CN113956684A - Low-carbon high-efficiency carbon black production method - Google Patents

Low-carbon high-efficiency carbon black production method Download PDF

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CN113956684A
CN113956684A CN202111294168.4A CN202111294168A CN113956684A CN 113956684 A CN113956684 A CN 113956684A CN 202111294168 A CN202111294168 A CN 202111294168A CN 113956684 A CN113956684 A CN 113956684A
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tar
carbon black
gas
oil
temperature
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郭涛
张万亮
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Yingkou Liaobin Carbon Black Co ltd
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Yingkou Liaobin Carbon Black Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/487—Separation; Recovery
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/50—Furnace black ; Preparation thereof

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Abstract

The invention belongs to the technical field of carbon black production, and particularly relates to a low-carbon high-efficiency carbon black production method which comprises the following steps: cutting fractions of the raw carbon black oil to obtain light tar, medium tar and heavy tar, and uniformly mixing the light tar and the biological tar and then carrying out hydrogen transfer treatment to obtain upgraded tar; the heavy tar is used as a carbon black production fuel, and the medium tar and the upgraded tar are further mixed for a carbonization reaction to obtain a carbonized gas-phase product and a carbonized solid-phase product; the carbonized gas phase product is used for reaction heat supply and synthesis gas raw material preparation after gas-solid separation and fine filtration; and (4) carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a high-quality carbon black product. The invention breaks through the difficult problems of raw material matching and process control when the biological tar is directly used in the carbon black production process by effectively combining multiple approaches of biological tar for upgrading and efficiency enhancement and the gradient utilization of the carbon black raw oil, and obviously reduces the process consumption and the carbon emission.

Description

Low-carbon high-efficiency carbon black production method
Technical Field
The invention belongs to the technical field of carbon black production, and particularly relates to a low-carbon high-efficiency carbon black production method.
Background
The oil furnace method carbon black production process is the most main production method for carbon black production at present, and the general process is that fuel is firstly combusted in a reaction furnace to form high-temperature combustion gas, then the raw material is atomized and sprayed into the high-temperature combustion gas, and the raw material is quickly gasified and cracked to generate the carbon black. However, in actual production, there are problems such as high raw material quality requirements, consumption of a part of raw oil by combustion, and difficulty in efficient use of exhaust gas. In recent years, with the continuous deepening and implementation of energy conservation and emission reduction and green and low-carbon development concepts, how to realize the clean production of the carbon black industry, solve the problem of environmental pollution and realize sustainable development is becoming a new direction for the development of the carbon black industry.
One solution strategy is to reduce the production cost and carbon emission by using cheap and low-carbon raw materials instead of ideal carbon black production raw materials such as anthracene oil, anticorrosive oil, ethylene tar and the like, and comprises the steps of blending biological tar to produce carbon black, obtaining carbon black for rubber by using coal tar without adding anthracene oil, and utilizing the coal tar in a grading manner to prepare high-quality carbon black and the like (Chinese patents CN111662733A, CN103980741A and CN 106349766A). The other solution strategy is to adopt a solid heat carrier process to replace a conventional combustion gasification process to strengthen heat and mass transfer (Chinese patents CN111662733A and CN104804478A), and solve the problems that the concentration of effective components in tail gas is low and the tail gas is difficult to utilize, but simultaneously bring about new series problems of solid-solid separation of carbon black products and the solid heat carrier, recycling of the solid heat carrier and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for producing carbon black with low carbon and high efficiency, which aims to improve the technical level of producing carbon black by mixing biological tar with carbon black raw oil, breaks through the difficult problems of raw material matching and process regulation of the process of directly using the biological tar in the carbon black production process by effectively combining multiple approaches of quality improvement and efficiency enhancement of the biological tar with the gradient utilization of the carbon black raw oil, overcomes the problem of high-efficiency utilization of non-ideal carbon black production raw materials, realizes a new process for producing high-quality carbon black by using low-price low-quality raw materials, obviously reduces the process consumption and carbon emission, and has good application prospect.
