CN115197742A - Method for desulfurizing petroleum coke by vacuum strengthening additive - Google Patents
Method for desulfurizing petroleum coke by vacuum strengthening additive Download PDFInfo
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- CN115197742A CN115197742A CN202210840454.4A CN202210840454A CN115197742A CN 115197742 A CN115197742 A CN 115197742A CN 202210840454 A CN202210840454 A CN 202210840454A CN 115197742 A CN115197742 A CN 115197742A
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- petroleum coke
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- leaching
- desulfurization
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- 239000002006 petroleum coke Substances 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000654 additive Substances 0.000 title claims abstract description 39
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 238000005728 strengthening Methods 0.000 title claims description 27
- 230000003009 desulfurizing effect Effects 0.000 title claims description 17
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 64
- 230000023556 desulfurization Effects 0.000 claims abstract description 64
- 238000002386 leaching Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 22
- 229910002804 graphite Inorganic materials 0.000 description 17
- 239000010439 graphite Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 9
- 230000006698 induction Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 6
- 125000001741 organic sulfur group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Freon Substances 0.000 description 1
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/08—Metal salts, or metal salts deposited on a carrier containing the metal in the lower valency
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for deep desulfurization of petroleum coke by using a vacuum reinforced coupling additive, belonging to the technical field of petroleum coke desulfurization. The desulfurization method aims at high-sulfur petroleum coke with 3-15% of sulfur content and more than 80% of fixed carbon content; 75-85% of petroleum coke particles with the particle size of less than 0.15mm, and 15-25% of petroleum coke particles with the particle size of more than 0.15 mm; the desulfurization method comprises the steps of firstly adding an alkaline substance, carrying out vacuum roasting, then carrying out water leaching, carrying out acid leaching after water leaching, cleaning and drying to obtain a product. The vacuum degree of the vacuum roasting is 0-100 Pa, and the temperature is 600-1200 ℃. The sulfur content of the product obtained by the treatment of the invention is reduced to below 0.1 percent, and the desulfurization rate of the petroleum coke is above 99 percent. The method has the advantages of simple process, high efficiency, low energy consumption, easy collection of products, easy realization of industrialization and the like, and is convenient for industrial application.
Description
Technical Field
The invention relates to a method for desulfurizing petroleum coke by using a vacuum strengthening additive, belonging to the technical field of desulfurization of high-sulfur petroleum coke.
Background
The increasing deterioration of the imported crude oil leads to the rapid increase of the output of high-sulfur petroleum coke in China, and the method is widely applied to various industries. The petroleum coke is a main raw material for preparing carbon anodes, high-purity graphite, reducing agents for industrial silicon and the like, in the calcining process, the sulfur content in the petroleum coke is increased, so that the burning loss rate and porosity of calcined coke are increased, the density of products is reduced, the indexes such as the density, porosity and resistivity of the products are reduced, the emission of a large amount of harmful sulfur oxides is caused due to the excessively high content of the petroleum coke, and the damages such as cracking, breakage, unqualified rate increase and the like of carbon products are caused when the carbon electrode is prepared seriously. The desulfurization method of the high-sulfur petroleum coke comprises the following steps: chemical desulfurization, chemical pre-oxidation, high temperature desulfurization and the like, and at present, no economical and reasonable desulfurization method still exists. The high-temperature desulfurization method is the only method used in production, but the desulfurization rate is still low. Therefore, exploring and developing a method for improving the desulfurization rate of petroleum coke is a necessary way for the industrial efficient utilization of petroleum coke.
