CN103980937A - Method for preparing clean fuel from dephenolized phenol oil - Google Patents
Method for preparing clean fuel from dephenolized phenol oil Download PDFInfo
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- CN103980937A CN103980937A CN201410185278.0A CN201410185278A CN103980937A CN 103980937 A CN103980937 A CN 103980937A CN 201410185278 A CN201410185278 A CN 201410185278A CN 103980937 A CN103980937 A CN 103980937A
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Abstract
The invention discloses a method for preparing clean fuel from dephenolized phenol oil and belongs to the field of environmental protection and energy technology. The invention is characterized in that the method is a technology of producing clean fuel by steps of carrying out low-temperature hydrogenation on dephenolized phenol oil used as a raw material, carrying out hydrofinishing and distilling. The method is characterized by comprising the following specific steps: injecting dephenolized phenol oil into a section of hydrogenation tower filled with a hydrogenation catalyst, and carrying out high-pressure low-temperature hydrogenation to remove triple bond of carbon and double bond of carbon in dephenolized phenol oil; letting dephenolized phenol oil obtained after hydrogenation enter a hydrofinishing tower to carry out hydrogenation and raise quality, carrying out a monoolefine hydrogenation saturation reaction to remove a monoene compound, desulfurizing, denitrifying, removing colloid to produce an odor-free high-quality naphtha and diesel oil mixture, and distilling to obtain gasoline and diesel oil distillate oil, wherein a catalyst used in hydrofinishing is a sulfide catalyst. According to the invention, utilization rate of dephenolized phenol oil is raised; consumption is reduced and energy is saved; life of the catalyst is prolonged; technological process is simple and investment is saved; and operation safety factor of a device is raised. The method has a simple technology and has good economic benefit and industrial application prospect.
Description
Technical field
The invention belongs to environment protection and energy technology field, relate to the method for a kind of removal phenol carbolic oil clean fuel processed.
Background technology
Along with the progressively exhaustion of petroleum resources and day by day serious heaviness and in poor quality trend, and increasingly strict legislations of environmental protection, develop other petroleum replacing resource and purification techniques thereof and demonstrate extremely important realistic meaning and economic worth.In Coal Chemical Industry process, coal tar is as one of staple product of coking industry, and its output accounts for 3%～4% of shove charge coal, and its composition is very complicated, produces about 15.00Mt per year.Coal tar is mainly used to processing light oil, carbolic oil, naphtalene oil and modified pitch etc., then after deep processing, produces the multiple industrial chemicals such as benzene, phenol, naphthalene, anthracene, and product amount is numerous, of many uses.Cut before 170 DEG C, coal tar is light oil; The cut of 170～210 DEG C is mainly carbolic oil; The cut of 210～230 DEG C is mainly naphtalene oil; The cut of 230～300 DEG C is mainly washing oil; The cut of 280～360 DEG C is mainly a carbolineum; The cut of 280～360 DEG C is a carbolineum; Anthracene oil cut initial boiling point is 310 DEG C.Removal phenol carbolic oil refers to that carbolic oil sloughed the oil after phenol by sodium hydroxide, and the solution after sodium hydroxide dephenolize, sodium phenolate solution, is the raw material that extracts meal, carries out meal again and refine after extracting.In coal tar, the content of removal phenol carbolic oil is in 3% left and right, and the fraction conventionally cutting in the actual course of processing is all greater than 3%, for Coal Chemical Industry, the qualified naphthalene content that dispatches from the factory of removal phenol carbolic oil requires < 10%, be approximately between 7% to 9%, due to production unstable, sometimes also can be far longer than 10%.At present, in technique, the processing of removal phenol carbolic oil is roughly had to following several means: the first is back to mix in mixing oil (mixture of pitch, scallion oil and other Residual oil after tar processing), reduce mixing oil viscosity, but the price of mixing oil, lower than the price of removal phenol carbolic oil, has also caused the waste of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） simultaneously.The second treatment process is to rebuild a set of rectifier unit, by removal phenol carbolic oil re-distillation, can reclaim a part of naphthalene.The third is as intermediates direct marketing by removal phenol carbolic oil.
