CN103965962B - A kind of method of removal phenol carbolic oil benzene methanamine and clean fuel - Google Patents
A kind of method of removal phenol carbolic oil benzene methanamine and clean fuel Download PDFInfo
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- CN103965962B CN103965962B CN201410212307.8A CN201410212307A CN103965962B CN 103965962 B CN103965962 B CN 103965962B CN 201410212307 A CN201410212307 A CN 201410212307A CN 103965962 B CN103965962 B CN 103965962B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000003502 gasoline Substances 0.000 claims abstract description 13
- BUXYRJPVMAZQSY-UHFFFAOYSA-N benzene;methanamine Chemical compound NC.C1=CC=CC=C1 BUXYRJPVMAZQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000007791 liquid phase Substances 0.000 claims description 16
- 229910003294 NiMo Inorganic materials 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000002283 diesel fuel Substances 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 150000005673 monoalkenes Chemical class 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 71
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ROQRYYMOYXKROR-UHFFFAOYSA-N [Pt].C(C)C(=O)C(=O)C Chemical compound [Pt].C(C)C(=O)C(=O)C ROQRYYMOYXKROR-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A method for removal phenol carbolic oil benzene methanamine and clean fuel, belongs to environment protection and energy technology field.It is characterized in that removal phenol carbolic oil and hydrogen to be mixed into hydrogenation tower, carry out low temperature hydrogenation and remove cyanobenzene and diolefin in removal phenol carbolic oil; After hydrogenation, removal phenol carbolic oil enters water wash column, water wash column ambient operation, and the water wash column tower underlying layers benzene methanamine aqueous solution enters rectifying tower, charging in tower, and rectifying tower ejects water, beats and is recycled into water wash column, goes out high-purity benzene methylamine at the bottom of rectifying tower; After washing, removal phenol carbolic oil is mixed into hydrofining tower through pressurization and hydrogen, carry out hydrogenation upgrading, monoene compound is removed by monoolefin hydrogenation saturated reaction, and desulfurization, nitrogen take off, 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.It is simple that the present invention has technique, catalyst activity and good stability, and have good economic benefit and prospects for commercial application.
Description
Technical field
The invention belongs to environment protection and energy technology field, relate to a kind of method of removal phenol carbolic oil benzene methanamine and clean fuel.
Background technology
In Coal Chemical Industry process, coal tar is as one of the 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.Cut before 170 DEG C, coal tar is light oil; The cut of 170 ~ 210 DEG C is mainly carbolic oil.Removal phenol carbolic oil refer to carbolic oil sloughed phenol by sodium hydroxide after oil, the solution after sodium hydroxide dephenolize, sodium phenolate solution, is extract the raw material of crude phenols, carries out refining of crude phenol again after extracting.In coal tar, the content of removal phenol carbolic oil is about 3%, and the fraction usually cut in the actual course of processing is all greater than 3%, the cyanobenzene of removal phenol carbolic oil about containing 2%-3%, the existence of cyanobenzene not only increases hydrorefined hydrogen consumption, increase production cost, and to the toxic effect of Hydrobon catalyst.Cyanobenzene can Hydrogenation for benzylamine, benzylamine is a kind of chemicals of high added value, can be used as the intermediate of dyestuff, medicine and polymkeric substance.At present, technique roughly has following several means to the process of removal phenol carbolic oil: the first is back to mix in mixing oil, but the price of mixing oil is lower than the price of removal phenol carbolic oil, production added value is low.The second treatment process rebuilds a set of rectifier unit, by removal phenol carbolic oil re-distillation, can reclaim a part of naphthalene, but low to removal phenol carbolic oil overall utilization rate.The third is as intermediates direct marketing by removal phenol carbolic oil.Above method does not all have recycling to removal phenol carbolic oil.
