CN108085051A - A kind of method with iron scale catalytic pyrolysis high temperature coal-tar - Google Patents
A kind of method with iron scale catalytic pyrolysis high temperature coal-tar Download PDFInfo
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- CN108085051A CN108085051A CN201711392866.1A CN201711392866A CN108085051A CN 108085051 A CN108085051 A CN 108085051A CN 201711392866 A CN201711392866 A CN 201711392866A CN 108085051 A CN108085051 A CN 108085051A
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- tar
- high temperature
- coal
- catalytic pyrolysis
- iron scale
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- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of methods with iron scale catalytic pyrolysis high temperature coal-tar, belong to coal tar processing technology field.This method is specifically：The catalyst of selection energy catalytic pyrolysis high temperature coal-tar is 0.1~10 in 500~800 DEG C of catalytic pyrolysis temperature, tar and catalyst quality ratio:1, inert gas flow velocity is that high temperature coal-tar is converted into tar light oil under 50~200ml/min；The catalyst is iron scale.The present invention is by using cheap iron scale to high temperature coal-tar efficient catalytic thermal cracking, high value added utilization for high temperature coal-tar and industrial residue provides new approaches, catalytic pyrolysis technological operation simultaneously is simple, is easily achieved, thus has a good application prospect.
Description
Technical field
The invention belongs to coal tar processing technology field, relate in particular to a kind of by the use of cheap industrial residue as catalysis
Agent improves the added value of high temperature coal-tar with this to high temperature coal-tar efficient catalytic thermal cracking.
Background technology
Principal by product of the high temperature coal-tar as coking accounts for the 3%-4% of Coking Coal Quality.According to incompletely statistics,
About 22,000,000 t of China's high temperature coal-tar aggregated capacity at present.High temperature coal-tar is mainly made of aromatic hydrocarbon, is formed more than 10,000 kinds,
Most coking of coal products are difficult to substitute, and content is less in coal tar.It can be seen that carrying out coal tar deep processing has
Very important meaning.But during current coal tar separation and process for refining, pitch accounts for more than 50% in coal tar,
Since pitch macromolecular is highly condensed aromatic compound, the complicated heavy organics of complicated and oxygen-containing, nitrogen, sulphur etc. are formed,
Cause its working ability poor.Therefore, in high temperature coal-tar pitch generally as replacement for heavy fuel, for glass, ceramics etc.
Thermal energy industry and as production carbon black raw material or for producing the carbon materials such as needle coke, carbon fiber.In order to improve high temperature coal tar
The added value of oil, economically viable mode are to carry out lighting processing to high temperature coal-tar to carry out fine chemicals to obtain
Enormous profits.
Hydrogenation of high temperature coal tar made fuel oil technology emerging in recent years opens the new way for improving its added value, the skill
Art is in high temperature, high pressure and H2Under the conditions of existing, hydrogenation reaction is carried out to high temperature coal-tar on catalyst bed, changes it
Molecular structure, and the hetero atoms such as N, S are removed, so as to obtain gasoline, diesel oil, kerosene lamp fuel oil.But due to high temperature coal-tar
Middle pitch accounts for more than 50%, causes the easy coking of catalyst, causes expensive catalyst service life very short, hydrogenation process hydrogen consumption
Greatly, cause the process industrialization difficulty big, less economical.
The content of the invention
To overcome the shortcomings of existing process technology, the invention aims to by selecting energy, efficiently thermal cracking high-temperature coal is burnt
High temperature coal-tar is efficiently converted into tar light oil, to improve the economy of process by the waste residue and waste product of oil as catalyst.
To achieve the above object, the technical solution adopted by the present invention is：
The present invention provides a kind of methods with iron scale catalytic pyrolysis high temperature coal-tar, are specifically：Selection can be high
The industrial residue of catalytic pyrolysis high temperature coal-tar is imitated as cheap catalyst, in 500~800 DEG C of catalytic pyrolysis temperature, coke
Oil is 0.1~10 with catalyst quality ratio:Under 1, high temperature coal-tar is efficiently converted into tar light oil；The catalyst is oxygen
Change iron.
Further, the catalytic pyrolysis temperature is 750 DEG C, and the tar is 7.5 with catalyst quality ratio:1；It is described
Inert gas flow velocity is 50ml/min.It is after carrying out coal tar catalytic pyrolysis under this process condition, the modification being collected into is burnt
Oil is analyzed, and 83% is tar light oil, and wherein fat compound is 9%, aromatic compounds 74%, phenolic compound
For 17%.
Compared with prior art, the present invention has following technique effect：
1st, it is the high value added utilization of high temperature coal-tar and the recycling of industrial residue waste product, provides a new think of
Road has economy and environment double benefit.
2nd, catalytic thermal cracking catalyst is cheap and easy to get, active height, and process economics are high.
3rd, catalytic pyrolysis technological operation is simple, it is easy to accomplish, it has a good application prospect.
Specific embodiment
It is specific embodiments of the present invention below, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 600 DEG C under an inert atmosphere,
0.2g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 100ml/min nitrogen atmospheres.It is cold by constant temperature
But slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 82% is burnt for lightweight
Oil, wherein fat compound are 11%, aromatic compounds 62%, phenolic compound 27%.
Embodiment 2：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 550 DEG C under an inert atmosphere,
0.2g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 100ml/min nitrogen atmospheres.It is cold by constant temperature
But slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 79% is burnt for lightweight
Oil, wherein fat compound are 10%, aromatic compounds 60%, phenolic compound 30%.
