degrees from the true (true) vertical injection of the feedstock into the reaction stream.

Alternatively, the introduction of the low yield carbon black feedstock into the reactor may be at the following locations: which has a diameter narrower than the diameter of the reactor in which the first carbon black feedstock is introduced earlier. In some carbon black reactors, this location may be considered the "throat". Fig. 4A and 4B provide examples of such a throat or throat region in a reactor. The narrower diameter may have a diameter that is at least 10% smaller, at least 20% smaller, or at least 30% smaller, or 10% to 40% smaller than the diameter of the reactor in which the first carbon black feedstock was introduced earlier. In fig. 5, this is D _Chamber to D _{Throat part} 76.

Alternatively, the introduction of the low yield carbon black feedstock into the reactor and into the reaction stream may be at the following locations: which is at a distance D _A (in fig. 5, this distance is denoted as L _Pipe, 78) from where the first carbon black feedstock is introduced or injected into the reactor, and which D _A is at least 1 or at least 2 times the narrowest diameter of the combustion chamber of the reactor (or at least 2 times the diameter of the reactor in which the first carbon black feedstock is introduced or injected). The distance may be at least 2.25 times, at least 2.5 times, at least 2.75 times, at least 3 times, at least 3.25 times, at least 3.5 times, at least 3.75 times, or at least 4 times the diameter of the combustion chamber of the reactor (or at least 2.25 times, at least 2.5 times, at least 2.75 times, at least 3 times, at least 3.25 times, at least 3.5 times, at least 3.75 times, or at least 4 times the diameter of the reactor in which the first carbon black is introduced or injected).

The low yield carbon black feedstock may be introduced at location 83 by one or more injectors.

After combining the feedstock (first carbon black feedstock and low yield carbon black feedstock) with the reaction stream, the process of the present invention generally includes the step of quenching the reaction. In fig. 5, this is quench spray 81. The reaction zone, shown at 80 after throat 76, has a maximum diameter D _{reactor for producing a catalyst}.L_{Quenching of} showing the length from the point where the low yielding carbon black feedstock is introduced to the point where quenching occurs.

The reaction was stopped in the quenching zone of the reactor (see zone 8 of fig. 4A). As shown in fig. 4A, quench 8 is located downstream of reaction zone 4 and a quenching fluid, such as water, is sprayed into the newly formed carbon black particle stream. Typically, quenching is used to cool the carbon black particles and reduce the temperature of the gaseous stream and reduce the rate of reaction. Q is the distance from the start of reaction zone 4 to quench point 8 and will vary depending on the location of quenching. Optionally, quenching may be staged, or performed at multiple points in the reactor. Pressure spraying, gas atomization spraying, or other quenching techniques may also be utilized. With respect to completely quenching the reaction to form carbon black, any means known to those skilled in the art may be used to quench the reaction downstream of the introduction of the carbon black yielding feedstock. For example, a quenching fluid, which may be water or other suitable fluid, may be injected to stop the chemical reaction.

After quenching, the cooled gas and carbon black are passed downstream to any conventional cooling and separation equipment, whereby the product is recovered. Separation of the carbon black from the gas stream is readily accomplished by conventional means such as a precipitator, cyclone separator, bag filter or other means known to those skilled in the art. After separating the carbon black from the gas stream, the carbon black may optionally be subjected to a granulation step.

For any of the methods of the present invention, as an option, the carbon black produced is not a carbon black having a core and a cover.

For any of the methods of the present invention, as an option, the carbon black is formed entirely in situ in the reactor.

Alternatively, any one or more of the carbon black feedstock or other components used in the process of the present invention may be preheated prior to introduction into the reactor. Suitable preheat temperatures and/or preheat techniques may be used in the present invention, as set forth, for example, in the following: U.S. patent No.3,095,273 to Austin at 25, 6, 1963; U.S. patent No.3,288,696 to obach at 11/29 in 1966; U.S. Pat. No.3,984,528 to Cheng et al, 10/5 in 1976; U.S. Pat. No.4,315,901 to Cheng et al, 2.16 in 1982; U.S. Pat. No.4,765,964 to Gravley et al, 8.23 in 1988; U.S. Pat. No.5,997,837 to Lynum et al, 12/7 1999; U.S. patent No.7,097,822 to Godal et al, 8/29/2006; U.S. patent No.8,871,173B2 or CA 682982 to Nester et al, 10/28 2014, all of which are incorporated herein by reference in their entirety. Alternatively or additionally, the low yield carbon black feedstock may be preheated to a temperature higher than is typical of high yield feedstocks. For example, the low yield carbon black feedstock may be heated to a temperature in excess of 600 ℃, such as 600-800 ℃, even at ambient pressure. Because low yielding carbon black feedstock has a low concentration of asphaltenes, heating to such high temperatures does not produce significant amounts of coke or other solid non-carbon black species. Alternatively or additionally, any one or more carbon black feedstock may be combined with an extender fluid prior to introduction into the reactor, for example as described in U.S. patent No.10,829,642 to Unrau, the entire contents of which are incorporated herein by reference.

As an option, the method is performed in the absence of at least one of the following: which is or contains at least one group IA or group IIA element of the periodic table (or an ion thereof).

Optionally, in any of the methods of the present invention, the method may comprise the step of introducing at least one of: which is or contains at least one group IA or group IIA element of the periodic table (or an ion thereof). Preferably, the substance contains at least one alkali metal or alkaline earth metal. Examples include lithium, sodium, potassium, rubidium, cesium, francium, calcium, barium, strontium, or radium, or combinations thereof. Any mixture of one or more of these components may be present in the substance. The substance may be a solid, a solution, a dispersion, a gas, or any combination thereof. More than one species having the same or different group IA or group IIA metals may be used. If multiple materials are used, these materials may be added together, separately, sequentially, or at different reaction sites. For the 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, and the like. Preferably, the material is capable of introducing a metal or metal ion into the ongoing reaction to form a carbon black product. For the purposes of the present invention, it is preferred to introduce the species prior to complete quenching as described above. For example, the material may be added at any point prior to complete quenching, including prior to introduction of one or both carbon black yielding feedstock; during the introduction of either or both carbon black yielding feedstock; after introducing any or all of the carbon black yielding feedstock; or after all of the starting material has been introduced but before complete quenching. More than one point of substance introduction may be used. The amount of group IA or group IIA metal-containing material can be any amount so long as a carbon black product can be formed. For example, the amount of material may be added in an amount such that 200ppm or more of the group IA or group IIA element is present in the final formed carbon black product. Other amounts include about 200ppm to about 5000ppm or more of group IA or group IIA elements present in the formed carbon black product, and other ranges may be about 300ppm to about 1000ppm, or about 500ppm to about 1000ppm. These levels may be relative to metal ion concentration. As noted, these amounts of group IA or group IIA elements present in the formed carbon black product may be relative to one element or more than one group IA or group IIA element, and thus will be the combined amounts of group IA or group IIA elements present in the formed carbon black product. The substance may be added in any manner, including any conventional means. In other words, the substance can be added in the same manner as the carbon black-producing raw material is introduced. The substance may be added as a gas, liquid, or solid, or any combination thereof. The substance may be added at one point or multiple points and may be added as a single stream or multiple streams. The materials may be mixed with the feedstock, fuel and/or oxidant prior to or during their introduction.