For abundant removal phenol carbolic oil recycling problem, according to chemical constitution and the character of removal phenol carbolic oil, we successfully develop the novel process that high-purity benzene methylamine and clean fuel are produced in removal phenol carbolic oil liquid-phase hydrogenatin-washing-rectifying-hydrofining-distillation.Removal phenol carbolic oil prepares high-purity benzene methylamine through liquid-phase hydrogenatin, washing and rectifying, end temperature liquid-phase hydrogenatin to be removed in removal phenol carbolic oil diolefin and is made cyanobenzene hydrogenation generate benzene methanamine, benzene methanamine solution prepares high-purity benzene methylamine through rectifying, and the catalyzer that hydrogenation uses is metal supported catalyst; After washing, removal phenol carbolic oil enters hydrofining tower, carry out hydrogenation upgrading, the catalyzer that hydrofining uses is sulfide catalyst, monoene compound is removed by monoolefin hydrogenation saturated reaction, and desulfurization, nitrogen take off, 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.Producing without the three wastes in liquid-phase hydrogenatin-washing-rectifying-hydrofining-distillation, is the process of green a, recycling.Following known technology, all comes with some shortcomings:
Chinese patent, publication number: CN103589466A, describing a kind of removal phenol carbolic oil by coal chemical technology is applied in oil fuel, make use of the characteristic that the allotment of removal phenol carbolic oil is high, be prepared into that a kind of production cost is low, oxidation stability is high, benzene content is low, the method of the oil fuel of normal viscosity, but the quality of oil fuel is low, removal phenol carbolic oil added value utilization ratio is low, causes the wasting of resources.
Summary of the invention
A kind of method that the invention provides removal phenol carbolic oil benzene methanamine and clean fuel is low for removal phenol carbolic oil conversion process added value, secondary pollution and the problem such as catalyst life is short, with high-purity benzene methylamine and high-quality petrol and diesel oil for target product, realize removal phenol carbolic oil recycling, make production process energy saving standard, avoid secondary pollution, the extending catalyst life-span.Specifically, removal phenol carbolic oil is prepared high-purity benzene methylamine through liquid-phase hydrogenatin, washing and rectifying by the present invention, removal phenol carbolic oil is removed diolefin and cyanobenzene hydrogenation in removal phenol carbolic oil through high pressure low temperature liquid-phase hydrogenatin and is generated benzene methanamine, the benzene methanamine aqueous solution prepares high-purity benzene methylamine through rectifying, and the catalyzer that hydrogenation uses is metal supported catalyst; After washing, removal phenol carbolic oil enters hydrofining tower, carry out hydrogenation upgrading, the catalyzer that hydrofining uses is sulfide catalyst, monoene compound is removed by monoolefin hydrogenation saturated reaction, and desulfurization, nitrogen take off, except colloid produce free from extraneous odour, high-quality petrol and diesel oil mixing oil, then obtain gasoline and diesel oil distillate oil through distillation.Invention increases removal phenol carbolic oil utilization ratio, increase its added value, energy-conservation of consumption reduction, the extending catalyst life-span, flow process is simple and reduce investment outlay.
Technical scheme of the present invention is as follows:
Removal phenol carbolic oil and hydrogen are mixed into hydrogenation tower, carry out low temperature hydrogenation and remove cyanobenzene and diolefin in removal phenol carbolic oil, feeding temperature 140-180 DEG C, hydrogen partial pressure 4-8MPa, volume space velocity 0.5-1.0h
-1, hydrogen to oil volume ratio 400-600:1; Hydrogenation catalyst is metal supported catalyst; After hydrogenation, removal phenol carbolic oil enters water wash column, water wash column ambient operation, water and removal phenol carbolic oil volume ratio 0.5-2, the water wash column tower underlying layers benzene methanamine aqueous solution enters rectifying tower, charging in tower, and rectifying tower ejects water, beat and be recycled into water wash column, at the bottom of rectifying tower, go out high-purity benzene methylamine; After hydrogenation, removal phenol carbolic oil is mixed into hydrofining tower through washing, pressurization and hydrogen, 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; The catalyzer that hydrogenation uses 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.
