CN115125035A - Method for producing synthesis gas from petroleum coke - Google Patents
Method for producing synthesis gas from petroleum coke Download PDFInfo
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- CN115125035A CN115125035A CN202110333772.7A CN202110333772A CN115125035A CN 115125035 A CN115125035 A CN 115125035A CN 202110333772 A CN202110333772 A CN 202110333772A CN 115125035 A CN115125035 A CN 115125035A
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- gas
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- 239000002006 petroleum coke Substances 0.000 title claims abstract description 84
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000002309 gasification Methods 0.000 claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000571 coke Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 3
- 230000003111 delayed effect Effects 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 239000002699 waste material Substances 0.000 abstract description 5
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002956 ash Substances 0.000 description 15
- 239000003245 coal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 101100002917 Caenorhabditis elegans ash-2 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/52—Ash-removing devices
- C10J3/526—Ash-removing devices for entrained flow gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for producing synthesis gas from petroleum coke, which comprises the following steps: the petroleum coke particles contact with a gasifying agent under the condition of gasification reaction to carry out gasification reaction, the gasification reaction product flows out from a reactant outlet at the top of the fluidized bed gasification furnace, synthesis gas is obtained after separation, part of fine coke powder is extracted from a fine coke powder outlet of the fluidized bed gasification furnace and collected, and the vanadium content of the obtained fine coke powder is not less than 0.1 weight percent. The invention can gasify the inferior petroleum coke to prepare the synthesis gas, and simultaneously collect the fine coke powder particles rich in metal, thereby being convenient for recovering the nickel-vanadium metal and changing waste into valuable.
Description
Technical Field
The invention relates to the field of petroleum coke treatment, in particular to a method for producing synthesis gas from petroleum coke.
Background
The trend towards crude oil heavies is becoming increasingly evident, and refining processes associated therewith have shown an increasing amount of carbonaceous material. Delayed coking converts low grade resids to light oil at a lower cost, but at the same time produces about 20% of the petroleum coke as a by-product. Because the content of the impurity elements in the petroleum coke is high, the further utilization must consider the environmental protection factor, so the petroleum coke is strictly limited to be utilized by a combustion mode in a large-user power plant of the petroleum coke, particularly the petroleum coke with poor quality under the condition of lacking a proper treatment method.
CN110684563A discloses a high-sulfur inferior petroleum coke gasification furnace and a gasification method thereof, wherein the method gasifies petroleum coke in an entrained flow mode. Throwing petroleum coke fine powder from a petroleum coke powder inlet at the top of the gasification furnace along the vertical direction, and adding O 2 /H 2 O/CO 2 /N 2 The formed gasifying agent is injected into the gasification furnace from a high-oxygen concentration gasifying agent inlet at the top of the gasification furnace along the vertical direction, the reaction temperature is controlled within the range of 1200-1600 ℃, the pressure is 0.1-8.0MPa, and the gas-solid contact time is 5-20s, so that the petroleum coke and the gasifying agent are subjected to high-temperature gasification reaction to generate the gasification agent rich in CO and H 2 The gas of (2). High-temperature gas and ash flow downwards and enter the temperature-reducing transformation section through the flaring section, water or steam is sprayed into the gasification furnace from an atomizing nozzle on the flaring section to reduce the reaction temperature to 700-1000 ℃, and part of CO is transformed into H through high-temperature steam to generate H 2 The retention time of the gas in the temperature-reducing transformation section is 5-20 s.
CN110205165A discloses a combined bed coal gasification system and method, which comprises a raw material coal feeding unit, a fly ash circulating feeding unit, a combined bed coal gasification unit and a heat recovery and dust removal unit, wherein the combined bed coal gasification unit comprises a circulating fluidized bed gasification furnace and an entrained flow bed gasification furnace, a radiation waste boiler chamber is arranged at the upper part of the entrained flow bed gasification furnace, a heat-supplementing reaction zone is arranged at the upper part of the circulating fluidized bed gasification furnace, and an outlet at the top of the radiation waste boiler chamber is connected with the heat-supplementing reaction zone through a gas delivery conduit. The invention realizes the cyclic treatment and the effective utilization of the fly ash through a combined bed system of the circulating fluidized bed and the entrained flow bed.
