CN102703115A - Hydrotreating method for preparing gasoline by high-temperature coal tar - Google Patents
Hydrotreating method for preparing gasoline by high-temperature coal tar Download PDFInfo
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- CN102703115A CN102703115A CN2012101587201A CN201210158720A CN102703115A CN 102703115 A CN102703115 A CN 102703115A CN 2012101587201 A CN2012101587201 A CN 2012101587201A CN 201210158720 A CN201210158720 A CN 201210158720A CN 102703115 A CN102703115 A CN 102703115A
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Abstract
The invention relates to a hydrotreating method for preparing gasoline by high-temperature coal tar, belonging to the technical field of energy source materials and coal chemical industry. According to the invention, a protecting agent, a hydrogenation catalyst and a cracking catalyst are added to high-temperature coal tar, the mixture is heated to 140-170 DEG C with constant heating rate under the protection of nitrogen, and hydrogen is introduced with constant pressure ranged between 0.3MPa and 0.7MPa at a constant temperature, then the mixture is heated to 230-260 DEG C with the constant heating rate of 5-8 DEG C per minute in order to enhance the pressure of the introduced hydrogen to 11-15MPa, and heated to 360-420 DEG C with the constant heating rate of 10-15 DEG C per minute, then the mixture is subjected to cracking reaction for 1-3 hours; the reactant is filtered at the temperature of lower than 20 DEG C, the filtrate is subjected to fractionation, and then the distillate at the temperature of 60-190 DEG C is collected, so as to obtain the targeted product. The refined gasoline prepared by the method provided by the invention has the advantages that the production security is high, the catalyst activity is high and capable of being recycled and reused, the hydrogen consumption is small, and the percent conversion of the refined gasoline is high.
Description
Technical field
The present invention relates to a kind of coal-tar heavy oil hydrogenation and produce the method for gasoline, belong to energy and material and technical field of coal chemical industry.
Background technology
Black with pungent odour that coal tar generates when being the coal destructive distillation or chocolate viscous liquid are called for short tar.The coal tar that in coke production, obtains belongs to coal-tar heavy oil, one of coke oven gas purification product that it is condensation in the raw gas process of cooling, separate.During the coal high temperature carbonization, the productive rate of coal tar is generally the 3%-5% of dry coal quality.China big-and-middle-sized coal tar processing enterprise all adopts the once gasification in 40-50 age, the continuous distillation process of refrigerated separation, tube furnace heating progressively basically.The energy consumption of large-scale plant is generally 21-134kJ/t tar, and the energy consumption of packaged unit is generally up to more than the 300kJ/t tar.Middle-size and small-size coal tar processing unit (plant) has only NAPTHALENE FLAKES. (INDUSTRIAL GRADE, crude phenols, washing oil, fuel oil and pitch production system mostly.Individual enterprise's processing variety majority does not reach 20 kinds, and some also is less than 10 kinds, and amount to processing variety can reach 70 surplus kind.CHINESE COAL Tar production and processing enterprise's major part are built in the eighties; Because of at that time various condition restriction, the process for processing of coal tar, exist aspect a lot not enough in scale, technology etc.; But owing to aspect trade management, have certain basis in the construction of manufacturer; So, input if necessary, its technological improvement and production development will have good prospect.It is the big country of main energy sources with the coal that China is one, through the utilization ratio of tar processing can raising coal, is the important channel of comprehensive utilization of energy.Because ballooning oil prices; The coal tar processing industry faces an opportunity to develop preferably, but tar processing enterprise should make great efforts to develop efficient novel process, save energy when pursuing high benefit; Strengthen environmental consciousness; And need to strengthen input in science and technology, continually develop product innovation and novel process, promote the comprehensive strength of enterprise.