For abundant removal phenol carbolic oil recycling problem, according to the chemical constitution of removal phenol carbolic oil and character, we have successfully developed the new technology that clean fuel is produced in removal phenol carbolic oil high pressure low temperature hydrogenation-hydrofining-air distillation.Removal phenol carbolic oil injects the one-stage hydrogenation tower that hydrogenation catalyst is housed, and carries out high pressure low temperature hydrogenation and removes carbon carbon triple bond and carbon-carbon double bond in removal phenol carbolic oil; After hydrogenation, removal phenol carbolic oil enters hydrofining tower, carry out hydrogenation upgrading, the catalyzer that hydrofining is used is sulfide catalyst, remove monoene compound by monoolefin hydrogenation saturated reaction, and desulfurization, denitrogenation, produce to obtain free from extraneous odour, petrol and diesel oil mixing oil that quality is high except colloid, then obtain gasoline and diesel oil distillate oil through distillation.In high pressure low temperature hydrogenation-hydrofining-air distillation, producing without the three wastes, is the process of green a, recycling.Following known technology, all comes with some shortcomings:
Chinese patent, publication number: CN103589466A, having introduced a kind of removal phenol carbolic oil by coal chemical technology is applied in oil fuel, utilize the high characteristic of allotment of removal phenol carbolic oil, be prepared into that a kind of production cost is low, oxidation stability is high, benzene content is low, the method for the oil fuel of normal viscosity, but removal phenol carbolic oil added value utilization ratio is low.
Summary of the invention
The method that the invention provides a kind of removal phenol carbolic oil clean fuel processed is low and secondary pollution problems for removal phenol carbolic oil conversion process added value, taking high-quality petrol and diesel oil as target product, realize containing removal phenol carbolic oil recycling, make the energy-conservation and environmental protection of production process, avoided secondary pollution.Specifically, the present invention injects removal phenol carbolic oil in the one-stage hydrogenation tower that hydrogenation catalyst is housed, and carries out high pressure low temperature hydrogenation and removes carbon carbon triple bond and carbon-carbon double bond in removal phenol carbolic oil; After hydrogenation, removal phenol carbolic oil enters hydrofining tower, carry out hydrogenation upgrading, the catalyzer that hydrofining is used is sulfide catalyst, remove monoene compound by monoolefin hydrogenation saturated reaction, and desulfurization, denitrogenation, produce to obtain free from extraneous odour, petrol and diesel oil mixing oil that quality is high except colloid, then obtain gasoline and diesel oil distillate oil through distillation.The present invention has improved removal phenol carbolic oil utilization ratio, energy-conservation of consumption reduction, has extended catalyst life, and flow process is simple and reduce investment outlay, and increases device operating safety factor.
Technical scheme of the present invention is as follows:
A method for removal phenol carbolic oil clean fuel processed, injects removal phenol carbolic oil in the one-stage hydrogenation tower that hydrogenation catalyst is housed, and carries out low temperature hydrogenation and removes diolefin in removal phenol carbolic oil, feeding temperature 120-180 DEG C, hydrogen partial pressure 4-8MPa, volume space velocity 1-4.0h
-1, hydrogen to oil volume ratio 400-800:1; Hydrogenation catalyst is metal supported catalyst or metal sulfide catalyst; After hydrogenation, removal phenol carbolic oil enters hydrofining tower, carries out hydrogenation upgrading, feeding temperature 320-360 DEG C, hydrogen partial pressure 6-8MPa, volume space velocity 0.4-1.0h
-1, hydrogen to oil volume ratio 600-1200:1; Hydrobon catalyst is sulfide catalyst; Distillate after hydrofining, through air distillation, cuts into gasoline (<180 DEG C) and diesel oil (>180 DEG C) according to recovered temperature.Technique scheme can continuous operation.
The hydrogenation catalyst that one-stage hydrogenation tower in the present invention uses is loading type Ni, Co, NiMo, CoMo metal catalyst or NiMoW sulfide catalyst, and carrier is SiO
2-Al
2o
3or Al
2o
3-TiO
2.The Main Function of catalyzer is under low hydrogen/gasoline ratio and high-speed, and low temperature hydrogenation is removed carbon carbon triple bond and carbon-carbon double bond in removal phenol carbolic oil, prevents its polymerization in hydrofining tower, increases the Hydrobon catalyst life-span.The catalyzer that hydrofining tower uses is loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, and the Main Function of catalyzer is that monoolefin hydrogenation saturated reaction removes monoene compound, and desulfurization, nitrogen are de-, except colloid.Carrier is oxide carrier or the Carbon Materials with two mesopore composite structures, and oxide carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3or Al
2o
3-TiO
2.
