CN111218294A - Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point - Google Patents

Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point Download PDF

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Publication number
CN111218294A
CN111218294A CN201811438421.7A CN201811438421A CN111218294A CN 111218294 A CN111218294 A CN 111218294A CN 201811438421 A CN201811438421 A CN 201811438421A CN 111218294 A CN111218294 A CN 111218294A
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China
Prior art keywords
coal
softening point
purifying
quinoline insoluble
pitch
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CN201811438421.7A
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Chinese (zh)
Inventor
许祥军
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Baowu Carbon Material Technology Co ltd
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Baowu Carbon Material Technology Co ltd
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Priority to CN201811438421.7A priority Critical patent/CN111218294A/en
Publication of CN111218294A publication Critical patent/CN111218294A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • C10C3/02Working-up pitch, asphalt, bitumen by chemical means reaction
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • C10C3/06Working-up pitch, asphalt, bitumen by distillation

Abstract

The invention discloses a method for purifying high-softening-point quinoline insoluble coal-series asphalt, which comprises the steps of adding coal tar wash oil fraction and purified coal tar soft asphalt into an extracting agent preparation tank according to the mass ratio of 100:3-15, and uniformly mixing the mixture to be used as an extracting agent of high-softening-point quinoline insoluble asphalt (HQRP); adding the extracting agent and HQRP into an extraction tank according to the mass ratio of 2-4:1, and uniformly stirring at 60-80 ℃; and after stirring, conveying the mixture in the extraction tank into a centrifuge for centrifugal separation, and conveying the obtained centrifugate into a distillation tower to recover the wash oil fraction for reuse. The extraction rate of HQRP is greatly improved by the compound solvent, and the production cost can be greatly reduced by adopting the compound solvent.