At present, the invention patents of petroleum coke desulfurization at home and abroad are summarized as follows:
the high-temperature calcination is a common means for petroleum coke desulfurization, when the calcination temperature is lower than 1000 ℃, only part of inorganic sulfur in the petroleum coke can be removed, but organic sulfur can not be removed basically, even if the calcination temperature of the petroleum coke reaches 1400 ℃, the desulfurization rate of the petroleum coke can only reach about 70%, and the desulfurization rate is increased along with the increase of the calcination temperature, but the desulfurization technology not only needs to be greatly invested in energy, but also cannot remove the sulfur content to a very low degree. The invention patent of 'petroleum coke gasification hydrogen production coupling desulfurization method' (application number CN 200710064514.3) reports a petroleum coke desulfurization technology, the technology is hydrodesulfurization, petroleum coke with low sulfur content can be obtained, and the desulfurization technology is relatively complex. The U.S. Pat. No. 3,528,528,528 proposes preheating and pre-oxidizing petroleum coke to gasify the petroleum coke, thereby changing the structure of petroleum coke particles, then placing the treated petroleum coke in a hydrogenation reactor, and introducing hydrogen gas in the gasification reactor to desulfurize the petroleum coke. The invention discloses a desulfurization purification method of petroleum coke and an industrial furnace (patent number: 98114600.7), which reports a desulfurization method, the petroleum coke is calcined at the temperature of 600-1200 ℃, then the petroleum coke is placed in an electric furnace to be calcined at the temperature of 1700-2300 ℃, and finally low-sulfur petroleum coke with the sulfur content of 0.1 percent can be obtained. The invention discloses a method for desulfurizing petroleum coke by using ionic liquid (application number CN 200710064515.8), which relates to a method for removing sulfur in petroleum coke, wherein alkaline ions are used as an auxiliary agent and are added into the petroleum coke to change the structure of the petroleum coke, so that the sulfur in the petroleum coke is favorably removed, and the desulfurization rate is not very high.
In order to improve the desulfurization rate of petroleum coke, the paper "Vacuum-assisted and alkali roasting for desulfation of petroleum coke" by the Cao world, chengzheng Jie and the like discloses a Vacuum-assisted alkali roasting desulfurization scheme, which basically realizes rapid and efficient desulfurization within a short time. The invention makes further research on the basis of the technology, and finds that the sulfur content of the product can be further reduced by adopting a small amount of alkaline substances to match with vacuum treatment and leaching treatment.
The petroleum coke and the alkali are mixed and roasted, and the organic sulfur in the petroleum coke is difficult to effectively remove at normal temperature, so the raw material is roasted at a high temperature and a proper temperature, most of sulfur bonds in the petroleum coke start to be pyrolyzed and broken at the proper temperature, so most of sulfur is removed, but the thiophene sulfur in the organic sulfur is extremely difficult to remove, so the vacuum auxiliary roasting treatment is carried out, the carbon-sulfur bonds in the organic sulfur are broken, and the desulfurization efficiency is improved 2 S can completely avoid the reaction with water vapor or oxygen and can effectively avoid the toxic gas SO 2 The production and the discharge of the composite material have positive significance for production safety and environmental protection. In addition, because the temperature is not high in the experimental process,simple operation, high safety, and positive significance for reducing energy consumption and industrial production
The technical problem to be solved by the invention is as follows: the invention aims at the desulfurization technology of petroleum coke at home and abroad, the technology with high desulfurization rate has high cost and relatively complex process; the low-cost desulfurization technology has low desulfurization rate, and petroleum coke with extremely low sulfur content cannot be obtained.
Aiming at the problems and the defects in the prior art, the invention provides a method for desulfurizing petroleum coke by using a vacuum strengthening additive. The petroleum coke obtained by the method has extremely low sulfur content and can completely meet the industrial production requirement. The method comprises the following specific steps:
(1) Firstly, crushing petroleum coke until the particle size of the petroleum coke is less than 0.15mm accounts for 75-85%, and then mixing the petroleum coke and an additive according to the mass ratio of 90-95%: 5 to 10 percent of the mixture is evenly mixed to obtain a mixed material; the additive is an alkaline substance;
(2) And (2) putting the mixed material prepared in the step (1) into a vacuum furnace, performing vacuum roasting at the heat preservation temperature of 600-1200 ℃, and taking out to obtain a roasted product.
(3) Carrying out water leaching treatment on the product obtained in the step (2), and carrying out solid-liquid separation after the water leaching treatment; cleaning the solids; obtaining a water leaching product;
(4) And carrying out acid leaching treatment on the water leaching product, and cleaning and drying the water leaching product after the acid leaching treatment to obtain the product.
Preferably, the sulfur content of the petroleum coke is 3-15 wt%, and the fixed carbon content is more than 80%.
Preferably, the content of the petroleum coke particles with the granularity of less than 0.15mm is 75-85%, and the content of the petroleum coke particles with the granularity of more than 0.15mm is 15-25%.
The additive is selected from K 2 CO 3 、Li 2 CO 3 、Na 2 CO 3 、NaHCO 3 、KHCO 3 At least one of NaOH, KOH and LiOH. Preferably sodium carbonate mixed and/or potassium carbonate.
Preferably, the temperature of the vacuum roasting is 600-1200 ℃; the heat preservation time is 30-60min, and the vacuum degree is 0-100 Pa.
In the exploration process, the temperature of vacuum roasting is 600-700 ℃, and the desulfurization effect of the product is more excellent.
