CN110923014A - Fluxing agent for adjusting melting characteristic of high-sulfur petroleum coke gasification ash and application thereof - Google Patents
Fluxing agent for adjusting melting characteristic of high-sulfur petroleum coke gasification ash and application thereof Download PDFInfo
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- CN110923014A CN110923014A CN201911033301.3A CN201911033301A CN110923014A CN 110923014 A CN110923014 A CN 110923014A CN 201911033301 A CN201911033301 A CN 201911033301A CN 110923014 A CN110923014 A CN 110923014A
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- petroleum coke
- fluxing agent
- ash
- temperature
- calcium oxide
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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
- C10J3/466—Entrained flow processes
-
- 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
- C10J3/50—Fuel charging devices
- C10J3/506—Fuel charging 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
- C10J3/723—Controlling or regulating the gasification process
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0943—Coke
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention relates to a fluxing agent for adjusting melting characteristics of high-sulfur petroleum coke gasification ash and an application thereof. The fluxing agent is prepared by compounding a mineral raw material rich in silicon dioxide and a mineral raw material rich in calcium oxide. The method for adjusting the melting characteristic of the high-sulfur petroleum coke gasification ash by using the fluxing agent comprises the step of adding the fluxing agent accounting for 0.2-2% of the weight of the petroleum coke into the petroleum coke, mixing and grinding the petroleum coke and the fluxing agent to prepare fine powder with the particle size of less than 200 mu m. The fluxing agent can reduce the ash melting point of petroleum coke ash, and improve the high-temperature rheological property of the ash so as to meet the requirement of the high-temperature entrained flow gasifier for slag viscosity-temperature property of liquid slag removal and ensure the stable operation of the petroleum coke gasifier.
Description
Technical Field
The invention relates to a fluxing agent for adjusting melting characteristics of high-sulfur petroleum coke gasification ash and an application thereof, which are particularly suitable for a high-sulfur petroleum coke entrained flow bed high-temperature gasification hydrogen production or synthesis gas generation process, and belong to the technical field of high-efficiency utilization of inferior crude oil.
Background
The crude oil is inevitably heavy and inferior, and the yield of petroleum coke, especially high-sulfur petroleum coke, is continuously increased along with the increase of the yield of inferior high-sulfur crude oil. High-sulfur petroleum coke can only be used as industrial fuel due to high impurity content, however, high-sulfur petroleum coke can generate a large amount of SO during combustionXAnd NOXAnd the like. Therefore, there is a need for a more efficient clean petroleum coke utilization.
The synthesis gas is produced from the petroleum coke in a high-temperature gasification mode, high-value hydrogen and chemicals can be produced, and high-content sulfur in the petroleum coke can be recovered in a form of elemental sulfur, so that the method is an effective way for realizing the resource utilization and clean purification of the petroleum coke. However, petroleum coke does not belong to typical gasification raw materials, has the characteristics of low gasification reaction activity, low volatile matter, high ash melting point and low ash content, has high vanadium and nickel content in ash slag, has an ash melting point of more than 1500 ℃ under the gasification reaction condition, has poor viscosity-temperature characteristics, and cannot meet the requirements of a high-temperature entrained flow gasifier for liquid-state slag removal. In addition, in the high-temperature gasification process, elements such as vanadium, nickel and the like can generate complex chemical reactions with other mineral elements to form low-temperature eutectic substances, and the low-temperature eutectic substances strongly corrode refractory materials, so that serious dust deposition of pipelines is caused, and the safe and stable operation of equipment is influenced. Therefore, a method for reducing the melting point of the high-sulfur petroleum coke gasification ash and improving the viscosity-temperature characteristic of the high-sulfur petroleum coke gasification ash is sought, and the method has very important significance for the gasification application of the high-sulfur petroleum coke.
Fluxing agents are commonly used to adjust the melting characteristics of coal ash during combustion and gasification of coal. Patent CN108676601A discloses a calcium magnesium additive for improving the slagging performance of coal and an application method thereof, wherein the slag containing calcium oxide and magnesium oxide is added to improve the ash melting point of the coal and prevent the boiler from slagging. The patent CN108359512A discloses an additive for relieving coking characteristics of Xinjiang east Junggar high-alkali coal, and a preparation method and a use method thereof. Patent CN08018109A discloses a composite fusing agent for increasing the fusing temperature of low ash fusion point coal ash, which is prepared from calcium-based fusing agent and alumina fusing agent, and can make low ash fusion point coal meet the gasification requirement, and can improve the viscosity-temperature characteristic and increase the gasification efficiency. Patent CN106833786A discloses a method for reducing the melting characteristic temperature of coal ash based on the composition of coal ash by adopting a coal blending mode, which can effectively utilize high ash melting point coal and expand the source of coal gasification raw materials.