When the existing entrained flow bed pulverized coal gasification technology is adopted to mix and burn petroleum coke, because the ash content of the petroleum coke is far lower than that of coal, the conversion rate of the petroleum coke is lower under the conventional entrained flow bed operation condition.
The fluidized bed gasification furnace generally adopts coal as a raw material, adopts a circulating fluidized bed as an operation mode, and needs to consider the factors influencing the operation of the gasification furnace, such as slag discharge, particle adhesion, particle circulation, gas-solid separation and the like. The petroleum coke has very low ash content, and the ash composition is greatly different from the coal ash composition. When the prior art of circulating fluidized bed coal gasification is used for petroleum coke gasification, a large amount of water vapor is consumed due to too high gas velocity, and meanwhile, the particle abrasion is serious and the fine powder amount is increased due to high gas velocity.
The petroleum coke also contains several tens to over a thousand ppm of vanadium metal. Vanadium is a rare metal with high utilization value, and if the high-value vanadium can be recycled, the vanadium has the effect of changing waste into valuable.
Disclosure of Invention
The invention aims to solve the problems that the carbon conversion rate is low when petroleum coke is gasified and vanadium metal in the petroleum coke cannot be recycled in the prior art.
The invention provides a method for producing synthesis gas from petroleum coke, which comprises the following steps: the method comprises the steps that petroleum coke particles enter a fluidized bed gasification furnace from a petroleum coke feeding port of the fluidized bed gasification furnace, a gasifying agent enters the fluidized bed gasification furnace from a gasifying agent feeding port at the bottom of the fluidized bed gasification furnace, the petroleum coke particles are in contact with the gasifying agent under the gasification reaction condition to carry out gasification reaction, a gasification reaction product is extracted from a reactant outlet at the top of the fluidized bed gasification furnace, synthetic gas is obtained after separation, part of fine coke powder is extracted from a fine coke powder discharging port of the fluidized bed gasification furnace and collected, the vanadium content of the obtained fine coke powder is not less than 0.1 wt%, and the fine coke powder discharging port is arranged on the side wall of the fluidized bed gasification furnace and is positioned above the petroleum coke feeding port.
In the present invention, "above … …" describes a spatial positional relationship in the axial direction, and has no relationship with the positional relationship of the two in a plan view.
In the invention, the petroleum coke is from a delayed coking process, and the granularity of petroleum coke particles entering a fluidized bed gasification furnace is 0.1-3 mm. Preferably, the granularity of the petroleum coke particles is 0.1-1.5 mm, and further preferably 0.1-1.0 mm.
In one embodiment of the invention, the gasification reaction conditions are: the reaction temperature is 800-1300 ℃, the reaction pressure is 0.1-5.0 MPa, and the retention time of petroleum coke particles is 20-60 min, preferably 30-50 min. The invention can select different pressure levels according to the requirements of downstream processes.
In one embodiment of the present invention, the reaction temperature is 900 to 1200 ℃, preferably 1000 to 1100 ℃.
In one embodiment of the invention, a gas distribution plate is arranged above a gasification agent feed port of the fluidized bed gasification furnace, a gas outlet is arranged on the gas distribution plate, the gas velocity of the gas outlet is 1-5 m/s, and the air velocity of an empty bed of the fluidized bed is 0.2-1.0 m/s.
In one embodiment of the invention, the gas distribution plate is provided with a suitable number of caps to change the direction of the gas flow and to make the gas flow more uniform in the bed. After the gasification agent gas is fully mixed, the gas enters the bottom of the fluidized bed layer from the hood on the gas distribution plate, and fully contacts and reacts with petroleum coke particles.
In one embodiment of the invention, the gasifying agent is a mixed gas I of water vapor and oxygen, and the molar content of the water vapor in the mixed gas I is 50-85%; or the gasifying agent is a mixed gas II of water vapor and air, and the molar content of the water vapor in the mixed gas II is 5-20%.