Preferably, the solid-liquid ratio of the invention: 1:4-1: and 7, placing the roasted product in water, stirring and leaching at room temperature to 60 ℃, filtering after leaching, and cleaning a solid obtained by filtering to obtain a water leaching product. In industrial application, the water immersion time is 30-60 min. During cleaning, the pH of the eluate can be controlled to 7-8 by cleaning for 3-5 times.
Preferably, the solid-liquid ratio of the invention: 1:4-1:7, placing the water soaked product in acid liquor; stirring and leaching at room temperature to 50 ℃, filtering after leaching, and cleaning and drying the solid obtained by filtering to obtain the product. In industrial application, the acid leaching time is 30-60 min. During cleaning, the pH of the eluate can be controlled to 7-8 by cleaning for 3-5 times. When used industrially, the drying temperature may be 80 to 90 ℃. The time is generally 12 to 36 hours. Of course, if it is ensured that the product is not oxidized, the drying temperature can be suitably raised, which can save a lot of drying time.
The yield of the petroleum coke is more than 75 percent.
In the invention, petroleum coke is treated; the desulfurization degree is more than or equal to 99 percent and the sulfur content is reduced by 0.1 percent. After optimization, the desulfurization rate can be more than or equal to 99.5 percent.
The invention has the beneficial effects that:
(1) The invention has simple and convenient process, does not need to introduce additional reaction gas such as Freon, chlorine and the like, reduces the economic cost and improves the production safety;
(2) The invention is roasted under the condition of 0-100 Pa, and can promote the cracking of sulfur and alkali in petroleum coke, so that impurities and a small amount of additives react at a lower temperature, and the production energy consumption is reduced;
(3) The invention utilizes the vacuum auxiliary technology, promotes the carbon-sulfur bond in organic sulfur to be broken, and simultaneously avoids the reaction of desulfurization products and water vapor or oxygen to generate harmful gas SO 2 The method has positive significance for production safety and environmental protection;
(4) The invention selects lower temperature to carry out vacuum roasting, then adopts water leaching and acid leaching, can further reduce the sulfur content of the product, and particularly when the roasting temperature is 600-700 ℃, the effect achieved by the invention is matched with subsequent water leaching and acid leaching, and is greatly beyond the expectation.
(5) The petroleum coke prepared by the method has extremely low sulfur content, can be effectively applied to the subsequent processing production of the petroleum coke, effectively solves the problems of the reduction of indexes such as product density, porosity and resistivity caused by overhigh sulfur content, and the like, and has low energy consumption, simple operation, high economic benefit and great market application and popularization prospects.
Detailed Description
The invention will be further illustrated by the following specific embodiments
Example 1
The method for desulfurizing petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to reach grain size of less than 0.15mm in 81%, and mixing with Na 2 CO 3 The mass ratio is 90%: mixing 10% of the raw materials uniformly to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 700 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-to-liquid ratio of 1: and 5, adding water for leaching treatment, stirring while soaking in water, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.6 to obtain the soaked product.
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:5, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, repeating for 4 times until the pH value is 7.4, and obtaining an acid leaching product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.05%, and the desulfurization rate was 99.5%. The yield of the petroleum coke after desulfurization is 78 percent.
Example 2
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to 78% of particles smaller than 0.15mm, and mixing the petroleum coke and K 2 CO 3 The mass ratio is 90%: mixing 10% of the raw materials uniformly to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 600 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1:5, adding water for leaching treatment, stirring while soaking, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.6 to obtain a water soaked product;
(4) Putting the water leaching product prepared in the step (3) into a container, and adding the water leaching product into the container according to a solid-to-liquid ratio of 1:5, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, repeating for 4 times until the pH value is 7.2, and obtaining an acid-leached product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.04%, and the desulfurization rate was 99.7%. The yield of the petroleum coke after desulfurization is 80 percent.
Example 3
The method for desulfurizing petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to reach the particle size of less than 0.15mm accounting for 77%, and mixing the petroleum coke and NaOH in the mass ratio of 95% to 5% to obtain mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 900 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1:5, adding water for leaching treatment, stirring while leaching, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.5 to obtain a leached product;
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:5, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, repeating for 4 times until the pH value is 7.3, and obtaining an acid-leached product;
(5) And (5) putting the acid leaching product prepared in the step (4) into a drying box with the temperature of 85 ℃ for drying for 24 hours, and finally obtaining a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.09%, and the desulfurization rate was 99.1%. The yield of the petroleum coke after desulfurization is 79 percent.