Embodiment 3：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 750 DEG C under an inert atmosphere,
0.2g coal tar is added at a temperature of this, coal tar carries out catalysis pyrolysis in 100ml/min nitrogen atmospheres.Pass through constant temperature cooling bath
Collect the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 72% is tar light oil,
Middle fat compound is 14%, aromatic compounds 68%, phenolic compound 18%.
Embodiment 4：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 600 DEG C under an inert atmosphere,
1g coal tar is added at a temperature of this, coal tar carries out catalysis pyrolysis in 200ml/min nitrogen atmospheres.It is received by constant temperature cooling bath
The tar that collection coal tar catalysis pyrolysis condenses out, after ten minutes reaction terminate.The upgrading tar being collected into is analyzed,
79% is tar light oil, and wherein fat compound is 13%, aromatic compounds 62%, phenolic compound 25%.
Embodiment 5：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 750 DEG C under an inert atmosphere,
20g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 200ml/min nitrogen atmospheres.It is cold by constant temperature
But slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 70% is burnt for lightweight
Oil, wherein fat compound are 15%, aromatic compounds 65%, phenolic compound 20%.
Embodiment 6：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 600 DEG C under an inert atmosphere,
10g coal tar is added at a temperature of this, coal tar carries out catalysis pyrolysis in 100ml/min nitrogen atmospheres.Pass through constant temperature cooling bath
Collect the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 69% is tar light oil,
Middle fat compound is 16%, aromatic compounds 63%, phenolic compound 21%.
Embodiment 7：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 700 DEG C under an inert atmosphere,
10g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 200ml/min nitrogen atmospheres.It is cold by constant temperature
But slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 80% is burnt for lightweight
Oil, wherein fat compound are 14%, aromatic compounds 64%, phenolic compound 22%.
Embodiment 8：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 550 DEG C under an inert atmosphere,
2g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 50ml/min nitrogen atmospheres.It is cooled down by constant temperature
Slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 77% is tar light oil,
Wherein fat compound is 10%, aromatic compounds 61%, phenolic compound 29%.
Embodiment 9：The iron scale catalyst of 2g is weighed (containing ferrous oxide 30~100%, from Ma'an Mountain's steel share
Co., Ltd) it is placed in fixed bed reactors, catalytic cracking reaction device temperature is then raised to 750 DEG C under an inert atmosphere,
15g coal tar is continuously added at a temperature of this, coal tar carries out catalysis pyrolysis in 50ml/min nitrogen atmospheres.It is cooled down by constant temperature
Slot collects the tar that coal tar catalysis pyrolysis condenses out.The upgrading tar being collected into is analyzed, 83% is tar light oil,
Wherein fat compound is 9%, aromatic compounds 74%, phenolic compound 17%.
Claims (2)
- A kind of 1. method with iron scale catalytic pyrolysis high temperature coal-tar, which is characterized in that selection can catalytic pyrolysis height The catalyst of warm coal tar is 0.1~10 in 500~800 DEG C of catalytic pyrolysis temperature, tar and catalyst quality ratio:1, it is lazy Property gas flow rate for high temperature coal-tar is converted into tar light oil under 50~200ml/min；The catalyst is iron scale.
- 2. the method for iron scale catalytic pyrolysis high temperature coal-tar is used as described in claim 1, which is characterized in that described to urge It is 750 DEG C to change thermal cracking temperature, and the tar is 7.5 with catalyst quality ratio:1；The inert gas flow velocity is 50ml/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354856A (en) * | 2019-08-22 | 2019-10-22 | 安徽工业大学 | A kind of situ catalytic denitration is catalyzed the catalyst and its application method of coal char combustion simultaneously |
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| CN102059122A (en) * | 2010-11-15 | 2011-05-18 | 苏忠 | Catalyst for splitting oil tar and preparation method thereof |
| US20130172637A1 (en) * | 2010-09-03 | 2013-07-04 | G4 Insights Inc. | Method of hydrogasification of biomass to methane with low depositable tars |
| CN104130799A (en) * | 2014-08-04 | 2014-11-05 | 太原理工大学 | Coal tar catalytic upgrading method |
| CN105623736A (en) * | 2016-03-23 | 2016-06-01 | 上海河图工程股份有限公司 | Whole-fraction catalytic thermal-cracking method for high-temperature coal tar |
| CN106492815A (en) * | 2016-10-12 | 2017-03-15 | 中国林业科学研究院林产化学工业研究所 | A kind of biomass gasification tar cracking Fe base catalyst and preparation method thereof |
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2017
- 2017-12-21 CN CN201711392866.1A patent/CN108085051A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130172637A1 (en) * | 2010-09-03 | 2013-07-04 | G4 Insights Inc. | Method of hydrogasification of biomass to methane with low depositable tars |
| CN102059122A (en) * | 2010-11-15 | 2011-05-18 | 苏忠 | Catalyst for splitting oil tar and preparation method thereof |
| CN104130799A (en) * | 2014-08-04 | 2014-11-05 | 太原理工大学 | Coal tar catalytic upgrading method |
| CN105623736A (en) * | 2016-03-23 | 2016-06-01 | 上海河图工程股份有限公司 | Whole-fraction catalytic thermal-cracking method for high-temperature coal tar |
| CN106492815A (en) * | 2016-10-12 | 2017-03-15 | 中国林业科学研究院林产化学工业研究所 | A kind of biomass gasification tar cracking Fe base catalyst and preparation method thereof |
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| CN110354856A (en) * | 2019-08-22 | 2019-10-22 | 安徽工业大学 | A kind of situ catalytic denitration is catalyzed the catalyst and its application method of coal char combustion simultaneously |
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Application publication date: 20180529 |