Hydrogenation catalyst in the present invention is metal supported catalyst, and metal catalyst is metal supported catalyst is Pd, PtPd, Co, Ni, CoMo or NiMo; Carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3or Al
2o
3-TiO
2.The Main Function of catalyzer is under low hydrogen/gasoline ratio and high-speed, low temperature liquid phase hydrogenation removes diolefin in removal phenol carbolic oil, prevent it to be polymerized in hydrofining tower, increase the Hydrobon catalyst life-span, and make the cyanobenzene hydrogenation in removal phenol carbolic oil generate benzene methanamine.Hydrofining tower use Hydrobon catalyst for supported sulfide catalyzer be NiMo, NiW, CoMo, CoW, NiMoW or CoMoW, the Main Function of catalyzer is that monoolefin hydrogenation saturated reaction removes monoene compound, and desulfurization, nitrogen are de-, except colloid; Carrier is SiO
2-Al
2o
3or Al
2o
3-TiO
2.
Benzene methanamine purity >98.5% is obtained through liquid-phase hydrogenatin, washing and rectifying production by removal phenol carbolic oil of the present invention; Removal phenol carbolic oil through liquid-phase hydrogenatin, washing, hydrofining, distill the yield of gasoline fraction (<180 DEG C) at 85-90%, octane value is 85-92, density 0.70-0.75g/cm
3, can 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 as diesel oil.
Liquid-phase hydrogenatin of the present invention, water washing process, rectifying, hydrogenation upgrading, air distillation adopt the mode of operate continuously, flexible operation, easy.Liquid-phase hydrogenatin, washing and rectifying is adopted to prepare high-purity benzene methylamine, and under low hydrogen/gasoline ratio and high-speed, low temperature liquid phase hydrogenation removes diolefin in removal phenol carbolic oil, it is prevented to be polymerized in hydrofining tower, increase the Hydrobon catalyst life-span, and make the cyanobenzene hydrogenation in removal phenol carbolic oil generate high valuable chemicals benzene methanamine.After washing, removal phenol carbolic oil is through hydrogenation upgrading, removes monoene compound by monoolefin hydrogenation saturated reaction, and desulfurization, nitrogen take off, except colloid produce free from extraneous odour, high-quality petrol and diesel oil mixing oil, then obtain gasoline and diesel oil distillate oil through distillation.The present invention can obtain high purity high added value benzene methanamine and high-quality clean fuel oil, thus realizes the recycling of removal phenol carbolic oil.
Accompanying drawing explanation
Accompanying drawing is process flow diagram of the present invention.
In figure: 1 hydrogenation tower; 2 water wash columns; 3 rectifying tower; 4 hydrofining towers; 5 distillation towers.
Embodiment
Specific embodiments of the invention are described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Removal phenol carbolic oil is injected hydrogenation tower, hydrogenation catalyst is loading type Pd, PtPd, Co, Ni, CoMo or NiMo metal catalyst.Carrier adopts SiO
2-Al
2o
3, specific surface area is at 400-500m
2/ g, pore volume is at 2-3cm
3/ g, most probable pore size is distributed in 2-4nm and 10-15nm.Metal precursor adopts palladium or Palladous nitrate, palladium and Platinic chloride or Palladous nitrate respectively and methyl ethyl diketone platinum, Cobaltous diacetate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, acetic acid pinch or nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate, nickelous nitrate and ammonium molybdate.Equi-volume impregnating is adopted to prepare load type metal catalyst through steps such as dipping-drying-roast-reduction.For metal Pd metal loading at 3-10%; Loading for metal dual metal PtPd Pt metal and Pd distinguishes 2-8% and 0.5-2%; For metal Co and Ni metal loading at 20-40%; Be supported on 15-25% for CoMo and NiMo metal Co and Ni, metal M o is supported on 5-15%.Following table 1 is shown in reaction process condition and product property.
As shown in Table 1, removal phenol carbolic oil takes off diene through high pressure low temperature hydrogenation, and all metal catalysts take off diene successful, and nitrogen and sulphur content there are not change substantially, all very high to the hydrogenation activity activity of cyanobenzene.Consider catalyzer price and diolefin and cyanobenzene hydrogenation effect, choose reasonable price, active best W metal Mo catalyzer.