Example 4
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to reach the grain size of 81% below 0.15mm, and mixing petroleum coke and NaOH in the weight ratio of 92% to 8% to obtain mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 1200 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-to-liquid ratio of 1:7 adding water for leaching treatment, stirring while soaking in water, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.6 to obtain a water soaked product;
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:7, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, repeating for 4 times until the pH value is 7.4, and obtaining an acid leaching product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.08%, and the desulfurization rate was 99.3%. The petroleum coke yield after desulfurization is 82 percent.
Example 5
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Firstly, crushing petroleum coke to reach the mass ratio of particles smaller than 0.15mm to be 79 percent, and then uniformly mixing the petroleum coke and KOH according to the mass ratio of 95 percent to 5 percent to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 1000 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1:6, adding water for leaching treatment, stirring while soaking, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.3 to obtain a water soaked product;
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:6, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.1 to obtain an acid leaching product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.09%, and the desulfurization rate was 99.1%. The yield of the desulfurized petroleum coke is 81 percent.
Example 6
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to 79% of particles with the particle size of less than 0.15mm, and then mixing the petroleum coke and Na 2 CO 3 Uniformly mixing 90% and 10% by mass to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 1100 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1:4, adding water for leaching treatment, stirring while soaking, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.5 to obtain a water soaked product;
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:4, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, repeating the step for 4 times until the pH value is 7.7, and obtaining an acid-leached product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in this example was 0.07%, and the desulfurization rate was 99.2% compared to the raw material. The yield of the petroleum coke after desulfurization is 80 percent.
The etched grooves on the surface of petroleum coke particles can be obviously seen in an electron microscope image of a treated product, the distribution of the grooves is regular, the occurrence of the grooves plays an important role in deep desulfurization of the petroleum coke, the regular distribution of the grooves indicates that the desulfurization of the petroleum coke is sufficient, and finally the deep desulfurization of the petroleum coke is realized to obtain the low-sulfur petroleum coke.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Comparative example 1
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to 79% of particles with the particle size of less than 0.15mm, and then mixing the petroleum coke and Na 2 CO 3 Uniformly mixing 90% and 10% to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 1000 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1: adding 1mol/L hydrochloric acid into the mixture 7 for leaching, stirring the mixture during acid leaching, controlling the temperature at 40 ℃, stirring the mixture for 30min, filtering the stirred product, and repeating the process for 4 times until the pH value is 7.6 to obtain an acid-leached product;
(4) Putting the acid leaching product prepared in the step (3) into a container, and adding the acid leaching product into the container according to a solid-to-liquid ratio of 1:4, adding water, stirring, controlling the temperature at 40 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.2 to obtain a water soaked product;
(5) And (4) putting the water immersed product prepared in the step (4) into a drying box with the temperature of 85 ℃ for drying for 24 hours, and finally obtaining a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in the comparative example is 2.06%, and the desulfurization rate is 97.3%. The yield of the petroleum coke after desulfurization is 65 percent.
Comparative example 2
The method for desulfurizing the petroleum coke by using the vacuum strengthening additive comprises the following specific steps:
(1) Crushing petroleum coke to 80% of particles with particle size of less than 0.15mm, and mixing with Na 2 CO 3 Uniformly mixing 90% and 10% by mass to obtain a mixed material;
(2) Putting the mixed material prepared in the step (1) into a graphite crucible, putting the graphite crucible into an induction furnace for vacuum roasting, wherein the heat preservation temperature is 500 ℃, the heat preservation time is 30min, and the vacuum degree in the furnace is 10 -4 Pa, taking out to obtain a roasted product;
(3) Placing the roasted product obtained in the step (2) into a container, and mixing the roasted product and the container according to a solid-liquid ratio of 1:5, adding water for leaching treatment, stirring while soaking, controlling the temperature at 50 ℃, stirring for 30min, filtering the stirred product, and repeating for 4 times until the pH value is 7.5 to obtain a water soaked product;
(4) Putting the water immersed product prepared in the step (3) into a container, and adding the water immersed product into the container according to a solid-liquid ratio of 1:5, adding 1mol/L hydrochloric acid, stirring, controlling the temperature at 70 ℃, stirring for 30min, filtering the stirred product, repeating for 4 times until the pH value is 7.7, and obtaining an acid-leached product;
(5) And (4) drying the acid leaching product prepared in the step (4) in a drying box at the temperature of 85 ℃ for 24 hours to finally obtain a desulfurization product of petroleum coke in the vacuum strengthening additive.