With respect to the carbon blacks formed by any of the methods of the present invention, the carbon blacks formed or produced may be any reinforcing or non-reinforcing grade of carbon black. Examples of enhancement levels are N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358 and N375. Examples of semi-enhancement levels are N539, N550, N650, N660, N683, N762, N765, N774, N787, and/or N990.

The carbon black may be furnace black.

Carbon black can pass through specific surface area, structure, aggregate size, shape, and distribution; and/or chemical and physical properties of the surface. The properties of the carbon black are determined by test analysis as known in the art. For example, nitrogen adsorption surface area and Statistical Thickness Surface Area (STSA) (another measure of surface area) were determined by nitrogen adsorption according to ASTM test procedure D6556. Iodine number can be measured using ASTM procedure D-1510. Carbon black "structure" describes the size and complexity of a carbon black aggregate formed by primary carbon black particles fusing to one another. As used herein, the carbon black structure can be measured as the Oil Absorption Number (OAN) of an uncrushed carbon black, expressed as milliliters of oil per 100 grams of carbon black, according to the procedure set forth in ASTM D-2414. The oil absorption value (COAN) of the compressed sample measures the portion of the carbon black structure that is not easily altered by the application of mechanical stress. COAN is measured according to ATSM D3493. Aggregate Size Distribution (ASD) was measured according to the ISO 15825 method using a disc centrifugal photo deposition meter (Disc Centrifuge Photosedimentometry) manufactured by Brookhaven Instruments, model BI-DCP.

Carbon black materials having properties suitable for a particular application may be selected and defined by ASTM standards (see, e.g., ASTM D1765 standard classification system for carbon black used in rubber products), such as N100, N200, N300, N500, N600, N700, N800, or N900 series carbon blacks, such as ,N110、N121、N220、N231、N234、N299、N326、N330、N339、N347、N351、N358、N375、N539、N550、N650、N660、N683、N762、N765、N774、N787、 or N990 carbon blacks, or other commercial grade specifications.

The carbon black may have any STSA, e.g., ranging from 5m ²/g to 250m ²/g、11m²/g to 250m ²/g, 20m2/g to 250m ²/g or higher, e.g., at least 70m ²/g, e.g., 70m ²/g to 250m ²/g, or 80m2/g to 200m ²/g, or 90m ²/g to 200m ²/g, or 100m ²/g to 180m ²/g、110m²/g to 150m ²/g、120m²/g to 150m ²/g, etc. Alternatively, the carbon black can have an iodine value (I2 value) of from about 5 to about 35mg I ₂/g carbon black (according to ASTM D1510).

The carbon black particles disclosed herein can have a BET surface area of 5m ²/g to 300m ²/g, e.g., between 50m ²/g and 300m ²/g, e.g., between 100m ²/g and 300m ²/g, as measured by the Brunauer/Emmett/Teller (BET) technique according to the procedure of ASTM D6556. The BET surface area may be from about 100m ²/g to about 200m ²/g, or from about 200m ²/g to about 300m ²/g.

The oil absorption value (OAN) may be between 40mL/100g and 200mL/100g, such as between 60mL/100g and 200mL/100g, such as between 80mL/100g and 200mL/100g, such as between 100mL/100g and 200mL/100g, or between 120mL/100g and 200mL/100g, between 140mL/100g and 200mL/100g, between 160 and 200mL/100g, or such as between 40mL/100g and 150mL/100g, or between 40mL/100g and 150mL/100 g.

The COAN may be in the range of about 40mL/100g to about 150mL/100g, for example, between about 55mL/100g to about 150mL/100g, for example, between about 80mL/100g to about 150mL/100g, or between about 80mL/100g to about 120mL/100 g.

The carbon black can be a carbon product containing siliceous and/or metalliferous species, etc., which can be accomplished by further steps including the introduction or additional introduction of such species in either or both of the carbon black-yielding feedstock. For the purposes of the present invention, the carbon black may be a multiphase aggregate comprising at least one carbon phase and at least one metal-containing species phase or silicon-containing species phase (also referred to as a silicon-treated carbon black, e.g., ECOBLAKTM material from Cabot Corporation).

As noted, the carbon black can be rubber carbon black, and in particular, reinforcing grade carbon black or semi-reinforcing grade carbon black.

Alternatively, the carbon blacks of the present invention may have functional or chemical groups (e.g., derived from small molecules or polymers, ionic or nonionic) directly attached to the carbon surface (e.g., covalently attached). Examples of functional groups that can be directly attached (e.g., covalently) to the surface of the carbon black particles and methods for performing surface modification are described, for example, in U.S. Pat. No.5,554,739 to Belmont at 9/10/1996 and U.S. Pat. No.5,922,118 to Johnson et al at 7/13/1999, which are incorporated herein by reference in their entireties. As one example, surface-modified carbon blacks that can be used herein are obtained by treating carbon blacks with diazonium salts formed by the reaction of sulfanilic acid or para-aminobenzoic acid (PABA) with HCl and NaNO ₂. For example, surface modification of a sulfanilic acid or para-aminobenzoic acid process by use of diazonium salts results in a carbon black having an effective amount of hydrophilic moieties on the carbon cover.

Carbon black can be surface modified according to U.S. patent No.8,975,316 to Belmont et al, the entire contents of which are incorporated herein by reference.

Other techniques that may be used to provide functional groups attached to the surface of carbon black are described in U.S. patent No.7,300,964 to NIEDERMEIER et al, 11, 27, 2007.

Oxidized (modified) carbon blacks can be prepared in a similar manner as for carbon blacks, as described, for example, in U.S. patent No.7,922,805 to Kowalski et al at 4.12 and U.S. patent No.6,471,763 to Karl at 10.29 of 2002, and are incorporated herein by reference in their entirety. Oxidized carbon blacks are carbon blacks that have been oxidized using an oxidizing agent to introduce ionic and/or ionizable groups onto a surface. Such particles may have a higher degree of oxygen-containing groups on the surface. Oxidizing agents include, but are not limited to, oxygen; ozone; peroxides such as hydrogen peroxide; persulfates, including sodium persulfate and potassium persulfate; hypohalites such as sodium hypochlorite; oxidizing acids such as nitric acid; and transition metal-containing oxidizing agents such as permanganate, osmium tetroxide, chromium oxide, or ammonium cerium nitrate. Mixtures of oxidizing agents, particularly gaseous oxidizing agents such as mixtures of oxygen and ozone, may also be used. Other surface modification methods, such as chlorination and sulfonylation, may also be employed to introduce ionic or ionizable groups. The carbon black may be surface modified by any method known to those skilled in the art. For example, the carbon black may be heat treated as described in US10767028, the entire contents of which are incorporated herein by reference.

The carbon black can be used in a variety of applications, for example as a reinforcing material in rubber products such as tire components.

Carbon black can be incorporated into rubber articles, such as treads for tires, particularly passenger, light, truck and bus tires, off-highway ("OTR") tires, aircraft tires, and the like; a subtread; a wire cladding (wire skip); a sidewall; cushion gum for retreading tires; and other tire applications.