The invention is realized in such a way, and provides a method for producing carbon black with low carbon and high efficiency, which comprises the following steps:
1) cutting fractions of the raw carbon black oil to obtain light tar, medium tar and heavy tar, wherein the light tar and the biological tar are uniformly mixed and then subjected to hydrogen transfer treatment to obtain upgraded tar;
2) using the heavy tar in the step 1) as a carbon black production fuel, further mixing the medium tar and the upgraded tar in the step 1) for a carbonization reaction to obtain a carbonized gas-phase product and a carbonized solid-phase product;
3) performing gas-solid separation and fine filtration on the carbonized gas-phase product obtained in the step 2) and then using the carbonized gas-phase product for reaction heat supply and synthesis gas raw material preparation;
4) carrying out gas-solid separation on the carbonized solid-phase product obtained in the step 2) for multiple times to obtain a high-quality carbon black product;
preferably, the raw material oil of carbon black in the step 1) is one or more of clarified oil, coal tar, ethylene tar, anthracene oil, carbon black oil and creosote oil;
the biological tar is liquid heavy oil obtained by thermal processing of biomass, and comprises one or more of pyrolysis tar formed in a pyrolysis process, liquefied heavy oil formed in a liquefaction process and cracking tar formed in a catalytic conversion process;
preferably, the pyrolysis tar is one or more of forest tar, straw tar, microalgae tar, seaweed tar and shell tar: the liquefied heavy oil is one or more of acidized heavy oil, alkaline liquefied heavy oil, ionic liquid liquefied heavy oil and critical water liquefied heavy oil: the cracking tar is one or more of catalytic cracking tar, catalytic reforming tar, esterification tar and etherification tar.
More preferably, in the step 1), the cutting of the carbon black raw oil comprises atmospheric distillation, vacuum distillation and atmospheric and vacuum distillation, and specifically comprises the following steps:
when atmospheric distillation is adopted, the carbon black raw oil is subjected to atmospheric distillation at the temperature of 120-450 ℃, light oil fraction at the temperature of 120-220 ℃ is used as light tar for hydrogen transfer treatment of biological tar, medium oil fraction at the temperature of 220-400 ℃ is used as raw oil for carbon black production, and heavy oil fraction at the temperature of 400-450 ℃ is directly mixed with the biological tar to be used as carbon black for producing fuel oil;
when the reduced pressure distillation is adopted, the carbon black raw oil is subjected to reduced pressure distillation under the conditions that the temperature is 80-330 ℃ and the pressure is 10-40 kPa, light oil fraction at 80-180 ℃ is used as light tar for hydrogen transfer treatment of biological tar, medium oil fraction at 180-270 ℃ is used as carbon black production raw oil, and heavy oil fraction at 270-330 ℃ is directly mixed with the biological tar to be used as carbon black production fuel oil;
when the atmospheric and vacuum distillation is adopted, the carbon black raw oil is subjected to atmospheric distillation at the temperature of 110-120 ℃ to remove water, then the vacuum distillation is performed at the temperature of 120-330 ℃ and under the pressure of 10-40 kPa, the light oil fraction at the temperature of 120-180 ℃ is used as light tar for hydrogen transfer treatment of biological tar, the middle oil fraction at the temperature of 180-270 ℃ is used as raw oil for carbon black production, and the heavy oil fraction at the temperature of 270-330 ℃ is directly mixed with the biological tar to be used as fuel oil for carbon black production.
Further preferably, the content of the light tar, the medium tar and the heavy tar in the total tar in the step 1) is respectively 10-20%, 70-80% and 5-10%;
the upgraded tar of the step 1) is obtained by hydrogen transfer treatment of light tar and biological tar, wherein the hydrogen transfer treatment process comprises the following steps: firstly, fully and uniformly mixing light tar and biological tar according to the mass ratio of 1: 0.1-1, carrying out hydrogen transfer treatment for 1-4 hours at the temperature of 250-400 ℃ and under the pressure of 1-l 0MPa, and carrying out appropriate deoxidation on the biological tar, wherein the deoxidation rate of the biological tar is 20-60%, so that upgraded tar with better stability and higher molecular weight is obtained, and the oxygen content of the upgraded tar is 1-10%; then, mechanically filtering the upgraded tar, wherein the mechanical filtration is one of centrifugal filtration, vacuum filtration, plate-frame filtration, sedimentation filtration and cyclone filtration; and carrying out two-stage oil-water separation on the filtered upgraded tar at the temperature of 50-80 ℃ to obtain the processed upgraded tar.