The sulfur content of the desulfurized petroleum coke obtained in the comparative example is 15.8%, and the desulfurization rate is 84.1%. The yield of the petroleum coke after desulfurization is 69 percent.
Claims (10)
1. A method for desulfurizing petroleum coke by using a vacuum strengthening additive; it is characterized in that; the method comprises the following steps:
(1) Firstly, crushing petroleum coke until the particle size of the petroleum coke is less than 0.15mm accounts for 75-85%, and then, according to the mass ratio of the petroleum coke to the additive, the petroleum coke and the additive are 90-95%: 5 to 10 percent of the mixture is evenly mixed to obtain a mixed material; the additive is an alkaline substance;
(2) Putting the mixed material prepared in the step (1) into a vacuum furnace, carrying out vacuum roasting at the heat preservation temperature of 600-1200 ℃, and taking out to obtain a roasted product;
(3) Performing water leaching treatment on the product obtained in the step (2), and performing solid-liquid separation after the water leaching treatment; cleaning the solids; obtaining a water leaching product;
(4) And (4) carrying out acid leaching treatment on the water leaching product, and cleaning and drying the water leaching product after the acid leaching treatment to obtain the product.
2. The method of claim 1, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: the sulfur content of the petroleum coke is 3-15 wt%, and the fixed carbon content is more than 80%.
3. The method of desulfurizing petroleum coke with a vacuum enhancing additive according to claim 1; the method is characterized in that: the content of the petroleum coke particles with the granularity of less than 0.15mm is 75-85%, and the content of the petroleum coke particles with the granularity of more than 0.15mm is 15-25%.
4. The method of claim 1, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: the additive is selected from K 2 CO 3 、Li 2 CO 3 、Na 2 CO 3 、NaHCO 3 、KHCO 3 At least one of NaOH, KOH and LiOH. Preferably sodium carbonate and/or potassium carbonate.
5. The method of claim 1, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: the temperature of the vacuum roasting is 600-1200 ℃; the heat preservation time is 30-60min, and the vacuum degree is 0-100 Pa.
6. The method of claim 1, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: according to the solid-liquid ratio of 1:4-1: and 7, placing the roasted product in water, stirring and leaching at room temperature to 60 ℃, filtering after leaching, and cleaning a solid obtained by filtering to obtain a water leaching product.
7. The method of desulfurizing petroleum coke with a vacuum enhancing additive according to claim 1; the method is characterized in that: according to the solid-liquid ratio of 1:4-1:7, putting the water soaked product into acid liquor; stirring and leaching at room temperature-50 ℃, filtering after leaching, and cleaning and drying the solid obtained by filtering to obtain the product.
8. The method of claim 1, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: the yield of the desulfurized petroleum coke is over 75 percent.
9. The method of desulfurizing petroleum coke with a vacuum enhancing additive according to any one of claims 1-8; the method is characterized in that: after petroleum coke is treated; the desulfurization rate is more than or equal to 99 percent.
10. The method of claim 9, wherein the vacuum strengthening additive desulfurizes petroleum coke; the method is characterized in that: after petroleum coke is treated; the desulfurization degree may be 99.5% or more.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146434A (en) * | 1974-11-15 | 1979-03-27 | Standard Oil Company (Indiana) | Process for the desulfurization of petroleum coke |
| CN102153070A (en) * | 2011-03-07 | 2011-08-17 | 昆明冶金研究院 | Method for purifying calcined petroleum coke |
| CN106336928A (en) * | 2016-10-10 | 2017-01-18 | 昆明理工大学 | Method for vacuum reinforced desulfurization of high sulfur petroleum coke |
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2022
- 2022-07-18 CN CN202210840454.4A patent/CN115197742A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146434A (en) * | 1974-11-15 | 1979-03-27 | Standard Oil Company (Indiana) | Process for the desulfurization of petroleum coke |
| CN102153070A (en) * | 2011-03-07 | 2011-08-17 | 昆明冶金研究院 | Method for purifying calcined petroleum coke |
| CN106336928A (en) * | 2016-10-10 | 2017-01-18 | 昆明理工大学 | Method for vacuum reinforced desulfurization of high sulfur petroleum coke |
Non-Patent Citations (1)
| Title |
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| SHIJIE CAO等: "Vacuum-assisted and alkali roasting for desulfurization of petroleum coke", JOURNAL OF CLEANER PRODUCTION, vol. 332, pages 1 - 12 * |
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