In other applications, the particles may be used in industrial rubber products such as engine mounts, hydraulic mounts, bridge bearings and shock isolators, tank tracks (TANK TRACK) or treads, mining belts (mining belt), hoses, gaskets, seals, blades, weather strip products, bumpers, vibration resistant parts, and the like.

Carbon black may be added as an alternative or in addition to the first reinforcing agent for tire components and/or other industrial rubber end uses. The carbon black may be combined with natural and/or synthetic rubber in a suitable dry or wet mixing process based on an internal batch mixer, continuous mixer or roll mill.

Alternatively, carbon black may be mixed into the rubber via a liquid masterbatch process. For example, a slurry containing the particles described herein may also be mixed with an elastomer latex in a tank and then coagulated by addition of a coagulating (coagulating) agent such as an acid using the techniques described in U.S. patent No.6,841,606.

Carbon black can be introduced according to U.S. Pat. No.6,048,923 to Mabry et al, 4/11/2000, which is incorporated herein by reference in its entirety. For example, a process for preparing an elastomeric masterbatch may involve simultaneously feeding a particulate filler fluid and an elastomer latex fluid to a mixing zone of a coagulum reactor. The condensation zone extends from the mixing zone, preferably with a gradual increase in cross-sectional area in the downstream direction from the inlet end to the discharge end. The elastomer latex may be natural or synthetic, and the particulate filler comprises, consists essentially of, or consists of: a material as described above. The particulate filler is preferably supplied to the mixing zone as a continuous high velocity jet of injection fluid, while the latex fluid is supplied at a low velocity. The velocity, flow rate, and particle concentration of the particulate filler fluid are sufficient to cause high shear mixing of the latex fluid and turbulent flow of the mixture in at least the upstream portion of the coagulum zone to substantially completely coagulate the elastomer latex with the particulate filler prior to the discharge end. Substantially complete coagulation may occur without the need for an acid or salt coagulant. As disclosed in U.S. patent No.6,075,084, which is incorporated herein by reference in its entirety, additional elastomer may be added to the material emerging from the discharge end of the coagulum reactor. As disclosed in U.S. patent No.6,929,783, incorporated herein by reference in its entirety, the coagulum can then be fed to a dewatering extruder. Other examples of suitable masterbatch processes are disclosed in U.S. patent No.6,929,783 to Chung et al; berriot et al, application US2012/0264875A1; application US2003/0088006A1 to Yanagisawa et al; and EP1834985B1 to Yamada et al.

Carbon black can be evaluated in suitable rubber formulations using natural or synthetic rubber. The appropriate amount of carbon black to be used can be determined by routine experimentation, calculation, by taking into account factors such as typical loadings of standard ASTM furnace black in comparable manufacturing processes, the specific parameters of the technology and/or equipment used, the presence or absence of other additives, the desired properties of the final product, etc.

The performance of carbon black as a reinforcing agent for rubber compounds can be evaluated by determining, for example, the performance of a rubber composition utilizing particles relative to a comparative rubber composition that is similar in all respects except for the use of a carbon black grade suitable for a given application. In other methods, the values obtained for the compositions prepared according to the present invention may be compared to values known in the art that relate to the desired parameters in a given application.

Suitable tests include green rubber tests, cure tests, and cured rubber tests. Among the suitable green rubber tests, ASTM D4483 sets forth the test method for ML1+4 mooney viscosity test at 100 ℃. Scorch time was measured according to ASTM D4818.

Cure curves were obtained by rubber procedure analyzer (RPA 2000) according to ASTM D5289 at 0.5 °, 100cpm and 150C (NR) -160C (SBR).

The performance characteristics of the cured samples can be determined by a series of suitable tests. Tensile strength, elongation at break, and stress at various strains (e.g., 100% and 300%) are all obtained via ASTM D412 method a. Dynamic mechanical properties, including storage modulus, loss modulus, and tan delta, were obtained by strain sweep testing at 10Hz, 60C, and various strain amplitudes from 0.1% to 63%. Shore A hardness was measured according to ASTM D2240. The tear strength of die B-type cured rubber samples was measured according to ATSM D624.

According to various reported methods, the undispersed area is calculated by analyzing an image of the cured rubber compound of cut cross-sectional area obtained via a reflection mode optical microscope. The dispersion can also be expressed by the Z value (measured after reticulation (reticulation) according to the method described in the article by S.Otto and Al at Kautschuk Gummi Kunststoffe,58Jahrgang, NR 7-8/2005, titled NEW REFERENCE value for the description of Filler Dispersion WITH THE DISPERGRADER 1000 NT). The standard ISO 11345 describes a visual method for rapid and comparative evaluation of the degree of macroscopic dispersion of carbon black and carbon black/silica in rubber.

Abrasion resistance was quantified by Cabot Abrader (Lambourn type) as an index based on abrasion loss of the cured rubber. Attractive wear resistance results may indicate favorable wear properties. Good hysteresis results may be associated with low rolling resistance (and correspondingly higher fuel economy) for motor vehicle tire applications, reduced heat accumulation, tire durability, tread life and carcass life, fuel economy characteristics of the motor vehicle, and the like.

Iodine number (I2 value) was determined according to ASTM test procedure D1510. STSA (statistical thickness surface area) was determined based on ASTM test procedure D-5816 (measured by nitrogen adsorption). OAN was determined based on ASTM D2414. COAN is determined based on ASTM D3493 (e.g., D3493-20).

All material proportions described herein as percentages are by weight unless otherwise indicated.

The invention will be further elucidated by the following examples, which are intended to be merely exemplary in nature.

Examples

For the purposes of the present invention and the embodiments presented herein, the following explanation of some terms is provided.

Equivalence ratio: for the partial oxidation process, the total equivalence ratio Φ _o is the ratio of the molar flow of oxidant required for stoichiometric combustion of all input fuel and feedstock divided by the actual molar flow of oxidant. Thus, when Φ _o >1, the mixture is fuel-rich, and when Φ _o <1, the mixture is fuel-lean. Carbon black production preferably occurs when Φ _o is substantially fuel rich, typically > 1.6.

For a combustor producing hot combustion gases, the equivalence ratio Φ _p is defined by the amount of combustor fuel and oxidant delivered. Phi _p is typically fuel-lean, taking a value of 0.33 to 0.9.

The equivalence ratio Φ _I is the equivalence ratio of the combustion chamber plus any additional fuel or feed introduced into the center tube shown in fig. 5, but does not include feed introduced at the throat.

Yield: the yield Y is the mass of solid carbon obtained relative to the total mass of the feedstock (excluding natural gas for the combustion chamber in fig. 5) injected into the carbon black reactor, and is in units of [ kg C/kg feedstock ]. Y is equal to the total mass rate of solid carbon produced in the reactor divided by the total mass rate of feedstock and this is measured in the examples herein by measuring the input rates of feedstock, burner fuel and all oxidants and the composition of the tail gas produced.

Carbon content: the carbon content [ C ] is the mass average carbon content of all carbon black feedstock introduced into the reactor in kg of C/kg of feedstock and is equal to the total mass rate of carbon atoms entering the reactor via the feedstock divided by the total mass rate of feedstock. This value is calculated from the measured rates of decant oil and ethylene feed and the measured elemental composition of the feed.