China is coke production big country, and coke output accounts for about 40% of world's coke output, and the coke export amount accounts for more than 60% of world's coke trade total volume of exports.From 1993, Chinese coke output ranked first in the world always.Got into since 21 century, along with the development of steel, the coke output of China rises year by year, and according to incompletely statistics, the coke output of China in 2003 has surpassed 150M t.Coal tar, coke(oven)gas are as important coke by-products, and output accounts for respectively about 4% and 17% (massfraction) of coking coal.The thick fuel of many conducts directly uses coal tar the Chemicals except that being used on a small quantity extract at present, causes and contains a large amount of SO in the flue gas
xAnd NO
x, cause serious environmental to pollute; 50% of coke(oven)gas is used for the heating fuel of pit kiln self, all the other emptying burnings, and the volume(tric)fraction of hydrogen is about 55% in the coke(oven)gas, has caused great energy dissipation.Before this; To a large amount of condensed-nuclei aromaticss, unsaturated olefin, the phenolic cpd very easily condensation under heating condition that contains in the coal tar; When adopting conventional hydrogenation means to carry out hydrotreatment, exist hydrogenation catalyst to be prone to problems such as coking and deactivation, the rising of bed pressure reduction is fast, the device cycle of operation is short.Trouble the development and use of China coal tar, existing at present perfect pressure swing adsorption can be by obtaining the hydrogen of purity 99% or more in the coke(oven)gas always, utilizes that the cheap hydrogen source in coke-oven plant is concentrated to carry out hydrotreatment to coal tar and obtain fine oil fuel.But this method need be carried out under the condition of HTHP, and the requirement of production security is increased; Use raw material to be High Purity Hydrogen, and the hydrogen proportion is bigger, is generally more than 1800 times of coal tar; And transformation efficiency is relatively low, and the transformation efficiency of treated gasoline is the highest less than 20%, and the boiling point of gained gasoline is broad respectively, and the ignition temperature when gasoline is used promotes, and the wearing and tearing when causing automobile to use increase, and reduce its work-ing life.
Summary of the invention
The objective of the invention is to produce the method for gasoline and exist production security to require problems such as height, hydrogen consumption is big, transformation efficiency is low, and provide a kind of coal-tar heavy oil hydrogenation to produce the method for gasoline in order to solve traditional coal tar hydrogenating.
The objective of the invention is to realize through following technical scheme:
A kind of coal-tar heavy oil hydrogenation of the present invention is produced the method for gasoline, and concrete preparation method is following:
1) in reaction kettle, drops into coal-tar heavy oil; Add protective material, adding coal tar quality 0.01%～0.1% hydrogenation catalyst of coal tar quality 0.001%～0.01% and add coal tar quality 0.01%～0.1% hydrogen cracking negative catalyst, mechanical stirring 10～30min;
2) be under the condition below 40 ℃ in temperature, the constant pressure feeding nitrogen replacement with 0.1～0.5Mpa in reaction system goes out the air in the reaction kettle, replaces 3～5 times, and each aeration time is 5min～20min;
3) after displacement is accomplished, above-mentioned reaction system risen to 140～170 ℃ with the constant temperature rise rate of 3～5 ℃/min after, keep constant temperature and feed hydrogen with the constant pressure of 0.3～0.7Mpa; Behind ventilation 20min～60min; Keeping under the situation of this constant pressure, reaction system is being risen to 230～260 ℃ with the constant temperature rise rate of 5～8 ℃/min, will feed hydrogen pressure and bring up to 11～15Mpa; Under the situation that keeps this constant pressure; After reaction system risen to 360 ℃～420 ℃ with the constant temperature rise rate of 10～15 ℃/min, keep this constant temperature and pressure, cracking reaction 1～3h under mechanical stirring.
4) remove hydrogen shield, reaction system is cooled to below 20 ℃ filters out upper layer substance, be i.e. protective material, hydrogenant agent and cracking negative catalyst; Get the lower floor's thing that filters out; Promptly filtrating is carried out fractionation, collects 60～190 ℃ overhead product, gets colourless transparent liquid and is title product.
Wherein, described protective material is any one in 5%～10% the palladium-carbon catalyst for the palladium mass content.
Described hydrogenant agent be in Cu powder, Ni powder, Co powder, the Mu powder any one or two or morely mix with arbitrary proportion.
Described cracking negative catalyst is the Al/Mg alloy powder.