Produce the yield that obtains gasoline fraction (<180 DEG C) at 85-90% by method of the present invention, octane value is 85-92, density 0.70-0.75g/cm
3, can be used as the blend component of gasoline.The yield of diesel oil distillate (>180 DEG C) is at 10-15%, and cetane value is 45, density 0.82-0.84g/cm
3, can be used as diesel oil.
Low temperature hydrogenation of the present invention, hydrogenation upgrading, air distillation adopt the mode of operate continuously, flexible operation, easy.Adopt under low hydrogen/gasoline ratio and high-speed, low temperature hydrogenation is removed carbon carbon triple bond and carbon-carbon double bond in removal phenol carbolic oil, prevents its polymerization in hydrofining tower, increases the Hydrobon catalyst life-span.The available high-quality clean fuel oil of the present invention, thus realize the recycling of removal phenol carbolic oil.
Brief description of the drawings
Accompanying drawing is process flow diagram of the present invention.
In figure: 1 one-stage hydrogenation tower; 2 hydrofining towers; 3 distillation towers.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Hydrogenation catalyst is loading type Ni, Co, NiMo, CoMo metal catalyst or NiMoW sulfide catalyst.Carrier adopts SiO
2-Al
2o
3, specific surface area is at 300-500m
2/ g, pore volume is at 2-3cm
3/ g, most probable pore size distribution is at 2-4nm and 10-15nm.Metal precursor adopts respectively acetic acid to pinch or nickelous nitrate, Cobaltous diacetate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate and ammonium molybdate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate.Adopt equi-volume impregnating to prepare load type metal catalyst through dipping-dry-steps such as roasting.For metal Co and Ni metal loading, at 20-40%, Mo metal supports 5-15%.Be nickelous nitrate, ammonium molybdate and ammonium tungstate for NiMoW sulfide catalyst metal precursor, the loading of Ni, Mo and W is respectively 20%, 5% and 5%.Following table 1 is shown in reaction process condition and product property.
As shown in Table 1, removal phenol carbolic oil is through the de-diene of high pressure low temperature hydrogenation, and all metal catalysts take off diene successful, and nitrogen and sulphur content there are not change substantially, chooses active best NiMoW sulfide as catalyzer.
Embodiment 2
Investigate temperature of reaction and reaction pressure as an example of NiMoW sulfide catalyst example on removing the impact of diene effect.The loading of Ni, Mo and W is respectively 20%, 5% and 5%.Following table 2 is shown in reaction process condition and product property.
As shown in Table 2, temperature of reaction is larger to diolefin hydrogenation influential effect, and reaction pressure is less to diolefin hydrogenation influential effect, and reaction conditions does not affect Nitrogen in Products, sulphur content.Therefore, selective reaction condition is: 160 DEG C of temperature of reaction, reaction pressure 8MPa, volume space velocity 1h
-1, hydrogen to oil volume ratio 800.
Embodiment 3
Taking NiMoW sulfide catalyst as example, on the basis of embodiment 2, carry out diolefin hydrogenation stability experiment 8MPa and 160 DEG C, following table 3 is shown in the reaction process condition of operation in 500 hours and the product property finally obtaining.
The experimental result of 500 hours as shown in Table 3, on NiMoW sulfide catalyst in 160 DEG C, 8MPa, volume space velocity 1h-1, hydrogen to oil volume ratio 800, diolefin hydrogenation, known according to data before and after reaction, diene content is substantially constant compared with starting test, shows that catalyzer has high activity and stability.
Embodiment 4
Hydrobon catalyst adopts loading type NiMo sulfur catalyst.Carrier adopts SiO
2-Al
2o
3, specific surface area is at 200-400m
2/ g, pore volume is at 0.5-2.0cm
3/ g, most probable pore size distribution is at 2-4nm and 10-15nm.Nickel molybdenum sulphide precursor adopts nickelous nitrate or nickel acetate or acetylacetonate nickel and ammonium thiomolybdate.Adopt equi-volume impregnating to prepare loading type NiMo sulfide catalyst through dipping-dry-roasting-steps such as sulfuration.Following table 4 is shown in reaction process condition and product composition.