Description

Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point
Technical Field
The invention relates to a purification process technology of high-softening-point high-quinoline-insoluble pitch (HQRP), which is used for purifying the pitch to obtain purified pitch with quinoline insoluble content (QI) lower than 0.1 percent, a production device can stably operate, and the obtained pitch can be used for preparing high value-added carbon products such as needle coke, spinning pitch and the like.
Background
A typical representation of HQRP is the direct coal liquefaction residue, which typically has the characteristics of: the quinoline insoluble content is more than 30 percent, the softening point is higher than 180 ℃, the softening point of the coal tar medium temperature pitch is 85 ℃, and the quinoline insoluble content is lower than 10 percent. With the development of high-end carbon materials such as needle coke, carbon fiber and the like, the market demand for QI-free coal-based asphalt is increasing.
The direct coal liquefaction technology is one typical of the modern coal chemical technology, and an industrial demonstration device of the technology is a leading-edge project of the development of the modern coal chemical technology in the 'eleven-five' period of China. Currently, the Shenhua coal direct liquefaction demonstration plant located in Nemonte Ordos has successfully reached the 108 million tons/year design capacity of the design. In the direct coal liquefaction production process, no matter which direct coal liquefaction process is applied, no matter which solid-liquid separation method (reduced pressure distillation, solvent extraction, filtration and the like) is adopted, liquefaction residues which account for about 30% of the quantity of the raw coal to be liquefied are generated. It is a high-carbon, high-ash and high-sulfur substance, mainly composed of unconverted coal, inorganic mineral substances, coal liquefaction catalyst and condensed ring compound of condensed aromatic ring.
So far, the utilization of the direct coal liquefaction residues is mainly to mix the direct coal liquefaction residues with raw coal for combustion, the economy is poor, and the environmental pollution is large, so that the utilization research of the residues at home and abroad is always more important, the preparation of high-end carbon materials which are important in the development of modern science and technology becomes a research hotspot direction of the comprehensive utilization of the direct coal liquefaction residues, and research reports of the preparation of needle coke, MCMB, super activated carbon, high-end asphalt products and the like by using the residues become hotspots in the field. However, the purification technology of the liquefaction residues is still a technical bottleneck restricting the field.
The invention patent with application number 201110294873.4 discloses a method for purifying coal direct liquefaction residues, which adopts a multi-stage cyclone and filtration process and adopts benzene, toluene, xylene, naphthalene aromatic hydrocarbon, furfural, tetrahydrofuran and quinoline as an extracting agent for purification. The patent does not mention key technical indexes such as process temperature, purified asphalt yield and the like.
The invention patent with application number 201110300857.1 discloses a method for purifying coal direct liquefaction residues, which adopts a multi-stage cyclone and filtration process, selects an extracting agent as an oil product directly produced in the coal liquefaction process, and has a boiling range from a primary boiling point to 110 ℃, but the yield of purified asphalt is only 37%.
The invention patent with the application number of 201110300868.X discloses a method for purifying coal direct liquefaction residues, which adopts a multi-stage cyclone combined multi-stage extraction filtration process, two selected extracting agents are oil products directly generated in the coal liquefaction process, the boiling range ranges are fractions from a primary boiling point to 110 ℃ and from 160 ℃ to 260 ℃, although the yield of purified asphalt reaches 65%, the technology has the advantages of complex process route, more equipment, high investment and high operation energy consumption.
The invention patent with application number 201510179149.5 discloses a method for purifying coal direct liquefaction residues, and the method adopts a supercritical extraction method, but the yield of purified asphalt is only 10%.
The invention patent with application number 201010614927.6 discloses a method for purifying coal direct liquefaction residues, and relates to an ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from the coal direct liquefaction residues, and a method for separating the asphaltene, the preasphaltene and/or the heavy oil from the coal direct liquefaction residues by using the ionic liquid composite extracting agent. Although the method can obtain higher yield of the purified asphalt, the preparation process of the ionic liquid composite extracting agent is complex, the cost is higher, and the comprehensive economic benefit of the purification process is lower.
The direct coal liquefaction residue is one of the quinoline insoluble coal-series asphalt with high softening point, and the range of asphalt contained in the quinoline insoluble coal-series asphalt with high softening point is wider. The source of the quinoline insoluble pitch (HQRP) with high softening point is the direct coal liquefaction residue; the second is coal tar pitch after thermal polymerization or oxidation. For the quinoline insoluble asphalt with high softening point, no better purification method exists.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a low-cost purification process of quinoline insoluble coal-based asphalt with high softening point.
The technical scheme of the invention is that the method for purifying the high-softening-point high-quinoline insoluble coal-series asphalt comprises the steps of adding coal tar wash oil fraction and purified coal tar soft asphalt into an extracting agent preparation tank according to the mass ratio of 100:3-15, and uniformly mixing the coal tar wash oil fraction and the purified coal tar soft asphalt to serve as an extracting agent of the high-softening-point high-quinoline insoluble asphalt (HQRP);
adding the extracting agent and HQRP into an extraction tank according to the mass ratio of 2-4:1, and uniformly stirring at 60-80 ℃; after stirring, the mixture in the extraction tank is sent to a centrifuge for centrifugal separation, and the obtained centrifugate is sent to a distillation tower for recycling the wash oil fraction (the wash oil fraction is extracted from the top of the distillation tower). The product obtained at the bottom of the distillation column is the purified product RHQRP.
According to the method for purifying the quinoline insoluble coal-based pitch with the high softening point and the high softening point, the centrifugal waste solid obtained after the centrifugal separation can be preferably transported to a power plant to be combusted and generate power.
According to the method for purifying the quinoline insoluble coal-based pitch with the high softening point, the stirring time is preferably 5-50 min. More preferably, the stirring time is 10 to 30 min. Generally speaking, it is sufficient to stir until homogeneous, i.e., the density of the various portions of the mixture is uniform.
According to the method for purifying the quinoline insoluble coal-series asphalt with the high softening point, the rotating speed of the centrifugal machine is preferably 2000-6000 rpm.
Further, the rotating speed of the centrifugal machine is adjusted through a frequency converter of the centrifugal machine.
Further, the rotating speed of the centrifugal machine is 3000-5500 rpm.
According to the method for purifying the quinoline insoluble coal-series pitch with the high softening point, the working environment of the distillation tower is preferably normal pressure.
According to the method for purifying the quinoline insoluble coal-series asphalt with the high softening point, the tower top temperature of the distillation tower is preferably 220-280 ℃.
According to the method for purifying the quinoline insoluble coal-based pitch with the high softening point, the mass ratio of the coal tar wash oil fraction to the purified coal tar maltha is preferably 100: 5-10.
The basic process of the invention is that coal tar wash oil fraction (DMNO for short) and purified coal tar maltha (RP for short) are added into an extracting agent preparation tank according to a certain proportion and are uniformly mixed to be used as an extracting agent of HQRP. Adding an extracting agent and HQRP into an extraction tank according to a certain proportion, and stirring for a certain time at a certain temperature. And after stirring, conveying the mixture in the extraction tank into a centrifuge for centrifugal separation. The centrifugate is sent to a distillation tower to recover the wash oil fraction for reuse, and the centrifuged waste solids can be transported to a power plant for combustion and power generation.
The purification level refers to the quinoline insoluble content of the purified product RHQRP, the lower the content is, the better the content is, the quinoline insoluble content of the RHQRP can reach below 0.1%, and on the premise of similar simple process (same as the process of the invention, and without using DMNO and RP as mixed extraction solvent), the content of the quinoline insoluble of the product of other technologies is about 0.2% by actual measurement and analysis.
The invention has the beneficial effects that:
the extraction method adopts the mixture of the coal tar wash oil fraction (DMNO) and the purified coal tar soft pitch (RP) as the extractant, selects the common product of a coal tar processing plant according to the basic chemical principle of similarity and intermiscibility, and greatly improves the extraction rate of HQRP (by 10-20% under the premise of similar simple process) by compounding the solvent on the one hand and greatly reduces the production cost by adopting the compounding solvent on the other hand. The centrifugal separation method for liquid and solid can improve the separation efficiency of liquid and solid and the purification level of RHQRP, and meanwhile, the centrifugal separation process is simple and the industrial device is reliable to operate.
Drawings
FIG. 1 is a flow chart of the purification process of quinoline insoluble coal-based pitch with high softening point.
Detailed Description
Examples
Adding coal tar washing oil fraction (DMNO) and purified coal tar soft pitch (RP) into an extracting agent preparation tank according to a certain proportion, and uniformly mixing to obtain the HQRP extracting agent. Adding an extracting agent and HQRP into an extraction tank according to a certain proportion, and stirring for a certain time at a certain temperature. And after stirring, conveying the mixture in the extraction tank into a centrifuge for centrifugal separation. After the separation is finished, carrying out normal pressure distillation on the centrifugate, cutting DMNO with the distillation range of 220-280 ℃ from the top, and controlling the mass of the DMNO obtained by distillation to be equal to that of the DMNO put into HDR; the bottom product of the distillation column was RHQRP, weighed and subjected to QI content analysis. The purification yield (RHQRP mass-RP mass)/HQRP mass was as follows:
test results table
The main characteristic indexes of the raw materials and the products in the above embodiment are as follows:
1)DMNO
index name methylnaphthalene (α + beta) Quinoline content pH value
Control value ≥85% ≤0.8% ≥7
2)RP
3)HQRP
4)RHQRP
The method greatly improves the extraction rate of HQRP by using common products of a coal tar processing plant and compounding a solvent, and simultaneously greatly reduces the production cost. The centrifugal separation method for liquid and solid can improve the separation efficiency of liquid and solid and the purification level of RHQRP, and meanwhile, the centrifugal separation process is simple and the industrial device is reliable to operate.