In the step 2), the mass fraction of the upgraded tar in the mixed oil formed by the medium tar and the upgraded tar is not more than 50%, the temperature of the mixed oil for the carbonization reaction under the action of the high-temperature combustion gas is 1600-1800 ℃, and the reaction time is 0.03-0.3 s; the high-temperature combustion gas is from a combustion product of heavy tar used as a fuel for producing carbon black under the action of combustion-supporting gas;
preferably, in the step 2), the heavy tar can be introduced into the biological tar to be used as a fuel for producing carbon black, and the mass ratio of the heavy tar to the biological tar is 1: 1-10; the carbon black production fuel and combustion-supporting gas are combusted to form high-temperature combustion gas at the temperature of more than 1900 ℃ to provide heat for the carbon black production process, and the combustion-supporting gas comprises oxygen and oxygen enrichment (O)235-50% concentration), oxygen and carbon dioxide (CO)2Concentration not more than 30 percent), oxygen and water vapor mixed gas (H)2O concentration not more than 40%), etc., before combustion, the combustion-supporting gas needs to be heated to 800 ℃ or above through indirect heat exchange with the high-temperature carbonized solid-phase product.
Further preferably, in the step 3), the carbonized gas-phase product is subjected to gas-solid separation and fine filtration and then used for preheating a carbon black production raw material and a carbon black production fuel, wherein the carbon black production raw material is preheated to 150-200 ℃, and the carbon black production fuel is preheated to 120-150 ℃;
the carbonized gas-phase product can be further used for preparing a raw material of synthesis gas after gas-solid separation, fine filtration and heat exchange, and the specific process comprises the following steps: charring the gaseous product and CO2The absorbent solution is subjected to mixing reaction at the temperature of 50-80 ℃ by a concurrent flow method, the flow rate of carbonized gas phase products is 10-100L/h, and CO is2The flow rate of the absorbent solution is 1-3L/h, and CO is2The mass percentage of the absorbent solution is 10-40%, and the CO is2The absorbent comprises three types of alkali (earth) metal weak acid salts, alkali (earth) metal hydroxides and organic amines, wherein the alkali (earth) metal weak acid salts comprise carbonates, selenites, tellurites, arsenites, metavanadates, phosphates, sulfites and borates of alkali (earth) metals; alkali (earth) metal hydroxides including potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide; the organic amine includes ammonia, thiourea, urea, ethylenediamine, ethanolamine, diethanolamine, glycine, diethylenetriamine, piperazine, etc.
Preferably, in the step 3), the raw material composition of the synthesis gas mainly comprises hydrogen and carbon monoxide, and the hydrogen-carbon ratio is 1-2.
Further preferably, in the step 2), the yield of the carbon black product obtained by multiple gas-solid separation of the carbonized solid-phase product is 68-82%;
the gas-solid separation is one or more of gravity settling, centrifugal separation, filter screen separation and electrostatic adsorption; the gas-solid separator is one or more of a cyclone separator, a cloth bag filter, an electrostatic dust collector and an adsorption separator; the fine filtration is one or more of microfiltration, ultrafiltration, ultra-microfiltration and nanofiltration of a high-temperature resistant core material.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, through grading treatment and utilization of raw oil for carbon black production, the light tar with the highest hydrogen abundance is directly subjected to hydrogen transfer treatment with the biological tar, so that the biological tar is properly deoxidized to increase the stability, meanwhile, the dehydrogenation part of the light tar is subjected to polycondensation to form ideal carbon black production raw materials such as upgraded tar, and the yield and quality of carbon black products are generally improved; the heavy tar with higher heat value and the biological tar are mixed to be used as the carbon black production fuel, the consumption of carbon black production raw materials is reduced, the problem that the fuel pipeline is easy to block due to higher viscosity of the heavy tar is solved, the consumption of combustion-supporting gas is reduced due to higher oxygen content of the biological tar, and the improvement of the composition of a carbonized gas-phase product and the promotion of application are facilitated.
2. The carbonized gas-phase product of the invention is rich in hydrogen, carbon monoxide and carbon dioxide, and after heat exchange, the carbonized gas-phase product passes through mild CO2Treating the absorbent solution to obtain a synthesis gas raw material which mainly comprises hydrogen and carbon monoxide and can be used for preparing bio-based chemicals and materials; with CO2The carbon black is recovered and enriched, and the carbon emission in the carbon black production process is obviously reduced.