As shown in Table 4, distillate on supported cobalt molybdenum sulphide catalyzer in 360 DEG C of hydrofinings, diolefine in the product obtaining, do not detected, the content of sulphur and nitrogen reduces greatly, shows that load-type nickel molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficiency.The product water-white obtaining, free from extraneous odour, the petrol and diesel oil mixture that quality is high.
Embodiment 5
Product introduction atmospheric distillation tower after hydrofining cuts into gasoline (<180 DEG C) and diesel oil (>180 DEG C) according to recovered temperature.Petrol and diesel oil character is shown in by lower 5 tables.
As shown in Table 5, distillate on supported cobalt molybdenum sulphide catalyzer in 360 DEG C of hydrofinings, diolefine in the product obtaining, do not detected, the content of sulphur and nitrogen reduces greatly, shows that load-type nickel molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficiency.The product water-white obtaining, free from extraneous odour, the gasoline that quality is high and diesel oil.
Embodiment 6
Taking catalytic distillation diesel oil distillate as raw material, on the basis of embodiment 4 and 5, carry out stability experiment 8MPa and 360 DEG C, following table 6 is shown in the reaction process condition of operation in 1000 hours and the product property finally obtaining.
The experimental result of 1000 hours as shown in Table 6 in 360 DEG C of hydrofinings, does not detect diolefine in the petrol and diesel oil product obtaining in air distillation on load-type nickel molybdenum sulphide catalyzer, reaches 2mg100mL for gasoline gum content
-1, be also reduced to 12mg100mL for diesel oil gum level
-1, containing compared with starting test of sulphur and nitrogen is substantially constant, meets national petrol and diesel oil standard, shows the product free from extraneous odour that this technology obtains, have good stability, and the petrol and diesel oil that quality is high.The above results shows that technology of the present invention has satisfactory stability.
Claims (6)
1. the method for a removal phenol carbolic oil clean fuel processed, it is characterized in that: removal phenol carbolic oil is injected to the one-stage hydrogenation tower that hydrogenation catalyst is housed, carry out low temperature hydrogenation and remove diolefin in removal phenol carbolic oil, feeding temperature 120-180 DEG C, hydrogen partial pressure 4-8MPa, volume space velocity 1-4.0h
-1, hydrogen to oil volume ratio 400-800:1; Hydrogenation catalyst is metal supported catalyst or metal sulfide catalyst; After hydrogenation, removal phenol carbolic oil enters hydrofining tower, carries out hydrogenation upgrading, feeding temperature 320-360 DEG C, hydrogen partial pressure 6-8MPa, volume space velocity 0.4-1.0h
-1, hydrogen to oil volume ratio 600-1200:1; Hydrobon catalyst is loading type sulfide catalyst; Distillate after hydrofining, through air distillation, cuts into gasoline and diesel oil according to recovered temperature.
2. method according to claim 1, be further characterized in that: described metal supported catalyst is loading type Ni catalyzer, load type Co catalyzer, loading type NiMo catalyzer, load type Co Mo catalyzer, and described metal sulfide catalyst is NiMoW sulfide catalyst.
3. method according to claim 2, is further characterized in that: described loading type sulfide catalyst is loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, and carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3, Al
2o
3-TiO
2.
4. according to the method described in claim 1 or 2 or 3, be further characterized in that: the carrier of metal supported catalyst is SiO
2-Al
2o
3or Al
2o
3-TiO
2.
5. according to the method described in claim 1,2 or 3, be further characterized in that: one-stage hydrogenation, hydrofining and air distillation are all operate continuouslys.
6. method according to claim 4, is further characterized in that: one-stage hydrogenation, hydrofining and air distillation are all operate continuouslys.
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| CN201410185278.0A CN103980937A (en) | 2014-05-05 | 2014-05-05 | Method for preparing clean fuel from dephenolized phenol oil |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
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Application publication date: 20140813 |
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