The invention provides a fluxing agent for adjusting the melting characteristic of high-sulfur petroleum coke gasification ash, which is prepared by compounding a mineral raw material rich in silicon dioxide and a mineral raw material rich in calcium oxide. In the using process, the slag is mixed and ground with petroleum coke according to a certain proportion, the melting temperature of petroleum coke ash can be obviously reduced, the high-temperature rheological property of the slag can be improved, and the requirement of a high-temperature entrained flow gasifier for slag tapping on the ash viscosity-temperature property can be met.
Disclosure of Invention
The invention aims to provide a fluxing agent which can reduce the ash melting point of petroleum coke ash and improve the high-temperature rheological property of the ash so as to meet the requirement of a high-temperature entrained flow gasifier for slag tapping on the viscosity-temperature property of the ash and ensure the stable operation of the petroleum coke gasifier.
In order to achieve the purpose, the invention provides a fluxing agent for adjusting the melting characteristic of high-sulfur petroleum coke gasification ash, wherein the fluxing agent is prepared by compounding a mineral raw material rich in silica and a mineral raw material rich in calcium oxide.
Preferably, the silica-rich mineral raw material is selected from one of quartz sand, diatomaceous earth, kaolin and bentonite or a combination thereof.
Preferably, the calcium oxide-rich mineral raw material is selected from one or a combination of quick lime, limestone, dolomite and calcium oxide-rich carbide slag.
Preferably, the fluxing agent comprises the following components in percentage by weight: 10-50% of silicon dioxide, 30-90% of calcium oxide and 0-60% of other components; wherein the other components refer to other components except silicon dioxide and calcium oxide in the mineral raw material.
The invention also provides a method for adjusting the melting characteristic of the high-sulfur petroleum coke gasification ash by using the fluxing agent, which comprises the following steps: adding 0.2-2% of the fluxing agent by weight of the petroleum coke into the petroleum coke, mixing and grinding the mixture with the petroleum coke to prepare fine powder with the particle size of less than 200 mu m.
Compared with the prior art, the invention has the beneficial effects that:
(1) the fluxing agent disclosed by the invention takes calcium oxide as a main component, and the calcium oxide and a vanadium element can form a calcium vanadate compound in the high-temperature gasification reaction process of petroleum coke, so that the generation of high-melting vanadium trioxide is prevented, and the ash melting point of petroleum coke gasification ash is effectively reduced;
(2) the fluxing agent takes silicon dioxide as an auxiliary component, and the silicon dioxide and elements such as calcium, iron, nickel and the like form a low-ash-melting-point amorphous eutectic substance in the high-temperature gasification reaction process, so that the high-temperature rheological property of ash is improved;
(3) the fluxing agent can be prepared from various inorganic minerals or waste residues, and the generation cost is reduced.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
A fluxing agent for adjusting the melting characteristic of high-sulfur petroleum coke gasification ash is prepared by compounding diatomite and limestone, wherein the weight percentage of silicon dioxide is 15%, the weight percentage of calcium oxide is 40%, and the balance is the other components except the silicon dioxide and the calcium oxide in the diatomite and the limestone. In the embodiment, the adding amount of the fluxing agent is 1.5 percent of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 1.
TABLE 1
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1280℃ | 1320℃ | 1350℃ | 1370℃ |
Example 2
A fluxing agent for adjusting the melting characteristic of high-sulfur petroleum coke gasification ash is prepared by compounding kaolin, diatomite and carbide slag, wherein the weight percentage of silicon dioxide is 10%, the weight percentage of calcium oxide is 70%, and the balance is other components except the silicon dioxide and the calcium oxide in the kaolin, the diatomite and the carbide slag. In the embodiment, the adding amount of the fluxing agent is 0.8 percent of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 2.
TABLE 2
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1250℃ | 1300℃ | 1330℃ | 1350℃ |
Example 3
A fluxing agent for adjusting the melting characteristic of high-sulfur petroleum coke gasification ash is prepared by compounding quartz sand, quicklime and bentonite, wherein the weight percentage of silicon dioxide is 20%, the weight percentage of calcium oxide is 60%, and the balance is the other components except the silicon dioxide and the calcium oxide in the quartz sand, the quicklime and the bentonite. In the embodiment, the adding amount of the fluxing agent is 1% of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 3.
TABLE 3
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1250℃ | 1280℃ | 1305℃ | 1320℃ |
Example 4
A flux for regulating the melting characteristic of high-sulfur petroleum coke gasification ash is prepared from 10 wt% of silicon dioxide, 40 wt% of calcium oxide and the balance of kaolin, dolomite and bentonite except for silicon dioxide and calcium oxide. In the embodiment, the adding amount of the fluxing agent is 1.2% of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 4.
TABLE 4
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1230℃ | 1270℃ | 1290℃ | 1310℃ |
Example 5
A flux for regulating the melting characteristic of high-sulfur petroleum coke gasification ash is prepared from 20 wt% of silicon dioxide, 40 wt% of calcium oxide and the balance of limestone, bentonite and kaolin except silicon dioxide and calcium oxide. In the embodiment, the adding amount of the fluxing agent is 2% of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 5.