3. The invention fully utilizes various heat in the carbon black production process to reduce energy and material consumption, the byproduct carbonized gas phase product is used for preheating the carbon black production raw material and the carbon black production fuel, the carbonized solid phase product is used for preheating the combustion-supporting gas in the carbon black production, the whole process does not need exogenous heat supply, and the carbon black production cost is obviously reduced.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is a general process flow diagram of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
Referring to FIG. 1, there is shown a general process flow diagram of the present invention.
Examples 1,
Coal tar is used as a carbon black production raw material, normal pressure fraction cutting is carried out, light oil fraction at 140-220 ℃ is light tar MO-1, medium oil fraction at 220-380 ℃ is medium tar MO-2, and heavy oil fraction at 400-450 ℃ is heavy tar MO-3.
Examples 2,
Ethylene tar is used as a carbon black production raw material, reduced pressure fraction cutting is carried out under the condition of 10kPa, light oil fraction at 80-180 ℃ is light tar EO-1, medium oil fraction at 180-270 ℃ is medium tar EO-2, and heavy oil fraction at 270-330 ℃ is heavy tar EO-3.
Examples 3,
The method comprises the steps of taking creosote oil as a carbon black production raw material, firstly carrying out atmospheric distillation at 110-120 ℃ to remove water, then carrying out reduced pressure fraction cutting at 10kPa, wherein light oil fraction at 120-180 ℃ is light tar PO-1, middle oil fraction at 180-270 ℃ is middle tar PO-2, and heavy oil fraction at 270-330 ℃ is heavy tar PO-3.
Examples 4,
Fully and uniformly mixing light tar EO-1 and microalgae tar according to the mass ratio of 1:1, carrying out hydrogen transfer treatment for 1 hour at the temperature of 400 ℃ and under the pressure of 10MPa, wherein the deoxidation rate of the microalgae tar is 50 percent to obtain upgraded tar with the oxygen content of 8 percent, then carrying out mechanical filtration treatment and carrying out two-stage oil treatment at the temperature of 80 DEG CSeparating water to obtain the treated upgraded tar. And mixing the upgraded tar and the medium tar EO-2 according to a certain proportion to obtain the carbon black production raw material, wherein the mass fraction of the upgraded tar is 20% for later use. Mixing heavy tar EO-3 with microalgae tar according to the mass ratio of 1:1, preheating to 250 ℃, and mixing with preheated 800 ℃ oxygen and water vapor mixed gas (H)2O concentration 40%) to form high-temperature combustion gas above 1900 deg.c. Introducing the high-temperature combustion gas into a carbon black production raw material preheated to 250 ℃, carrying out carbonization reaction at 1600 ℃ for 0.3 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 68%; and introducing 25% ammonia water at 50 deg.C to remove CO2Wherein the flow rate of the carbonized gas phase product is 100L/h, and the flow rate of the ammonia water is 3L/h, so that the synthesis gas product with the hydrogen-carbon ratio of 2.0 is obtained.
Examples 5,
Fully and uniformly mixing light tar PO-1 and catalytic cracking tar according to the mass ratio of 1:0.8, carrying out hydrogen transfer treatment for 3 hours at the temperature of 400 ℃ and under the pressure of 4MPa, wherein the deoxidation rate of the catalytic cracking tar is 60 percent, thus obtaining the upgraded tar with the oxygen content of 9.8 percent, then carrying out mechanical filtration treatment and carrying out two-stage oil-water separation at the temperature of 80 ℃, thus obtaining the treated upgraded tar. And mixing the upgraded tar and the medium tar PO-2 according to a certain proportion to obtain a carbon black production raw material, wherein the mass fraction of the upgraded tar is 30% for later use. Mixing heavy tar PO-3 with catalytic cracking tar according to the mass ratio of 1:1, preheating to 250 ℃, and mixing with preheated 800 ℃ oxygen and water vapor mixed gas (H)2O concentration 10%) to form high-temperature combustion gas above 1900 deg.c. Introducing the high-temperature combustion gas into a carbon black production raw material preheated to 250 ℃, carrying out carbonization reaction at 1700 ℃ for 0.1 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 82%; the carbonized gas-phase product is introduced into potassium carbonate solution with the mass percentage of 20 percent at the temperature of 50 ℃ to remove CO2Wherein the flow rate of the carbonized gas-phase product is 100L/h,the flow rate of the potassium carbonate solution is 1L/h, and a synthesis gas product with the hydrogen-carbon ratio of 1.0 is obtained.