Dimensionless (dimensionless) yield: the carbon-free yield Y/[ C ] is the above yield divided by the carbon content. It represents the fraction of the maximum possible yield obtained. For example, if Y/[ C ] =0.5, this means that 1/2 of the feed carbon entering the reactor is converted to solid carbon. The remainder disappeared as a vapor phase species.

Toluene extract, I ₂, STSA, OAN and COAN

OAN and COAN were analyzed on dry pellets and followed the ASTM standards described above. The I ₂ values and STSA were analyzed on the dried pellets by the ASTM methods described above.

Reactor configuration and operation

In an example, decant oil was used as the first carbon black feedstock (table 5), and ethylene gas was used as the low yield carbon black feedstock, or as the gaseous carbon black feedstock.

As shown in fig. 5, natural gas and hot air are combined in a combustion chamber using a carbon black furnace process to provide a hot combustion gas stream. The combusted gas is fuel-lean (rich in oxidant) and the equivalence ratio Φ _p is typically between 0.32 and 0.8. The combustion chamber was refractory-lined and its inner diameter is given in table 3.

In some embodiments, as shown in fig. 5, a portion of the feedstock is introduced using a center tube 73. The tube is placed approximately on the centerline of the throat and horizontally. The tube had an outer diameter of 5.4 cm. When the feedstock passing through the tube is a liquid decant oil, a full cone atomizer, or a pressure atomizer having six evenly spaced orifices perpendicular to the long axis of the center tube, is used.

When the feedstock in the center tube is a low carbon black feedstock ethylene, a gas injector 77 as shown in FIG. 5 is used, the dimensions of which are shown in the table of the examples. The gas injector (fig. 6A, showing one hole 610 of all three holes radially evenly spaced around the tip) or 6B (coaxial gas injector with one hole 611) is mounted on the end of the center tube. When no raw material is injected in this way, the central tube is removed.

The combustion gases from the combustion chamber are then forced to constrict, with the raw material introduced in the central tube (see fig. 5), if used, into a narrower throat (76 in fig. 5). At the throat, 3 gas injectors evenly spaced around the inner circumference of the throat were used to inject the low carbon black feedstock ethylene. The injector is a straight metal tube having an inner diameter of approximately 2 cm. As shown in fig. 5, these injectors are placed perpendicular to the flow direction.

The throat is connected to a refractory lined reactor chamber. The reactor chamber provides residence time for the feedstock to complete its pyrolysis into carbon black particles. At a distance L _{Quenching of} downstream of the injection plane shown in fig. 5, water jets are used to quench, which is typical for the carbon black furnace process. Downstream of the quench, a filter is used to separate carbon black particles from the tail gas stream. The soot at the filter was sampled for I ₂ absorption and toluene extract (S20). The carbon black was then pelletized and dried for measurement of STSA, OAN and COAN.

The filtered off-gas was sampled and its composition and yield were determined for each condition.

Size of the device	Description of the invention	Unit (B)	Value of
				D_Chamber	Diameter of combustion chamber	cm	20.3
D_{Throat part}	Diameter of throat	cm	11.4
				D_{reactor for producing a catalyst}	Diameter of reactor	cm	Between 68.6 and 91.4
L_Pipe	As given in the examples
				L_{Quenching of}	As given in the examples

TABLE 3 size of the reactors shown in FIG. 5

The natural gas supplied to the combustor in fig. 5 had a measured average composition as shown in table 4 for the examples. The components were measured by gas chromatography.

Component (A)		Mol%
			Nitrogen gas	％	2.97
Oxygen gas	％	0.00
			Carbon dioxide	％	0.06
Methane	％	92.2
			Ethane (ethane)	％	4.40
Propane	％	0.32
			Isobutane	％	0.01
N-butane	％	0.01
			Isopentane	％	0.00
N-pentane	％	0.00
			Hexane	％	0.00
Hydrogen gas	％	0.00
			Ethylene	％	0.00

TABLE 4 Natural gas average composition of experimental data

The ethylene used in the examples was 99% pure ethylene (by weight) and was not analyzed further.

The liquid decant oil in these examples was feedstock G in table 2 and had the properties listed therein and those given in table 5 below.

Method of	Properties of (C)	Unit (B)	Value of
				ASTM D-4052	Specific gravity	Without any means for	1.0978
ASTM D-5291-02	Carbon weight percent	％	90.32
				ASTM D-5291-02	Hydrogen weight%	％	.63
IP-336	Sulfur wt%	％	1.36
				ASTM D-3228	Nitrogen weight%	％	0.19
ASTM D-240	HHV	MJ/kg	40.64

TABLE 5 decant oil feedstock Properties

Results

Tables 6-9 present examples of carbon black production in the furnace process of fig. 5. Examples 1-5 and 11-13 show what happens when the low carbon black feedstock ethylene alone is used in the furnace, some ethylene is staged either in the throat, in the center tube, or in the center tube, with the remainder being subsequently injected in the throat. Examples 6-10 and 14-18 demonstrate the benefits of the present invention by comparison to ethylene alone. In the present invention, a minority of the total feedstock is the first carbon black feedstock injected via the center tube, with the low-yield carbon black feedstock ethylene injected into the throat.

As shown in the results, the use of low yielding carbon black feedstock alone resulted in poor yields for a given surface area (fig. 7-8), and the structural capability (as shown by OAN or COAN) was too low to match most ASTM carbon black grades (fig. 9-10). Without wishing to be bound by theory, these results may be attributed, at least in part, to the low aromatic content of the low-yielding carbon black feedstock relative to the first carbon black feedstock.

The present invention achieves some benefits as shown at least in part by the embodiments herein. First, the dimensionless yield is greatly improved when practicing the present invention as compared to using a low yield carbon black feedstock alone. Second, the ability to reach high structures is greatly increased using the method of the present invention. The fractionation of the low yielding carbon black feedstock itself (used in stages) (examples 4 and 5) did not realize these benefits.

		Example 1	Example 2	Example 3	Example 4	Example 5

Air velocity to combustor	Nm³/h	1613	1411	1409	1410	1408
							Air temperature	℃	498	499	500	498	499
Natural gas velocity	Nm³/h	74	64	65	65	65
							Natural gas temperature	℃	15	15	15	15	15

							Central tube injector type	Name of the name	Without any means for	Coaxial with each other	Coaxial with each other	Radial direction	Radial direction

							Ethylene rate to throat injector	kg/h	335	0	0	196	152
Ethylene Rate to center tube	kg/h	0	303	284	108	154
							Ethylene temperature	℃	60	60	60	60	60

							Decant oil Rate to center tube	kg/h	0	0	0	0	0
Decant oil temperature	℃

Raw material fraction to the central tube	Fraction (fr)	0.00	1.00	1.00	0.35	0.50
							Center tube position L _Pipe	m			0.76	0.48	0.48
Quench Length L _{Quenching of}	m	14.3	14.3	17.4	17.4	17.4