In one embodiment of the present invention, the mixed gas I or the mixed gas II contains carbon dioxide, and the molar content of carbon dioxide and the molar content of water vapor in the mixed gas I are 10 to 30% and 20 to 65%, respectively; in the mixed gas II, the molar content of carbon dioxide is 10-30%, and the molar content of water vapor is 5-10%.
In one embodiment of the present invention, the feeding temperature of the gasifying agent is 100 to 500 ℃. After all gases of the gasifying agent are uniformly mixed by the mixer, the gasifying agent enters the fluidized bed gasification furnace from a gasifying agent feed port at the bottom of the fluidized bed gasification furnace at the temperature of 100-500 ℃, and enters the bottom of a fluidized bed layer through a gas distribution plate.
In one embodiment of the present invention, the height of the bed layer of the fluidized bed in the fluidized-bed gasification furnace is 5 to 20m, preferably 6 to 10 m.
In one embodiment of the present invention, the aspect ratio of the fluidized bed gasification furnace is between 0.4 and 4. When the diameter of the bed layer is smaller, the height-diameter ratio is taken in a larger range; when the diameter of the bed layer is larger, the height-diameter ratio is selected in a smaller range.
The petroleum coke solid particles are fully contacted with the gasifying agent, and gasification reaction is carried out under the gasification reaction condition, so that the size of the petroleum coke particles is reduced to form fine coke, and the relative metal content on the fine coke is increased. The invention collects part of fine coke powder through the fine coke powder outlet.
The remaining part of the fine coke powder, and solid particles smaller than the fine coke powder in particle size, are carried out by the gas, separated and collected by the cyclone separator. The high-temperature gas of the reaction product is further cooled and dedusted and then sent to the downstream process to be used as C 1 Chemical raw materials, or raw materials for hydrogen production by sulfur-tolerant shift, or raw materials for methane synthesis.
In one embodiment of the invention, the petroleum coke feeding hole is arranged at 1/3-2/3 of the height of the bed layer of the fluidized bed; the fine coke discharging port is arranged at the position 1/2-5/6 of the height of the bed layer of the fluidized bed.
In one embodiment of the invention, 1-6 petroleum coke feeding holes are formed in the side wall of the fluidized bed gasification furnace.
In one embodiment of the present invention, the particle size of the fine coke breeze is 0.02 to 0.2mm, and the vanadium content of the fine coke breeze is 0.1 to 2.1 wt%.
The invention converts various petroleum cokes containing high-sulfur petroleum cokes into synthesis gas which is further used as C 1 The fine coke powder with reduced particle size and increased metal content is pumped out from the fluidized bed gasification furnace, and the nickel-vanadium metal enriched in the fine coke powder is collected and recovered, so that the waste can be changed into valuable.
Drawings
Fig. 1 is a schematic diagram of one embodiment of a process for producing syngas from petroleum coke according to the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, but the invention is not limited thereto.
Fig. 1 is a schematic diagram of one embodiment of the process for producing synthesis gas from petroleum coke provided by the present invention. As shown in fig. 1, 4 petroleum coke feed ports 2 are uniformly formed on the sidewall of the fluidized-bed gasification furnace 1 in a horizontal position. The petroleum coke particles enter the fluidized bed layer from the petroleum coke feeding hole 2 through a screw feeder or a lock hopper. The bottom of the gasification furnace is provided with a horizontal gas distribution plate, and the gas distribution plate is provided with a proper number of caps 5 to change the gas flowing direction and make the gas flow in the bed layer more uniform. The gasification agent is fully mixed by the gas mixer 6, is uniformly distributed in the gas buffer cavity 7, enters the bottom of the fluidized bed layer from the hood 5, and reacts with petroleum coke particles in a contact way. The reaction gas flows out of the gasification furnace from a reactant outlet 3 at the top of the fluidized bed gasification furnace, is connected with a high-temperature cyclone separator for separation, and the obtained gas-phase material is cooled and dedusted to obtain the synthesis gas. Part of the fine coke powder is collected from the fluidized bed gasification furnace through the collector 4 and is pumped out through the fine coke powder discharge port 8, and the fine coke powder is collected outside the fluidized bed gasification furnace, so that the metal rich in the fine coke powder can be recovered. The manhole 9 is used for installation and maintenance.