The 4th) go on foot protective material, hydrogenant agent and the cracking negative catalyst that filters out, after gasoline washing and drying, can continue on for catalytic hydrogenation reaction.
Beneficial effect
Technology of the present invention need not carried out under the condition of HTHP, makes the raising greatly of production security; The use catalyst activity is higher, and selectivity is higher and can recycle, and reaction in confined conditions, and hydrogen gas consumption is less, is merely the half the of coal tar consumption; The transformation efficiency of coal tar refining gasoline can reach more than 30%, and the products obtained therefrom performance satisfies the 93# gasoline standard fully.
Embodiment
Below in conjunction with embodiment content of the present invention is described further.
Embodiment 1
The palladium mass content that in 5L hydrogenation still, drops into 3000g coal-tar heavy oil 15g is alloy powder (Cu/Ni=40/60) and the 150gAl/Mg alloy powder (Al/Mg=30/70) that 10% palladium-carbon catalyst, 100gCu/Ni form; Airtight after stirring; Heating goes out the air displacement in the reaction system with nitrogen, feeds nitrogen gas pressure and remains on 1.65MPa; Aeration time is 10min; Replace 3 times, this moment, to keep the temperature of reaction system be below 40 ℃ so that in the coal tar other impurity atmosphere content less than 0.05%; Be replaced with the device of logical hydrogen then, when the temperature of system rises to 160 ℃, begin slowly to feed hydrogen (keeping the pressure 0.4MPa of hydrogen this moment); When temperature rises to 258 ℃; Improve the pressure that hydrogen feeds, (ratio of coal tar and hydrogen=0.9: 1220ml), this moment, pressure was adjusted into 13.3MPa to the flow of increasing hydrogen; Temperature rises to 396 ℃+10 ℃ under this pressure; Cracking reaction 2h under this temperature and pressure condition with the coal-tar middle oil flow motion of reactor drum, makes its homogeneous reaction during cracking reaction.Reaction finishes to begin to be cooled to and filters out product and protective material, hydrogenant agent and cracking negative catalyst below 20 ℃.The upper layer substance that filters out can continue to use as catalyzer after gasoline washing and drying.Take off a layer thing and fractionate out gasoline, collect 60～190 ℃ elute, get the 1071g colourless transparent liquid.Be (coal tar) mass recovery 35.7% that feeds intake.Hydrogen gas consumption is 1300g, is merely 43% of coal tar consumption.Products obtained therefrom is through testing full up sufficient 93# gasoline standard.
Embodiment 2
In 100L hydrogenation still, drop into the 75kg coal-tar heavy oil; The palladium mass content that adds 110g is 5% palladium-carbon catalyst as protective material, add alloy powder (Cu/Ni=40/60) hydrogen catalyst that 225g brass and Ni form and add the 600gAl/Mg alloy powder as hydrogen cracking negative catalyst (Al/Mg=30/70), and the back that stirs is airtight, heats; With nitrogen the air displacement in the reaction system is gone out; Feed nitrogen gas pressure and remain on 1.71MPa, aeration time is 15min, replaces 3 times; This moment, to keep the temperature of reaction system be below 35 ℃ so that in the coal tar other impurity atmosphere content less than 0.05%; Be replaced with the device of logical hydrogen then, when the temperature of system rises to 153 ℃, begin slowly to feed hydrogen (keeping the pressure 0.4MPa of hydrogen this moment); When temperature rises to 261 ℃; Improve the pressure that hydrogen feeds, (ratio of coal tar and hydrogen=1: 1600ml), this moment, pressure was adjusted into 11.3MPa to the flow of increasing hydrogen; Temperature rises to 376 ℃+10 ℃ under this pressure; Cracking reaction 4h under this temperature and pressure condition with the coal-tar middle oil flow motion of reactor drum, makes its homogeneous reaction during cracking reaction.Reaction finishes to begin to be cooled to and filters out product and protective material, hydrogenant agent and cracking negative catalyst below 20 ℃.The upper layer substance that filters out can continue to use after gasoline washing and drying.Take off a layer thing and fractionate out gasoline, collect 60～90 ℃ overhead product, get the 27.01kg colourless transparent liquid.The recovery 36.01%.Hydrogen gas consumption is 35kg, is merely 37% of coal tar consumption.Products obtained therefrom is through testing full up sufficient 93# gasoline standard.