F_P	-	0.44	0.43	0.45	0.45	0.45
							F_O	-	2.81	2.89	2.74	2.91	2.93

							Carbon yield	kg/kg	0.149	0.203	0.174	0.219	0.213
Mass average carbon content	kg/kg	0.856	0.856	0.856	0.856	0.856
							Yield in dimensionless form		0.175	0.237	0.203	0.256	0.249

							STSA surface area	m²/g	32.3	21.8	28.8	27.7	29.8
12 Absorption of	g/100g	33.6	26.9	25.6	28.4	31.4
							OAN	ml/100g	34.9		39.3		39.1
COAN	ml/100g	32.5		35.8

TABLE 6 examples of carbon blacks produced with ethylene alone, phi _p -0.45

		Example 6	Example 7	Example 8	Example 9	Example 10

Air velocity to combustor	Nm³/h	1409	1411	1409	1408	1410
							Air temperature	℃	501	500	499	500	497
Natural gas velocity	Nm³/h	65	65	67	65	64
							Natural gas temperature	℃	15	15	15	15	15

							Central tube injector type	Name of the name	Full cone sprayer	Full cone sprayer	Pressure sprayer	Full cone sprayer	Full cone sprayer

							Ethylene rate to throat injector	kg/h	312	328	225	199	228
Ethylene Rate to center tube	kg/h	0	0	0	0	0
							Ethylene temperature	℃	60	60	60	60	60

							Decant oil Rate to center tube	kg/h	98	102	155	136	155
Decant oil temperature	℃	154	161	167	160	170

Raw material fraction to the central tube	Fraction(s)	0.24	0.24	0.41	0.41	0.40
							Center tube position L _Pipe	m	0.66	0.66	0.76	0.66	0.66
Quench Length L _{Quenching of}	m	17.4	17.4	17.4	17.4	17.4

F_P	-	0.44	0.44	0.46	0.44	0.44
							F_o	-	3.66	3.82	3.39	3.03	3.39

							Carbon yield	kg/kg	0.410	0.433	0.391	0.332	0.407
Mass average carbon content	kg/kg	0.867	0.867	0.875	0.875	0.875
							Yield in dimensionless form		0.472	0.499	0.447	0.379	0.465

							STSA surface area	m²/g	36.3	35.5	64.9	77.9	57.5
I2 absorption	g/100g	39.8	40.0	66.6	81.2	63.7
							OAN	ml/100g	109	110	158	155	123
COAN	ml/100g	75.3		98.7	107.5	89.3

TABLE 7 carbon black production wherein decant oil is introduced into the center tube wherein the majority of the feedstock is introduced at the throat as shown in FIG. 5

		Example 11	Example 12	Example 13

Air velocity to combustor	Nm³/h	1407	1408	1411
					Air temperature	℃	501	501	504
Natural gas velocity	Nm³/h	111	112	112
					Natural gas temperature	℃	15	15	15

					Central tube injector type	Name of the name	Without any means for	Without any means for	Coaxial with each other

					Ethylene rate to throat injector	kg/h	311	276	0
Ethylene Rate to center tube	kg/h	0	0	311
					Ethylene temperature	℃	60	60	60

					Decant oil Rate to center tube	kg/h	0	0	0
Decant oil temperature	℃

Raw material fraction to the central tube	Fraction(s)	0.00	0.00	1.00
					Center tube position L _Pipe	m			0.76
Quench Length L _{Quenching of}	m	14.3	14.3	14.3

F_P	-	0.76	0.77	0.76
					F_o	-	3.28	3.01	3.27

					Carbon yield	kg/kg	0.373	0.296	0.416
Mass average carbon content	kg/kg	0.856	0.856	0.856
					Yield in dimensionless form		0.436	0.346	0.486

					STSA surface area	m²/g		32.1	16.9
I2 absorption	g/100g	21.8	31.1	14.6
					OAN	ml/100g	27	40	45
COAN	ml/100g\|		35.7

TABLE 8 examples of carbon blacks produced with ethylene alone, phi _p -0.75

		Example 14	Example 15	Example 16	Example 17	Example 18

Air velocity to combustor	Nm³/h	1410	1410	1408	1411	1402
							Air temperature	℃	500	500	504	498	496
Natural gas velocity	Nm³/h	112	112	111	111	111
							Natural gas temperature	℃	15	15	15	15	15

							Central tube injector type	Name of the name	Full cone sprayer	Full cone sprayer	Full cone sprayer	Full cone sprayer	Full cone sprayer

							Ethylene rate to throat injector	kg/h	174	171	199	218	258
Ethylene Rate to center tube	kg/h	0	0	0	0	0
							Ethylene temperature	℃	60	60	60	60	60

							Decant oil Rate to center tube	kg/h	121	118	140	67	81
Decant oil temperature	℃	156	156	162	127	140

Raw material fraction to the central tube	Fraction(s)	0.41	0.41	0.41	0.23	0.24
							Center tube position L tube	m	0.66	0.66	0.66	0.66	0.66
Quench Length Lquench	m	17.4	17.4	17.4	17.4	17.4

F_P	-	0.77	0.77	0.76	0.75	0.76
							F_O	-	3.04	2.99	3.37	3.00	3.44

							Carbon yield	kg/kg	0.404	0.388	0.464	0.347	0.445
Mass average carbon content	kg/kg	0.876	0.875	0.876	0.867	0.868
							Yield in dimensionless form		0.462	0.444	0.530	0.400	0.513

							STSA surface area	m²/g	66.9	69.2	57.8	58.5	43.3
I2 absorption	g/100g	76.9	76.6	64.3	66.5	49.7
							OAN	ml/100g	167	155	166	121	128
COAN	ml/100g	103.9	100.5	101.0	93.3	85.5

TABLE 9 carbon black production wherein decant oil is introduced into the center tube wherein the majority of the feedstock is introduced at the throat as shown in FIG. 5

Improvement of yield

FIG. 7 plots the dimensionless yields versus surface area obtained from examples 1-5 and 6-10. The numerical labels on the data points refer to the example numbers in tables 6-9. In examples 1-5, ethylene was the only feedstock used. In example 1, ethylene was injected only into the throat. In examples 2 and 3, ethylene was injected using only the center tube, using a coaxial injector (fig. 6B). In examples 4 and 5, a portion of the ethylene feedstock was fractionated (used in stages, staged) in the central tube (35 and 50 mass%) and the remainder was injected using the throat.

Examples 6-10 in the figures show the effect of the invention when compared to examples 1-5. In examples 6-10, a portion of the feedstock (25 or 40 mass%) was decant oil, injected through a center tube, as shown in table 7. The dimensionless yields of these examples are much higher than those achieved with only low yield carbon black feedstock. Specifically, examples 1, 3, 4, and 5 in fig. 7 are compared with examples 6 and 7. The use of a relatively small amount (25%) of the first carbon black feedstock greatly increases the yield obtained over a given surface area range of 30 to 35m ²/g STSA.

In general, the dimensionless yield in the carbon black furnace process decreases with increasing surface area, with other conditions remaining constant. This is because higher surface area requires higher temperatures, resulting in more oxidation and less solid carbon yield. Thus, the plot of dimensionless yield versus surface area will roughly give a tendency to decrease with increasing surface area. This effect is highlighted by the ellipse in fig. 7. The groupings of carbon blacks produced with the present invention (examples 6-10) are on trend lines with much higher yields than those made with ethylene alone (examples 1-5).