TABLE 5
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1240℃ | 1270℃ | 1285℃ | 1300℃ |
Example 6
A flux for regulating the melting characteristics of high-sulfur petroleum coke gasification ash is prepared from 15 wt% of silicon dioxide, 70 wt% of calcium oxide and the balance of silicon dioxide and calcium oxide. In the embodiment, the adding amount of the fluxing agent is 0.5 percent of the weight of the petroleum coke, and the fluxing agent and the petroleum coke are jointly ground into fine powder with the particle size of less than 200 mu m.
The Deformation Temperature (DT), Softening Temperature (ST), Hemispherical Temperature (HT), and Flow Temperature (FT) of the petroleum coke sample before and after the flux doping were measured, and the results are shown in table 6.
TABLE 6
| Sample (I) | DT | ST | HT | FT |
| Petroleum coke | 1460℃ | >1500℃ | >1500℃ | >1500℃ |
| Petroleum coke and fluxing agent | 1250℃ | 1290℃ | 1325℃ | 1360℃ |
Claims (5)
1. The fluxing agent for adjusting the melting characteristic of the high-sulfur petroleum coke gasification ash is characterized by being prepared by compounding a mineral raw material rich in silicon dioxide and a mineral raw material rich in calcium oxide.
2. The fluxing agent of claim 1, wherein the silica-rich mineral feedstock is selected from one or a combination of quartz sand, diatomaceous earth, kaolin and bentonite.
3. The fluxing agent of claim 1, wherein the calcium oxide-rich mineral feedstock is selected from one or a combination of quicklime, limestone, dolomite, and calcium oxide-rich carbide slag.
4. The fluxing agent according to claim 1, wherein the fluxing agent comprises the following components in percentage by weight: 10-50% of silicon dioxide, 30-90% of calcium oxide and 0-60% of other components; wherein the other components refer to other components except silicon dioxide and calcium oxide in the mineral raw material.
5. The method for adjusting the melting property of the high-sulfur petroleum coke gasification ash by using the fluxing agent as claimed in claim 1, wherein the fluxing agent is added into the petroleum coke, and the petroleum coke is mixed and ground with the fluxing agent, wherein the fluxing agent accounts for 0.2-2% of the weight of the petroleum coke, and the petroleum coke is made into fine powder with the particle size of less than 200 μm.
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| CN201911033301.3A CN110923014A (en) | 2019-10-28 | 2019-10-28 | Fluxing agent for adjusting melting characteristic of high-sulfur petroleum coke gasification ash and application thereof |
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| CN201911033301.3A CN110923014A (en) | 2019-10-28 | 2019-10-28 | Fluxing agent for adjusting melting characteristic of high-sulfur petroleum coke gasification ash and application thereof |
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Cited By (2)
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| CN112661162A (en) * | 2020-12-16 | 2021-04-16 | 青岛惠城环保科技股份有限公司 | Method for treating petroleum coke hydrogen production ash and mesoporous silicon material |
| CN112759374A (en) * | 2020-12-31 | 2021-05-07 | 上海化学工业区升达废料处理有限公司 | Anti-coking agent for hazardous waste incineration line and preparation method thereof |
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| WO2011075213A1 (en) * | 2009-12-18 | 2011-06-23 | Conocophillips Company | Flux addition as a filter conditioner |
| CN102399605A (en) * | 2011-09-30 | 2012-04-04 | 惠生工程（中国）有限公司 | High-ash-fusion-point petroleum coke slurry used for gasification, and preparation method thereof |
| CN106520254A (en) * | 2016-11-27 | 2017-03-22 | 山西焦化股份有限公司 | Fluxing agent capable of reducing melting point of coal ash and improving viscosity-temperature characteristic of coal, and application thereof |
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2019
- 2019-10-28 CN CN201911033301.3A patent/CN110923014A/en active Pending
Patent Citations (3)
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| WO2011075213A1 (en) * | 2009-12-18 | 2011-06-23 | Conocophillips Company | Flux addition as a filter conditioner |
| CN102399605A (en) * | 2011-09-30 | 2012-04-04 | 惠生工程（中国）有限公司 | High-ash-fusion-point petroleum coke slurry used for gasification, and preparation method thereof |
| CN106520254A (en) * | 2016-11-27 | 2017-03-22 | 山西焦化股份有限公司 | Fluxing agent capable of reducing melting point of coal ash and improving viscosity-temperature characteristic of coal, and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112661162A (en) * | 2020-12-16 | 2021-04-16 | 青岛惠城环保科技股份有限公司 | Method for treating petroleum coke hydrogen production ash and mesoporous silicon material |
| CN112759374A (en) * | 2020-12-31 | 2021-05-07 | 上海化学工业区升达废料处理有限公司 | Anti-coking agent for hazardous waste incineration line and preparation method thereof |
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Application publication date: 20200327 |