Claims (2)
1. a coal-tar heavy oil hydrogenation is produced the method for gasoline, it is characterized in that concrete preparation method is following:
1) in reaction kettle, drops into coal-tar heavy oil; Add protective material, adding coal tar quality 0.01%～0.1% hydrogenation catalyst of coal tar quality 0.001%～0.01% and add coal tar quality 0.01%～0.1% hydrogen cracking negative catalyst, mechanical stirring 10～30min;
2) be under the condition below 40 ℃ in temperature, the constant pressure feeding nitrogen replacement with 0.1～0.5Mpa in reaction system goes out the air in the reaction kettle, replaces 3～5 times, and each aeration time is 5min～20min;
3) after displacement is accomplished, above-mentioned reaction system risen to 140～170 ℃ with the constant temperature rise rate of 3～5 ℃/min after, keep constant temperature and feed hydrogen with the constant pressure of 0.3～0.7Mpa; Behind ventilation 20min～60min; Keeping under the situation of this constant pressure, reaction system is being risen to 230～260 ℃ with the constant temperature rise rate of 5～8 ℃/min, will feed hydrogen pressure and bring up to 11～15Mpa; Under the situation that keeps this constant pressure; After reaction system risen to 360 ℃～420 ℃ with the constant temperature rise rate of 10～15 ℃/min, keep this constant temperature and pressure, cracking reaction 1～3h under mechanical stirring.
4) remove hydrogen shield, reaction system is cooled to below 20 ℃ filters out upper layer substance, be i.e. protective material, hydrogenant agent and cracking negative catalyst; Get the lower floor's thing that filters out; Promptly filtrating is carried out fractionation, collects 60～190 ℃ overhead product, gets colourless transparent liquid and is title product;
Wherein, described protective material is any one in 5%～10% the palladium-carbon catalyst for the palladium mass content;
Described hydrogenant agent be in Cu powder, Ni powder, Co powder, the Mu powder any one or two or morely mix with arbitrary proportion;
Described cracking negative catalyst is the Al/Mg alloy powder.
2. a kind of coal-tar heavy oil hydrogenation as claimed in claim 1 is produced the method for gasoline, it is characterized in that: the 4th) go on foot protective material, hydrogenant agent and the cracking negative catalyst that filters out, after gasoline washing and drying, can continue on for catalytic hydrogenation reaction.
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| CN201210158720.1A CN102703115B (en) | 2012-05-22 | 2012-05-22 | Hydrotreating method for preparing gasoline by high-temperature coal tar |
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| CN201210158720.1A CN102703115B (en) | 2012-05-22 | 2012-05-22 | Hydrotreating method for preparing gasoline by high-temperature coal tar |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105745310A (en) * | 2013-11-19 | 2016-07-06 | 环球油品公司 | Process for hydrotreating a coal tar stream |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004018814A (en) * | 2002-06-20 | 2004-01-22 | Furukawa Co Ltd | Desulfurization method |
| CN101864327A (en) * | 2010-04-29 | 2010-10-20 | 长岭炼化岳阳工程设计有限公司 | Coal tar hydrogenation modification method |
| CN102051218A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrotreating method for inferior heavy oil material |
| CN102443424A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing clean diesel from coal tar |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004018814A (en) * | 2002-06-20 | 2004-01-22 | Furukawa Co Ltd | Desulfurization method |
| CN102051218A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrotreating method for inferior heavy oil material |
| CN101864327A (en) * | 2010-04-29 | 2010-10-20 | 长岭炼化岳阳工程设计有限公司 | Coal tar hydrogenation modification method |
| CN102443424A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing clean diesel from coal tar |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105745310A (en) * | 2013-11-19 | 2016-07-06 | 环球油品公司 | Process for hydrotreating a coal tar stream |
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