It was also noted that fractionation (staged use) of the ethylene feedstock alone (examples 4 and 5) did not have much effect on improving the yield obtained at a given surface area. In the first classification (staged use) it appears that a first carbon black feedstock or a material of high aromatic content is required to produce the effect.

Tables 8 and 9 present a similar set of embodiments in which Φ _p has a higher value. The results are plotted in fig. 8. Examples 11-12 illustrate operation without aspects of the invention because ethylene was injected alone into the throat or into the center tube; examples 14-18 demonstrate the benefits of the present invention in that a small amount of decant oil is fed via a central tube. Again, as in fig. 7, the present invention greatly increases the yield that can be achieved at a given surface area, and the ranking remains independent of Φ _p. Again, the groupings of carbon blacks produced with the present invention (examples 14-18) are on a trend line with much higher yields than those made with ethylene alone (examples 11-12).

Without being bound by a particular theory, it is hypothesized that the production of seed particles from the first carbon black feedstock introduced in the first classification (staged use) is either not important or at least not the only factor of the present invention that produces the yield increasing effect. For examples 6 and 7, Φ _I had a value of <1.6, indicating that very few carbon black particles were produced from the oil in the center tube; nevertheless, yield benefits are realized. Thus, the effect may be due, at least in part, to the aromatic content of the decant oil.

Improvements in structure at fixed surface area

A second benefit of the present invention is that it provides a significant increase in the structure that can be achieved at a given surface area, as shown in fig. 9. In this figure, the numerical labels on the data points refer to the example numbers in tables 6-9; the "N" designation on the open diamond points refers to the ASTM grade requirement for the particle structure at a given surface area. All of the examples shown here do not use alkali metal additives and therefore they represent the maximum achievable structure of the operating configuration. As can be seen, the low aromatic-deficient carbon black feedstock alone (examples 1,3 and 5) produced very low structural grade carbon blacks. The use of the present invention results in a much higher maximum structure (examples 6-10).

It is also noted that fractionation (staged use) of the ethylene feedstock alone has little effect on improving the structure achievable with low yield carbon black feedstock, as shown in example 3. In contrast, it appears that the aromatic-rich or first carbon black feedstock must be injected in a first stage (staged use).

Included in fig. 9 are points (open diamonds) representing typical structures of common ASTM listed carbon black grades. This helps illustrate how the present invention can use feedstocks that are not themselves capable of producing conventional carbon black grades, and provides a method for producing these grades using such feedstocks.

Likewise, fig. 10 shows the structure versus surface area from tables 8 and 9. Again, the present invention shows that by injecting an aromatic-rich feedstock upstream of a low-yield carbon black feedstock, the structure and surface area required for normal carbon black grades can be obtained, whereas the use of a low-yield carbon black feedstock alone is not possible in a normal carbon black furnace process.

Examples 19-26 in tables 10A and 10B, and graphs based thereon, illustrate examples in which the low-yielding carbon black feedstock is heavy tire pyrolysis oil or HTPO. HTPO is recycled oil produced by pyrolysis of used tire fragments. The oil is then distilled to produce a "heavy" or higher specific gravity oil fraction. HTPO used in these examples had the properties shown in table 11; the conventional feedstock for these examples is also shown as decant oil.

TABLE 10A

TABLE 10B

Method of	Properties of (C)	Unit (B)	Decant oil	Heavy TPO	Distilled corn oil
						ASTM D-4052	Specific gravity	Without any means for	1.07	0.96	0.92
	Atomic H: C	Without any means for	1.04	1.40	1.46
							BMCI	Without any means for	137	90	55*

						ASTM D-5291-02	Carbon weight percent	％	90.8	88.3	87.9
ASTM D-5291-02	Hydrogen weight%	％	7.9	10.4	10.8
						IP-336	Sulfur wt%	％	0.62	0.83	0.04
ASTM D-3228	Nitrogen weight%	％	0.25	0.46	0.08
						ASTM D-240	HHV	MJ/kg	40.4	43.1	39.5

* Estimation of average boiling point from corn oil at 375℃

TABLE 11

The reactor configurations of examples 19-26 are shown in FIG. 5. The critical dimensions of this configuration are shown in table 12. In these embodiments, a portion of the total feedstock (decant oil or blend of decant oil and HTPO) is sometimes injected into the center tube 73 using the injector shown in table 12. The balance of the total feedstock is injected into the throat 76 shown in fig. 5. The throat injectors are a set of 4 small tubes of 0.7 to 1.5mm diameter, evenly spaced around the circumference of the throat, mounted so that they point perpendicular to the cross flow. The size of the throat injectors is selected so that the liquid feed will sufficiently penetrate into the cross flow of the throat.

Size of the device	Description of the invention	Unit (B)	Value of
				D_Chamber	Diameter of combustion chamber	cm	20.3
D_{Throat part}	Diameter of throat	cm	11.4
				D_{reactor for producing a catalyst}	Diameter of reactor	cm	Between 22.9 and 91.4
L_Pipe	As given in the examples
				L_{Quenching of}	As given in the examples

Table 12

As shown in fig. 11, the structure measured by OAN is lower when pure HTPO is used in a single injection site (e.g., examples 19 and 20). In examples 21 and 22, a blend of 30% decant oil and 70% htpo was used in the throat and the structure increased. In examples 23 and 24, the same blend was used, except that 30% of the total feed was injected into the center tube and the remainder was injected at the throat. In examples 25 and 26, decant oil was injected into the center tube as pure feed and HTPO was injected into the throat as pure feed such that decant oil accounted for 30% and HTPO accounted for 70% of the total feed injected. It is this process in which the first carbon black feedstock is the conventional feedstock and the low-yielding feedstock is injected downstream that produces the greatest structural capacity.

Examples 27-28 in table 13 show examples in which the configuration given in fig. 4B, for example, was used. Table 14 gives the dimensions of the reactors used in these examples. Fig. 12 plots these embodiments along with embodiments 21 and 22.

TABLE 13

Size of the device	Description of the invention	Unit (B)	Value of
				D_Chamber55	Diameter of combustion chamber	cm	20.3
D_{Throat part}64	First throat diameter	cm	11.4
				D_{Part of the}58	Diameter of the first reactor chamber	cm	16
L_{Part of the}66	Length of first reactor chamber	cm	61
				D_{Throat part}65	Second throat diameter	cm	16
L_{Quenching of}67	As given in the examples

TABLE 14 numbering of size columns see FIG. 4B

All examples in fig. 12 used a total feed mixture of 30% decant oil and 70% htpo. When this mixture is injected in a single throat with the configuration in fig. 5, a relatively low structure is produced (examples 21 and 22). Although this low structure is partially the result of the relatively high basic additives relative to examples 27 and 28, examples 21 and 22 will be the lowest structures even without the use of basic additives. When the same mixture was injected into both throat locations, a higher structure was obtained (example 28). However, when all of the first feedstock or conventional feedstock is injected into the first throat and low-yielding feedstock is used only in the second throat, then a higher structure is achieved for a given surface area (example 27). The dashed line on the data points indicates only a secondary line (guide) whose slope matches the slope between example 22 and example 21.