The invention will now be further illustrated with reference to the following examples, without thereby being restricted thereto.
Example 1
In the embodiment, a fluidized bed gasification furnace is adopted, the height of a fluidized bed layer is 9.5m, a petroleum coke feeding hole is arranged at 37% of the height of the fluidized bed layer, and 4 petroleum coke feeding holes are averagely arranged along the side wall; the fine coke discharge outlet is arranged at 59% of the height of the fluidized bed layer.
The properties of the petroleum coke 1 treated in this example are shown in table 1, and the metal content of ash 1 in the petroleum coke 1 is shown in table 2. The average grain diameter of the petroleum coke 1 is 500 mu m, and the ash content in the petroleum coke 1 is 0.91 percent, the metal content is 0.43 percent and the vanadium content is 0.01128 percent in percentage by weight. The gasifying agent in this embodiment consists of water vapor and oxygen, wherein the water vapor is 75% by volume.
The gasification reaction conditions are as follows: the reaction temperature is 1000 ℃, the reaction pressure is 0.5MPa, and the feeding amount of the petroleum coke 1 is 120 t/h. The volume space velocity of the gasifying agent gas is 510.1h -1 。
Gasification of reaction gas from a fluidized bedThe top of the furnace flows out of the gasification furnace, is connected with the high-temperature cyclone separator for separation, and the obtained gas-phase material is cooled and dedusted to obtain the synthesis gas. Part of the fine coke powder is extracted from the fine coke powder outlet. The resulting wet-based product gas flow rate was 380700Nm 3 H is used as the reference value. CO + H in dry gas 2 The volume content was 82.3%. The flow rate of the collected fine coke powder is 7.1t/h, and the granularity is less than 0.12 mm. Wherein, the ash content of the fine coke powder is 10.7 percent, the total metal content of the fine coke powder is 5.16 percent, and the vanadium content of the fine coke powder is 0.13 percent.
TABLE 1 Petroleum coke composition (%)
TABLE 2 ash content (%)
| Serial number | Ni | V | Na | Al | | Cu | Ca | |
| 1 | 4.28 | 1.24 | 12.7 | 7.2 | 18.7 | 0.056 | 4.1 | |
| 2 | 4.15 | 1.32 | 11.5 | 6.9 | 17.4 | 0.043 | 5.9 |
Example 2
The same fluidized bed gasifier, same petroleum coke feedstock and gasifier as in example 1 were used.
The gasification reaction conditions are as follows: the reaction temperature is 950 ℃, the reaction pressure is 0.5MPa, and the feeding amount of the petroleum coke 1 is 100 t/h. The volume space velocity of the gasifying agent gas is 420.3h -1 。
The resulting wet-based product gas flow rate was 317000Nm 3 H is used as the reference value. CO + H in dry gas 2 The content by volume was 80.3%. The flow rate of the collected fine coke powder is 5.7t/h, and the granularity is less than 0.10 mm. Wherein, the ash content of the fine coke powder is 9.3 percent, the metal content of the fine coke powder is 4.48 percent, and the vanadium content of the fine coke powder is 0.11 percent.
Example 3
The same fluidized bed gasifier, same petroleum coke feedstock and gasifier as in example 1 were used.
The gasification reaction conditions are as follows: the reaction temperature is 1100 ℃, the reaction pressure is 0.5MPa, the feeding quantity of the petroleum coke 1 is 135t/h, and the volume space velocity of the gasification agent gas is 570.5h -1 。
The resulting wet-based product gas flow rate was 428200Nm 3 H is used as the reference value. CO + H in dry gas 2 Volume containsThe amount was 87.3%. The flow rate of the collected fine coke powder is 8.2t/h, and the granularity is less than 0.11 mm. Wherein, the ash content of the fine coke powder is 11.3 percent, the metal content of the fine coke powder is 5.44 percent, and the vanadium content of the fine coke powder is 0.13 percent.