Embodiment 2
Investigate temperature of reaction and reaction pressure to the impact removing diene and cyanobenzene hydrogenation effect for W metal Mo catalyzer, the loading of Ni and Mo is respectively 20% and 10%.Following table 2 is shown in reaction process condition and product property.
As shown in Table 2, temperature of reaction is comparatively large to diolefin hydrogenation and cyanobenzene hydrogenation influential effect, but when temperature of reaction is greater than 160 DEG C, impact effect becomes not obvious.And reaction pressure is less to diolefin hydrogenation influential effect, and there is impact to cyanobenzene hydrogenation.Therefore, selective reaction condition is: temperature of reaction 160 DEG C, reaction pressure 8MPa, volume space velocity 1h
-1, hydrogen to oil volume ratio 600.
Embodiment 3
For NiMo catalyzer, diolefin hydrogenation and the experiment of cyanobenzene stabilized hydrogenation are carried out at 8MPa and 160 DEG C in the basis of embodiment 2, and following table 3 is shown in the reaction process condition run for 500 hours and the product property finally obtained.
The experimental result of 500 hours as shown in Table 3, in 160 DEG C on W metal Mo catalyzer, 8MPa, volume space velocity 1h
-1, hydrogen to oil volume ratio 600, diolefin hydrogenation and cyanobenzene hydrogenation, according to data before and after reaction, diene content and cyanobenzene hydrogenation rate with start compared with test substantially constant, show that catalyzer has high activity and stability.
Embodiment 4
On the basis of embodiment 2, removal phenol carbolic oil after low temperature hydrogenation is injected water wash column, water wash column ambient operation, water and removal phenol carbolic oil volume ratio 0.5-2:1, upper oil phase at the bottom of water wash column tower is through adding press-in hydrofining tower, and at the bottom of water wash column tower, aqueous phase enters rectifying tower, charging in the middle part of rectifying tower, rectifying tower ejects water and removes water wash column, goes out high-purity benzene methylamine at the bottom of rectifying tower.Following table 4 is shown in reaction process condition and product property.
As shown in Table 4, the benzene methanamine concentration that removal phenol carbolic oil is produced after liquid-phase hydrogenatin, washing and rectifying is all greater than 98.5%, and when in water wash column, water removal phenol carbolic oil volume ratio is greater than 1, benzene methanamine percentage extraction is greater than 95%, but water removal phenol carbolic oil volume ratio is greater than 1, benzene methanamine percentage extraction increases not obvious.Therefore selection condition is: water/removal phenol carbolic oil volume ratio is 1, and water cooling tower temperature is 25 DEG C.
Embodiment 5
On the basis of embodiment 2 and 4, investigate the stability experiment of technique, following table 5 is shown in the reaction process condition run for 500 hours and the product property finally obtained.
As shown in Table 5: the present invention produces high-purity benzene methylamine through liquid-phase hydrogenatin, washing and distillation technology, and has satisfactory stability.
Embodiment 6
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 is distributed in 2-4nm and 10-15nm.Nickel molybdenum sulphide precursor adopts nickelous nitrate or nickel acetate or acetylacetonate nickel and ammonium thiomolybdate.Equi-volume impregnating is adopted to prepare loading type NiMo sulfide catalyst through steps such as dipping-drying-roasting-sulfurations.Following table 6 is shown in reaction process condition and product composition.
As shown in Table 6, oil distillate on load-type nickel molybdenum sulfide catalyst in 360 DEG C of hydrofinings, diolefine do not detected in the product obtained, sulphur and nitrogen and gum level reduce greatly, show that load-type nickel molybdenum sulfide catalyst has good desulfurization removing nitric deolefination efficiency.The product water-white obtained, free from extraneous odour, the petrol and diesel oil mixture that quality is high.
Embodiment 7
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 7 tables.