Examples 29-33 in Table 15 show examples when the low yielding feedstock is vegetable oil, in this case distilled corn oil. Table 11 gives the properties of the vegetable oil used in the experiment. The reactor configuration for these examples is shown in fig. 4B, with dimensions as shown in table 12.

TABLE 15

Fig. 13 illustrates the ability of an exemplary embodiment to improve the structural capability of a weak (weak) feed. All of these examples used 30% decant oil and 70% distilled corn oil as carbon black feedstock. In examples 29 and 30, the two feeds were blended directly and injected into a single throat in the reactor. This results in a low structure, with OAN less than 90ml/100g. When two throats were used in example 31, but the raw materials were directly blended, the structure was moderately improved but still lower.

However, in the exemplary embodiment wherein all of the decant oil enters only the first throat, the structure is greatly increased, as shown in examples 32 and 33. To this end, a blend of 50% decant oil and 50% corn oil was injected into the first throat and 100% corn oil was injected into the second throat. The total raw material usage in these examples was the same as in examples 29-33: 30% of the total feedstock used was decant oil and 70% was distilled corn oil.

As shown in fig. 14, use of the embodiments provided herein also improves the achievable yield at a given surface area. Blending 30% decant oil and 70% corn oil directly into a single throat yields low yields (examples 29 and 30), while using a double throat only slightly improves this (example 31). However, when all of the decant oil was injected into only the first throat (50% of the decant oil and 50% of the corn oil in the first throat, 100% of the corn oil in the second throat), the dimensionless yield was significantly improved (examples 32 and 33). The dashed lines in fig. 14 represent the slope of yield versus surface area observed with examples 29 and 30; this negative slope is typical for furnace carbon black processes.

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

1. a method of producing carbon black comprising:

introducing the heated gas stream into a furnace carbon black reactor;

combining at least one (batch) of a first carbon black feedstock with the heated gas stream to form a reaction stream;

Combining at least one (batch) low-yield carbon black feedstock downstream into the reaction stream present to form carbon black, wherein the at least one (batch) low-yield carbon black feedstock comprises at least 60 wt% of the total feedstock; and

Recovering carbon black in the reaction stream, wherein the first carbon black feedstock is liquid at the temperature and pressure within the chamber and has the following properties:

Mineral office association index (BMCI) no less than 100,

-H: C atomic ratio is not more than 1.23, and

-Specific gravity >1.02;

and wherein the low yielding carbon black feedstock has at least one of the following properties:

mineral office association index (BMCI) <100, or

H: C atomic ratio >1.23, or

Specific gravity of 1.02 or less

Is a gas at the temperature and pressure within the chamber.

2. The method of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock is at least one of:

a) The bureau association index (BMCI) <95, or

B) Said gas at the temperature and pressure in the chamber, or

C) The H: C atomic ratio is >1.3, or

D) The specific gravity is less than or equal to 1.0.

3. Wherein the low yield carbon black feedstock is ethylene.

4. The method of any preceding or following embodiments/features/aspects, wherein the low-yielding carbon black feedstock is natural gas.

5. The method of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock has the specific gravity of less than 1.02.

6. The method of any preceding or following embodiment/feature/aspect, wherein the low-yielding carbon black feedstock is a tire pyrolysis oil, or an oil derived (obtained from) distillation or fractionation of a tire pyrolysis oil.

7. The method of any preceding or following embodiment/feature/aspect, wherein the low-yield carbon black feedstock is a feedstock other than coal tar liquid, oil refinery liquid, or ethylene cracker residue, or phenol cracker residue.

8. The method of any preceding or following embodiment/feature/aspect, wherein the low yield carbon black feedstock is a plastic pyrolysis oil, a high H: C decant oil, a renewable feedstock, a feedstock of biological origin, or other byproducts of a refining process, or any combination thereof.

9. The method of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock comprises at least one of: vegetable or other plant derived (vegetable or other plant derived) oils, bioethanol of biological origin, plant or animal derived waxes or resins, oils made (boiled) from animal fat, algae oils (algae oils), oils made (provided) by pyrolysis of sewage sludge or agricultural waste, by-product liquids from processing of biogenic materials, liquids produced by hydrothermal liquefaction of biological materials, crude tall oil, tall oil rosin, tall oil pitch, or tall oil fatty acids, oils produced from recycled materials, oils derived (from) pyrolysis of low quality, off-grade or scrap tires, oils derived (from) pyrolysis of waste or recycled plastic or rubber products, oils derived (from) pyrolysis of municipal solid waste, or oils derived (from) pyrolysis of biomass, or any combination thereof.

10. The method of any preceding or following embodiments/features/aspects, wherein the at least first carbon black feedstock comprises one or more of decant oil, slurry oil, coal tar derivatives, ethylene cracker residue, or phenol cracker residue.

11. The method of any preceding or following embodiment/feature/aspect, wherein the first carbon black feedstock comprises a fraction obtained from distillation of a tire pyrolysis oil.

12. The process of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock is 65-90 wt% of the total feedstock input in the process.

13. The process of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock is 70-90 wt% of the total feedstock input in the process.

14. The method of any preceding or following embodiment/feature/aspect, wherein the furnace carbon black reactor has a combustion chamber, and a throat downstream of the combustion chamber, and a reaction chamber downstream of the throat, and a quenching zone downstream of the reaction chamber, and wherein the first carbon black feedstock is injected into the combustion chamber of the furnace carbon black reactor, and the low yield carbon black feedstock is injected into the throat.

15. The method of any preceding or following embodiment/feature/aspect, wherein the furnace carbon black reactor has a combustion chamber, and a throat downstream of the combustion chamber, and a reaction chamber downstream of the throat, and a quench zone downstream of the reaction chamber, and wherein the first carbon black feedstock is injected into the throat, and the low-yielding carbon black feedstock is injected after the throat.

16. The method of any preceding or following embodiments/features/aspects, wherein the furnace carbon black reactor comprises a second throat downstream of the combustion chamber and before the quenching zone, and the low-yielding carbon black feedstock is injected into the second throat.

17. The method of any preceding or following embodiment/feature/aspect, wherein the at least one (batch) first carbon black feedstock is introduced into the furnace carbon black reactor at least one location upstream of the location of injection of the at least one (batch) low yield carbon black feedstock and at least one separate location downstream of the location of the at least one (batch) low yield carbon black feedstock.

18. The method of any preceding or following embodiment/feature/aspect, wherein the amount of the first carbon black feedstock introduced prior to the location of injection of the at least one (batch of) low yielding feedstock is greater than 50% of the total amount of the first carbon black feedstock.

19. The method of any preceding or following embodiments/features/aspects, wherein the at least one (batch of) low yield carbon black feedstock is introduced into the furnace carbon black reactor at least two separate locations, wherein one of the separate locations is downstream of the other.

20. The method of any preceding or following embodiment/feature/aspect, wherein the at least one (batch) first carbon black feedstock is a blend comprising less than 50wt% non-high yielding carbon black feedstock based on the total weight of the first carbon black feedstock.