Example 4
In the embodiment, a fluidized bed gasification furnace is adopted, the height of a fluidized bed layer is 7.5m, a petroleum coke feeding hole is arranged at 41% of the height of the fluidized bed layer, and 4 petroleum coke feeding holes are averagely arranged along the side wall; the fine coke discharge outlet is arranged at 57.5 percent of the height of the bed layer of the fluidized bed.
The same petroleum coke feedstock and gasifying agent as in example 1 were used.
The gasification reaction conditions are as follows: the reaction temperature is 1000 ℃, the reaction pressure is 3.5MPa, and the feeding amount of the petroleum coke 1 is 110 t/h. The volume space velocity of the gasifying agent gas is 520.3h -1 。
The resulting wet-based product gas flow rate was 620056.7Nm 3 H is used as the reference value. CO + H in dry gas 2 The volume content was 82.3%. The flow rate of the collected fine coke powder is 6.1t/h, and the granularity is less than 0.12 mm. Wherein, the ash content of the fine coke breeze is 10.3 percent, the metal content of the fine coke breeze is 4.95 percent, and the vanadium content of the fine coke breeze is 0.12 percent by weight percentage.
Example 5
The same fluidized-bed gasification furnace as in example 1 was used.
The properties of the petroleum coke 2 treated in this example are shown in table 1, and the metal content of ash 2 in the petroleum coke 2 is shown in table 2. The average grain diameter of the petroleum coke 2 is 500 mu m, and the ash content in the petroleum coke 2 is 0.87 percent, the metal content is 0.41 percent and the vanadium content is 0.01148 percent in percentage by weight.
The gasifying agent in this embodiment consists of water vapor and oxygen, wherein the water vapor is 75% by volume.
The gasification reaction conditions are as follows: the reaction temperature is 1000 ℃, the reaction pressure is 0.5MPa, the feeding quantity of the petroleum coke 2 is 120t/h, and the volume space velocity of the gasifying agent gas is 510.1h -1 。
The resulting wet-based product gas flow rate was 380700Nm 3 H is used as the reference value. CO + H in dry gas 2 The volume content was 82.3%. The flow rate of the collected fine coke was 7.0t/h, the granularity is less than 0.10 mm. Wherein, the ash content of the fine coke powder is 9.7 percent, the metal content of the fine coke powder is 4.57 percent, and the vanadium content of the fine coke powder is 0.128 percent.
Example 6
The same fluidized bed gasifier, same petroleum coke feedstock and gasifier as in example 1 were used. Except that the average particle size of the treated petroleum coke 1 was 600 μm.
The gasification reaction conditions are as follows: the reaction temperature is 1000 ℃, the reaction pressure is 0.5MPa, and the feeding amount of the petroleum coke 1 is 110 t/h. The volume space velocity of the gasifying agent gas is 510.1h -1 。
The resulting wet-based product gas flow rate was 350700Nm 3 H is used as the reference value. CO + H in dry gas 2 The volume content was 82.3%. The flow rate of the collected fine coke powder is 7.0t/h, and the granularity is less than 0.12 mm. Wherein, the ash content of the fine coke powder is 10.9 percent, the metal content of the fine coke powder is 5.26 percent, and the vanadium content of the fine coke powder is 0.13 percent.
Example 7
The same fluidized bed gasifier, the same petroleum coke feedstock as in example 1 was used.
The gasifying agent in this embodiment is composed of water vapor, carbon dioxide and oxygen, wherein the water vapor is 40% by volume and the carbon dioxide is 35% by volume.
The gasification reaction conditions are as follows: the reaction temperature is 1000 ℃, the reaction pressure is 0.5MPa, and the feeding amount of the petroleum coke 1 is 120 t/h. The volume space velocity of the gasifying agent gas is 510.1h -1 。
The resulting wet-based product gas flow rate was 370700Nm 3 H is used as the reference value. CO + H in dry gas 2 The volume content was 81.3%. The flow rate of the collected fine coke powder is 7.1t/h, and the granularity is less than 0.12 mm. Wherein, the ash content of the fine coke powder is 10.7 percent, the metal content of the fine coke powder is 5.16 percent, and the vanadium content of the fine coke powder is 0.13 percent.