Claims (9)

1. A method for purifying quinoline insoluble coal-based asphalt with high softening point is characterized by comprising the following steps: adding the coal tar wash oil fraction and the purified coal tar maltha into an extracting agent preparation tank according to the mass ratio of 100:3-15, and uniformly mixing to obtain an extracting agent of high-softening-point quinoline insoluble pitch (HQRP);
adding the extracting agent and HQRP into an extraction tank according to the mass ratio of 2-4:1, and uniformly stirring at 60-80 ℃; and after stirring, conveying the mixture in the extraction tank into a centrifuge for centrifugal separation, and conveying the obtained centrifugate into a distillation tower to recover the wash oil fraction for reuse.
2. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: and carrying the centrifugal waste solids obtained after centrifugal separation to a power plant for combustion and power generation.
3. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: the stirring time is 5-50 min.
4. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: the rotating speed of the centrifugal machine is 2000-6000 rpm.
5. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 4, which is characterized in that: the rotating speed of the centrifugal machine is adjusted through a frequency converter of the centrifugal machine.
6. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 4, which is characterized in that: the rotating speed of the centrifuge is 3000-5500 rpm.
7. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: the working environment of the distillation tower is normal pressure.
8. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: the tower top temperature of the distillation tower is 220-280 ℃.
9. The method for purifying the quinoline insoluble coal-based pitch with high softening point according to claim 1, which is characterized in that: the mass ratio of the coal tar wash oil fraction to the purified coal tar maltha is 100: 5-10.
CN201811438421.7A 2018-11-27 2018-11-27 Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point Pending CN111218294A (en)