Examples 6,
Fully and uniformly mixing the light tar MO-1 and the forest tar according to the mass ratio of 1:0.2, carrying out hydrogen transfer treatment for 4 hours at the temperature of 250 ℃ and under the pressure of 1MPa, wherein the deoxidation rate of the forest tar is 20 percent, so as to obtain the upgraded tar with the oxygen content of 7.3 percent, then carrying out mechanical filtration treatment, and carrying out two-stage oil-water separation at the temperature of 80 ℃ so as to obtain the treated upgraded tar. Mixing the upgraded tar and the medium tar MO-2 according to a certain proportion to obtain a carbon black production raw material, wherein the mass fraction of the upgraded tar is 50% for later use. Mixing heavy tar MO-3 and forest tar according to the mass ratio of 1:10, preheating to 200 ℃, and mixing with preheated 800 ℃ oxygen and water vapor mixed gas (H)2O concentration 20%) to form high-temperature combustion gas above 1900 deg.c. Introducing the high-temperature combustion gas into a carbon black production raw material preheated to 250 ℃, carrying out carbonization reaction at 1800 ℃ for 0.03 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 80%; the carbonized gas-phase product is introduced into potassium carbonate solution with the mass percentage of 20 percent at the temperature of 50 ℃ to remove CO2Wherein the flow rate of the carbonized gas phase product is 100L/h, and the flow rate of the potassium carbonate solution is 1L/h, so that the synthesis gas product with the hydrogen-carbon ratio of 1.1 is obtained.
Example 7,
Fully and uniformly mixing the light tar MO-1 and the forest tar according to the mass ratio of 1:0.5, carrying out hydrogen transfer treatment for 2.5 hours at the temperature of 400 ℃ and under the pressure of 4MPa, wherein the deoxidation rate of the catalytic cracking tar is 60 percent, thus obtaining the upgraded tar with the oxygen content of 6.7 percent, then carrying out mechanical filtration treatment and carrying out two-stage oil-water separation at the temperature of 80 ℃, thus obtaining the treated upgraded tar. And mixing the upgraded tar and the medium tar MO-2 according to a certain proportion to obtain a carbon black production raw material, wherein the mass fraction of the upgraded tar is 40% for later use. Mixing heavy tar MO-3 and forest tar according to the mass ratio of 1:1, preheating to 250 ℃, and mixing with preheated 800 ℃ mixed gas of oxygen and water vapor (H)2O concentration 30%) medium combustionBurning to form high temperature combustion gas above 1900 deg.C. Introducing the high-temperature combustion gas into a carbon black production raw material preheated to 250 ℃, carrying out carbonization reaction at 1800 ℃ for 0.03 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 82%; the carbonized gas-phase product is introduced into potassium carbonate solution with the mass percentage of 40 percent at the temperature of 50 ℃ to remove CO2Wherein the flow rate of the carbonized gas phase product is 100L/h, and the flow rate of the potassium carbonate solution is 3L/h, and a synthesis gas product with the hydrogen-carbon ratio of 1.5 is obtained.
Comparative example 1, (carbon Black stock oil used without fractionation)
Blending coal tar and forest tar according to a certain proportion to obtain a carbon black production raw material, wherein the mass fraction of the forest tar in the blending process is 40% for later use. Preheating forest tar to 250 deg.C, and mixing with preheated 800 deg.C oxygen and water vapor (H)2O concentration of 30%) to form high-temperature combustion gas of 1900 deg.c or higher. Introducing the high-temperature combustion gas into a carbon black production raw material preheated to 250 ℃, carrying out carbonization reaction at 1800 ℃ for 0.03 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 72%; the carbonized gas-phase product is introduced into potassium carbonate solution with the mass percentage of 40 percent at the temperature of 50 ℃ to remove CO2Wherein the flow rate of the carbonized gas phase product is 100L/h, and the flow rate of the potassium carbonate solution is 3L/h, and a synthesis gas product with the hydrogen-carbon ratio of 1.5 is obtained.