21. The method of any preceding or following embodiments/features/aspects, wherein the at least one (batch) first carbon black feedstock comprises from 95 wt% to 100 wt% of a high yield carbon black feedstock based on the total weight of the first carbon black feedstock.

22. The method of any preceding or following embodiments/features/aspects, wherein the at least one (batch) low-yield carbon black feedstock is a blend comprising less than 50 weight percent of high-yield carbon black feedstock based on the total weight of the low-yield carbon black feedstock.

23. The method of any preceding or following embodiment/feature/aspect, wherein the low yielding carbon black feedstock has the BMCI of < 100.

24. The method of any preceding or following embodiment/feature/aspect, wherein the low yielding carbon black feedstock has the H: C atomic ratio > 1.23.

25. The method of any preceding or following embodiments/features/aspects, wherein the low yielding carbon black feedstock is the gas at a temperature and pressure within the chamber.

26. The method of any preceding or following embodiments/features/aspects, wherein the carbon black recovered is N110、N121、N220、N231、N234、N299、N326、N330、N339、N347、N351、N358、N375、N539、N550、N650、N660、N683、N762、N765、N774、N787、 or N990 grade carbon black.

24. Carbon black resulting from any of the foregoing or following embodiments/features/aspects.

The invention may include any combination of the various features or embodiments above and/or below as set forth in any sentence and/or paragraph herein. Any combination of features disclosed herein is considered as part of the invention and is not intended to be limiting as to the combinable features.

Applicants specifically incorporate the entire contents of all cited references into this disclosure. Furthermore, when an equivalent, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. The scope of the invention is not intended to be limited to the specific values recited when defining the scope.

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

Claims

1. A method of producing carbon black comprising:

introducing the heated gas stream into a furnace carbon black reactor;

Combining at least one first carbon black feedstock with the heated gas stream to form a reaction stream;

Combining at least one low yield carbon black feedstock downstream into the reaction stream present to form carbon black, wherein the at least one low yield carbon black feedstock comprises at least 60 weight percent of the total feedstock; and

Mineral office association index (BMCI) no less than 100,

-H: C atomic ratio is not more than 1.23, and

-Specific gravity >1.02;

mineral office association index (BMCI) <100, or

H: C atomic ratio >1.23, or

Specific gravity of 1.02 or less

Is a gas at the temperature and pressure within the chamber.

2. The method of claim 1, wherein the low yield carbon black feedstock is at least one of:

a) The bureau association index (BMCI) <95, or

B) Said gas at the temperature and pressure in the chamber, or

C) The H: C atomic ratio is >1.3, or

D) The specific gravity is less than or equal to 1.0.

3. The method of claim 1, wherein the low-yielding carbon black feedstock is ethylene.

4. The method of claim 1, wherein the low-yielding carbon black feedstock is natural gas.

5. The method of claim 1, wherein the low-yielding carbon black feedstock has the specific gravity of less than 1.02.

6. The method of claim 1, wherein the low-yielding carbon black feedstock is a tire pyrolysis oil, or an oil derived from distillation or fractionation of a tire pyrolysis oil.

7. The method of claim 1, wherein the low-yield carbon black feedstock is a feedstock other than coal tar liquid, oil refinery liquid, or ethylene cracker residue, or phenol cracker residue.

8. The method of claim 1, wherein the low yield carbon black feedstock is a plastic pyrolysis oil, a high H: C decant oil, a renewable feedstock, a feedstock of biological origin, or other byproducts of a refining process, or any combination thereof.

9. The method of claim 8, wherein the low yield carbon black feedstock comprises at least one of: vegetable or other plant derived oils, ethanol of biological origin, plant or animal derived waxes or resins, oils made from animal fats, algae oils, oils made from pyrolysis of sewage sludge or agricultural waste, by-product liquids from processing of biogenic materials, liquids produced by hydrothermal liquefaction of biological materials, crude tall oil, tall oil rosin, tall oil pitch, or tall oil fatty acids, oils produced from recycled materials, oils derived from pyrolysis of low quality, off-grade or scrapped tires, oils derived from pyrolysis of waste or recycled plastic or rubber products, oils derived from pyrolysis of municipal solid waste, or oils derived from pyrolysis of biomass, or any combination thereof.

10. The method of any of the preceding claims, wherein the at least first carbon black feedstock comprises one or more of decant oil, slurry oil, coal tar derivatives, ethylene cracker residues, or phenol cracker residues.

11. The method of any one of the preceding claims, wherein the first carbon black feedstock comprises a fraction obtained from distillation of a tire pyrolysis oil.

12. The method of claim 1, wherein the low yield carbon black feedstock is 65-90 wt% of the total feedstock input in the method.

13. The method of claim 1, wherein the low yield carbon black feedstock is 70-90 wt% of the total feedstock input in the method.

14. The method of claim 1, wherein the furnace soot reactor has a combustion chamber and a throat downstream of the combustion chamber and a reaction chamber downstream of the throat and a quenching zone downstream of the reaction chamber, and wherein the first soot feedstock is injected into the combustion chamber of the furnace soot reactor and the low-yielding soot feedstock is injected into the throat.

15. The method of claim 1, wherein the furnace soot reactor has a combustion chamber and a throat downstream of the combustion chamber and a reaction chamber downstream of the throat and a quenching zone downstream of the reaction chamber, and wherein the first soot feedstock is injected into the throat and the low-yielding soot feedstock is injected after the throat.

16. The method of claim 15, wherein the furnace carbon black reactor comprises a second throat downstream of the combustion chamber and before the quenching zone, and the low-yielding carbon black feedstock is injected into the second throat.

17. The method of claim 1, wherein the at least one first carbon black feedstock is introduced into the furnace carbon black reactor at least one location upstream of the location of injection of the at least one low yield carbon black feedstock and at least one separate location downstream of the location of the at least one low yield carbon black feedstock.

18. The method of claim 17, wherein the amount of the first carbon black feedstock introduced prior to the injection of the at least one low yielding feedstock location is greater than 50% of the total amount of the first carbon black feedstock.

19. The method of claim 1, wherein the at least one low yield carbon black feedstock is introduced into the furnace carbon black reactor at least two separate locations, one downstream of the other.

20. The method of claim 1, wherein the at least one first carbon black feedstock is a blend comprising less than 50 wt% non-high yielding carbon black feedstock based on the total weight of the first carbon black feedstock.

21. The method of claim 1, wherein the at least one first carbon black feedstock comprises from 95 wt% to 100 wt% of a high yield carbon black feedstock based on the total weight of the first carbon black feedstock.

22. The method of claim 1, wherein the at least one low yield carbon black feedstock is a blend comprising less than 50 weight percent of high yield carbon black feedstock based on the total weight of the low yield carbon black feedstock.

23. The method of claim 1, wherein the low yield carbon black feedstock has the BMCI of < 100.

24. The method of claim 1, wherein the low yield carbon black feedstock has the H to C atomic ratio > 1.23.

25. The method of claim 1, wherein the low-yielding carbon black feedstock is the gas at room temperature and pressure.

26. The method of claim 1, wherein the carbon black recovered is N110、N121、N220、N231、N234、N299、N326、N330、N339、N347、N351、N358、N375、N539、N550、N650、N660、N683、N762、N765、N774、N787、 or N990 grade carbon black.