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101475820A (en) * 2009-01-23 2009-07-08 北京石油化工学院 Purification method for coal pitch
CN101508903A (en) * 2009-03-20 2009-08-19 上海宝钢化工有限公司 Process for continuously removing quinoline insolubles in coal tar pitch
CN101787298A (en) * 2009-01-23 2010-07-28 北京石油化工学院 Coal art pitch purification method
CN101885976A (en) * 2010-07-02 2010-11-17 神华集团有限责任公司 Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof
CN102653397A (en) * 2011-03-01 2012-09-05 辽宁科技大学 Preparation method of coal tar-based mesocarbon microbead
CN102965135A (en) * 2012-10-31 2013-03-13 山西永东化工股份有限公司 Purification method for coal tar maltha
CN103013566A (en) * 2011-09-23 2013-04-03 北京三聚创洁科技发展有限公司 Technology for preparing needle coke raw material from coal-tar pitch
CN103242880A (en) * 2013-05-08 2013-08-14 武汉钢铁(集团)公司 High-quality impregnant asphalt production process
CN104789248A (en) * 2015-04-23 2015-07-22 中国科学院山西煤炭化学研究所 Method for preparing mesophase pitch by coal-tar pitch
CN105199766A (en) * 2015-10-22 2015-12-30 鞍山兴德材料科技股份有限公司 Preparation method of mesophase pitch coke raw material for power lithium battery cathode material
CN105778968A (en) * 2016-04-08 2016-07-20 神华集团有限责任公司 Method for preparing impregnating pitch, impregnating pitch and application thereof
KR101645814B1 (en) * 2014-10-17 2016-08-05 오씨아이 주식회사 Pitch as carbonaceous raw material and method for manufacturing pitch as carbonaceous raw material
CN105861014A (en) * 2016-04-08 2016-08-17 神华集团有限责任公司 Method for preparing impregnation pitch using direct coal liquefaction residue, impregnation pitch and application thereof
US20170174999A1 (en) * 2015-12-18 2017-06-22 National Chung Shan Institute Of Science And Technology Method of manufacturing refined pitch
US10041004B2 (en) * 2014-11-06 2018-08-07 Uop Llc Processes for producing deashed pitch
CN108410491A (en) * 2018-03-14 2018-08-17 煤炭科学技术研究院有限公司 A kind of method and system preparing pitch using coal liquefaction residue

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787298A (en) * 2009-01-23 2010-07-28 北京石油化工学院 Coal art pitch purification method
CN101475820A (en) * 2009-01-23 2009-07-08 北京石油化工学院 Purification method for coal pitch
CN101508903A (en) * 2009-03-20 2009-08-19 上海宝钢化工有限公司 Process for continuously removing quinoline insolubles in coal tar pitch
CN101885976A (en) * 2010-07-02 2010-11-17 神华集团有限责任公司 Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof
CN102653397A (en) * 2011-03-01 2012-09-05 辽宁科技大学 Preparation method of coal tar-based mesocarbon microbead
CN103013566A (en) * 2011-09-23 2013-04-03 北京三聚创洁科技发展有限公司 Technology for preparing needle coke raw material from coal-tar pitch
CN102965135A (en) * 2012-10-31 2013-03-13 山西永东化工股份有限公司 Purification method for coal tar maltha
CN103242880A (en) * 2013-05-08 2013-08-14 武汉钢铁(集团)公司 High-quality impregnant asphalt production process
KR101645814B1 (en) * 2014-10-17 2016-08-05 오씨아이 주식회사 Pitch as carbonaceous raw material and method for manufacturing pitch as carbonaceous raw material
US10041004B2 (en) * 2014-11-06 2018-08-07 Uop Llc Processes for producing deashed pitch
CN104789248A (en) * 2015-04-23 2015-07-22 中国科学院山西煤炭化学研究所 Method for preparing mesophase pitch by coal-tar pitch
CN105199766A (en) * 2015-10-22 2015-12-30 鞍山兴德材料科技股份有限公司 Preparation method of mesophase pitch coke raw material for power lithium battery cathode material
US20170174999A1 (en) * 2015-12-18 2017-06-22 National Chung Shan Institute Of Science And Technology Method of manufacturing refined pitch
CN105778968A (en) * 2016-04-08 2016-07-20 神华集团有限责任公司 Method for preparing impregnating pitch, impregnating pitch and application thereof
CN105861014A (en) * 2016-04-08 2016-08-17 神华集团有限责任公司 Method for preparing impregnation pitch using direct coal liquefaction residue, impregnation pitch and application thereof
CN108410491A (en) * 2018-03-14 2018-08-17 煤炭科学技术研究院有限公司 A kind of method and system preparing pitch using coal liquefaction residue

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