Comparative example 2 (coal tar as carbon black stock oil, forest tar as carbon black fuel oil)
Preheating forest tar to 250 deg.C, and mixing with preheated 800 deg.C oxygen and water vapor (H)2O concentration of 30%) to form high-temperature combustion gas of 1900 deg.c or higher. Introducing the high-temperature combustion gas into coal tar preheated to 200 ℃, carrying out carbonization reaction at 1800 ℃ for 0.03 second to obtain a carbonized gas-phase product and a carbonized solid-phase product, and carrying out gas-solid separation on the carbonized solid-phase product for multiple times to obtain a carbon black product with the yield of 76%; the carbonized gas-phase product is then introduced into a potassium carbonate solution with the mass percentage of 40 percent at the temperature of 50 DEG CCO removal2Wherein the flow rate of the carbonized gas phase product is 100L/h, and the flow rate of the potassium carbonate solution is 3L/h, and a synthesis gas product with the hydrogen-carbon ratio of 1.2 is obtained.

Claims (9)

1. A method for producing carbon black with low carbon and high efficiency comprises the following steps:
1) cutting fractions of the raw carbon black oil to obtain light tar, medium tar and heavy tar, wherein the light tar and the biological tar are uniformly mixed and then subjected to hydrogen transfer treatment to obtain upgraded tar;
2) using the heavy tar in the step 1) as a carbon black production fuel, further mixing the medium tar and the upgraded tar in the step 1) for a carbonization reaction to obtain a carbonized gas-phase product and a carbonized solid-phase product;
3) performing gas-solid separation and fine filtration on the carbonized gas-phase product obtained in the step 2) and then using the carbonized gas-phase product for reaction heat supply and synthesis gas raw material preparation;
4) and (3) carrying out gas-solid separation on the carbonized solid-phase product obtained in the step 2) for multiple times to obtain a high-quality carbon black product.
2. The method for producing carbon black with low carbon and high efficiency according to claim 1, characterized in that in the step 1), the raw material oil of carbon black is one or more of clarified oil, coal tar, ethylene tar, anthracene oil, carbon black oil and creosote oil;
the biological tar is liquid heavy oil obtained by thermal processing of biomass, and comprises one or more of pyrolysis tar formed in a pyrolysis process, liquefied heavy oil formed in a liquefaction process and cracking tar formed in a catalytic conversion process.
3. The method for low-carbon and high-efficiency production of carbon black according to claim 2, wherein the pyrolysis tar is one or more of forest tar, straw tar, microalgae tar, seaweed tar, and nut shell tar: the liquefied heavy oil is one or more of acidized heavy oil, alkaline liquefied heavy oil, ionic liquid liquefied heavy oil and critical water liquefied heavy oil: the cracking tar is one or more of catalytic cracking tar, catalytic reforming tar, esterification tar and etherification tar.
4. The method for low-carbon and high-efficiency production of carbon black according to claim 1, wherein in the step 1), the cut of the carbon black raw oil is obtained by atmospheric distillation, reduced pressure distillation or atmospheric and reduced pressure distillation, and the method comprises the following specific steps:
when atmospheric distillation is adopted, the carbon black raw oil is subjected to atmospheric distillation at the temperature of 120-450 ℃, light oil fraction at the temperature of 120-220 ℃ is used as light tar for hydrogen transfer treatment of biological tar, medium oil fraction at the temperature of 220-400 ℃ is used as raw oil for carbon black production, and heavy oil fraction at the temperature of 400-450 ℃ is directly mixed with the biological tar to be used as carbon black for producing fuel oil;
when the reduced pressure distillation is adopted, the carbon black raw oil is subjected to reduced pressure distillation under the conditions that the temperature is 80-330 ℃ and the pressure is 10-40 kPa, light oil fraction at 80-180 ℃ is used as light tar for hydrogen transfer treatment of biological tar, medium oil fraction at 180-270 ℃ is used as carbon black production raw oil, and heavy oil fraction at 270-330 ℃ is directly mixed with the biological tar to be used as carbon black production fuel oil;
when the atmospheric and vacuum distillation is adopted, the carbon black raw oil is subjected to atmospheric distillation at the temperature of 110-120 ℃ to remove water, then the vacuum distillation is performed at the temperature of 120-330 ℃ and under the pressure of 10-40 kPa, the light oil fraction at the temperature of 120-180 ℃ is used as light tar for hydrogen transfer treatment of biological tar, the middle oil fraction at the temperature of 180-270 ℃ is used as raw oil for carbon black production, and the heavy oil fraction at the temperature of 270-330 ℃ is directly mixed with the biological tar to be used as fuel oil for carbon black production.