As shown in Table 7, oil distillate on supported cobalt molybdenum sulfide catalyst in 360 DEG C of hydrofinings, diolefine do not detected in the product obtained, the content of sulphur and nitrogen reduces greatly, shows that load-type nickel molybdenum sulfide catalyst has good desulfurization removing nitric deolefination efficiency.The product water-white obtained, free from extraneous odour, the gasoline that quality is high and diesel oil.
Embodiment 8
With catalytic distillation diesel oil distillate for raw material, stability experiment is carried out at 8MPa and 360 DEG C in the basis of embodiment 6 and 7, following table 8 is shown in the reaction process condition run for 1000 hours and the product property finally obtained.
The experimental result of 1000 hours as shown in Table 8, in 360 DEG C of hydrofinings on load-type nickel molybdenum sulfide catalyst, does not detect diolefine, reaches 2mg100mL for gasoline gum content in the petrol and diesel oil product that air distillation obtains
-1, also 12mg100mL is reduced to for diesel oil gum level
-1, sulphur and nitrogen containing with start compared with test substantially constant, meet national petrol and diesel oil standard, show to have good stability the product free from extraneous odour that this technology obtains, the petrol and diesel oil that quality is high.The above results shows that technology of the present invention has satisfactory stability.
Claims (5)
1. a method for removal phenol carbolic oil benzene methanamine and clean fuel, is characterized in that:
Removal phenol carbolic oil pressurization is mixed into hydrogenation tower with hydrogen, carries out low temperature hydrogenation and remove cyanobenzene and diolefin in removal phenol carbolic oil, feeding temperature 140-180 DEG C, hydrogen partial pressure 4-8MPa, volume space velocity 0.5-1.0h
-1, hydrogen to oil volume ratio 400-600:1; Hydrogenation catalyst is metal supported catalyst; After hydrogenation, removal phenol carbolic oil enters water wash column, water wash column ambient operation, water and removal phenol carbolic oil volume ratio 0.5-2, the water wash column tower underlying layers benzene methanamine aqueous solution enters rectifying tower, charging in tower, and rectifying tower ejects water, beat and be recycled into water wash column, at the bottom of rectifying tower, go out high-purity benzene methylamine; After hydrogenation, removal phenol carbolic oil is mixed into hydrofining tower with hydrogen after washing, 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; The catalyzer that hydrogenation uses is sulfide catalyst; Distillate after hydrofining, through air distillation, cuts into gasoline according to recovered temperature.
2. method according to claim 1, is further characterized in that: described metal supported catalyst is Pd, PtPd, Co, Ni, CoMo or NiMo; Carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3or Al
2o
3-TiO
2.
3. method according to claim 1 and 2, is further characterized in that: described sulfide catalyst is NiMo, NiW, CoMo, CoW, NiMoW or CoMoW; Carrier is SiO
2-Al
2o
3or Al
2o
3-TiO
2.
4. the method for a kind of removal phenol carbolic oil benzene methanamine according to claim 1 and 2 and clean fuel, is further characterized in that: liquid-phase hydrogenatin, washing, rectifying, hydrofining and distillation operate continuously.
5. the method for a kind of removal phenol carbolic oil benzene methanamine according to claim 3 and clean fuel, is further characterized in that: liquid-phase hydrogenatin, washing, rectifying, hydrofining and distillation operate continuously.
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| EP0590673A1 (en) * | 1992-10-02 | 1994-04-06 | Mitsubishi Oil Company, Limited | Process for producing low viscosity lubricating base oil having high viscosity index |
| 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 |
| CN102807900A (en) * | 2011-06-01 | 2012-12-05 | 中国科学院过程工程研究所 | High-value utilization method for oxygen-enriched coal tar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590673A1 (en) * | 1992-10-02 | 1994-04-06 | Mitsubishi Oil Company, Limited | Process for producing low viscosity lubricating base oil having high viscosity index |
| 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 |
| CN102807900A (en) * | 2011-06-01 | 2012-12-05 | 中国科学院过程工程研究所 | High-value utilization method for oxygen-enriched coal tar |
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