It should be noted that the above-mentioned embodiments are only arbitrary embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various modifications and variations. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A method of producing syngas from petroleum coke, comprising: petroleum coke particles enter the fluidized bed gasification furnace from a petroleum coke feeding port of the fluidized bed gasification furnace, a gasification agent enters the fluidized bed gasification furnace from a gasification agent feeding port at the bottom of the fluidized bed gasification furnace, the petroleum coke particles are contacted with the gasification agent under the gasification reaction condition to carry out gasification reaction, a gasification reaction product is extracted from a reactant outlet at the top of the fluidized bed gasification furnace, synthesis gas is obtained after separation, part of fine coke powder is extracted from a fine coke powder discharging port of the fluidized bed gasification furnace and collected, the vanadium content of the obtained fine coke powder is not less than 0.1 wt%, and the fine coke powder discharging port is arranged on the side wall of the fluidized bed gasification furnace and is positioned above the petroleum coke feeding port.
2. The method of claim 1, wherein the petroleum coke is from a delayed coking process, and the particle size of the petroleum coke particles entering the fluidized bed gasifier is 0.1-3 mm.
3. The process according to claim 2, wherein the petroleum coke particles have a particle size of 0.1 to 1.5mm, preferably 0.1 to 1.0 mm.
4. The process of claim 1, wherein the gasification reaction conditions are: the reaction temperature is 800-1300 ℃, the reaction pressure is 0.1-5.0 MPa, and the retention time of petroleum coke particles is 20-60 min.
5. The process according to claim 4, wherein the reaction temperature is 900 to 1200 ℃, preferably 1000 to 1100 ℃.
6. The method according to claim 1, wherein a gas distribution plate is provided above a gasification agent feed port of the fluidized-bed gasification furnace, gas outlets are provided on the gas distribution plate, the gas velocity of the gas outlets is 1 to 5m/s, and the empty bed gas velocity of the fluidized bed is 0.2 to 1.0 m/s.
7. The method according to claim 1, wherein the height of the fluidized bed in the fluidized-bed gasification furnace is 5 to 20m, preferably 6 to 10 m.
8. The method of claim 1 or 7, wherein the petroleum coke feed inlet is arranged at 1/3-2/3 of the bed height of the fluidized bed; the fine coke discharging port is arranged at 1/2-5/6 of the height of the bed layer of the fluidized bed; the petroleum coke feed inlets are arranged on the side wall of the fluidized bed gasification furnace in an amount of 1-6.
9. The method according to claim 1, wherein the fine coke breeze has a particle size of 0.02 to 0.2mm and a vanadium content of 0.1 to 2.1 wt.%.
10. The method according to claim 1, characterized in that the gasifying agent is a mixed gas I of water vapor and oxygen, and the molar content of the water vapor in the mixed gas I is 50-85%; or the gasifying agent is a mixed gas II of water vapor and air, and the molar content of the water vapor in the mixed gas II is 5-20%.
11. The method according to claim 1, wherein the mixed gas I or II contains carbon dioxide, and the molar content of the carbon dioxide in the mixed gas I is 10-30%, and the molar content of the water vapor in the mixed gas I is 20-65%; in the mixed gas II, the molar content of carbon dioxide is 10-30%, and the molar content of water vapor is 5-10%.
12. The method according to claim 1, wherein the feeding temperature of the gasifying agent is 100 to 500 ℃.
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| CN103492537A (en) * | 2011-04-22 | 2014-01-01 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with char beneficiation |
| KR101633213B1 (en) * | 2015-01-14 | 2016-06-24 | 전북대학교산학협력단 | Desulfurization apparatus and method of petroleum coke using a bubbling fluidized bed with CO2 gasification |
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| CN103492537A (en) * | 2011-04-22 | 2014-01-01 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with char beneficiation |
| KR101633213B1 (en) * | 2015-01-14 | 2016-06-24 | 전북대학교산학협력단 | Desulfurization apparatus and method of petroleum coke using a bubbling fluidized bed with CO2 gasification |
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