5. The method for producing carbon black with low carbon and high efficiency according to claim 1, characterized in that the content of light tar, medium tar and heavy tar in the total tar in the step 1) is respectively 10-20%, 70-80% and 5-10%;
the upgraded tar of the step 1) is obtained by hydrogen transfer treatment of light tar and biological tar, and the hydrogen transfer treatment process is as follows: firstly, fully and uniformly mixing light tar and biological tar according to the mass ratio of 1: 0.1-1, carrying out hydrogen transfer treatment for 1-4 hours at the temperature of 250-400 ℃ and under the pressure of 1-l 0MPa, and carrying out appropriate deoxidation on the biological tar, wherein the deoxidation rate of the biological tar is 20-60%, so that upgraded tar with better stability and higher molecular weight is obtained, and the oxygen content of the upgraded tar is 1-10%; then, mechanically filtering the upgraded tar, wherein the mechanical filtration is one of centrifugal filtration, vacuum filtration, plate-frame filtration, sedimentation filtration and cyclone filtration; carrying out two-stage oil-water separation on the filtered upgraded tar at the temperature of 50-80 ℃ to obtain treated upgraded tar;
in the step 2), the mass fraction of the upgraded tar in the mixed oil formed by the medium tar and the upgraded tar is not more than 50%, the temperature of the mixed oil for the carbonization reaction under the action of the high-temperature combustion gas is 1600-1800 ℃, and the reaction time is 0.03-0.3 s; the high-temperature combustion gas is derived from combustion products of heavy tar used as fuel for producing carbon black under the action of combustion-supporting gas.
6. The method for low-carbon and high-efficiency production of carbon black according to claim 1, wherein in the step 2), the biological tar is introduced into the heavy tar to be used as a carbon black production fuel, and the mass ratio of the heavy tar to the biological tar is 1: 1-10; the heavy tar, the biological tar and the combustion-supporting gas are combusted to form high-temperature combustion gas with the temperature of more than 1900 ℃ so as to provide heat for the carbon black production process, the combustion-supporting gas comprises oxygen, oxygen enrichment, mixed gas of the oxygen and carbon dioxide and mixed gas of the oxygen and water vapor, and before combustion, the combustion-supporting gas needs to be heated to 800 ℃ or more through indirect heat exchange with a high-temperature carbonization solid-phase product.
7. The method for low-carbon and high-efficiency production of carbon black according to claim 1, wherein in the step 3), the carbonized gas-phase product is subjected to gas-solid separation and fine filtration and then used for preheating a carbon black production raw material and a carbon black production fuel, wherein the carbon black production raw material is preheated to 150-200 ℃, and the carbon black production fuel is preheated to 120-150 ℃;
the carbonized gas-phase product can be further used for synthesis after gas-solid separation, fine filtration and heat exchangeThe specific process for preparing the gas raw material comprises the following steps: charring the gaseous product and CO2The absorbent solution is subjected to mixing reaction at the temperature of 50-80 ℃ by a concurrent flow method, the flow rate of carbonized gas phase products is 10-100L/h, and CO is2The flow rate of the absorbent solution is 1-3L/h, and CO is2The mass percentage of the absorbent solution is 10-40%, and the CO is2The absorbent comprises three types of alkali metal weak acid salts, alkali metal hydroxide and organic amine, wherein the alkali metal weak acid salts comprise alkali metal carbonate, selenite, tellurite, arsenite, metavanadate, phosphate, sulfite and borate; alkali metal hydroxides include potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide; the organic amine includes ammonia water, thiourea, urea, ethylenediamine, ethanolamine, diethanolamine, glycine, diethylenetriamine and piperazine.
8. The method for producing carbon black with low carbon and high efficiency according to claim 1, characterized in that in the step 3), the raw material composition of the synthesis gas mainly comprises hydrogen and carbon monoxide, and the hydrogen-carbon ratio is 1-2.
9. The method for low-carbon and high-efficiency production of carbon black according to claim 1, wherein in the step 2), the yield of the carbon black product obtained by performing multiple gas-solid separation on the carbonized solid-phase product is 68-82%;
the gas-solid separation is one or more of gravity settling, centrifugal separation, filter screen separation and electrostatic adsorption; the gas-solid separator is one or more of a cyclone separator, a cloth bag filter, an electrostatic dust collector and an adsorption separator; the fine filtration is one or more of microfiltration, ultrafiltration, ultra-microfiltration and nanofiltration of a high-temperature resistant core material.
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