CN101798519B - Method for reducing content of sulphur in diesel distillate - Google Patents
Method for reducing content of sulphur in diesel distillate Download PDFInfo
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- CN101798519B CN101798519B CN2010101322396A CN201010132239A CN101798519B CN 101798519 B CN101798519 B CN 101798519B CN 2010101322396 A CN2010101322396 A CN 2010101322396A CN 201010132239 A CN201010132239 A CN 201010132239A CN 101798519 B CN101798519 B CN 101798519B
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Abstract
The invention discloses a method for reducing the content of sulphur in diesel distillate, comprising the following steps: feeding metallic oxides containing sodium sulfonate anthraquinone, anthraquinone, molybdenum, nickel and palladium, catalyst for X-type molecular sieve carrier and diesel distillate which is rich in sulphur to a catalytic oxidation reactor, heating the materials in catalytic oxidation reactor to 80-90 DEG C, leading compressed air into the catalytic oxidation reactor, keeping the temperature of the catalytic oxidation reactor for 30-65 min, reducing the temperature of the catalytic oxidation reactor, adding and stirring powdered white clay to the materials in the catalytic oxidation reactor, standing the catalytic oxidation reactor, and filtering the products of reaction with a plate frame to obtain the diesel distillate with less sulphur. The method for reducing the content of sulphur in diesel distillate omits the high-temperature high-pressure hydrogenation desulfurization process which is used generally at present and solves the problems of high investment and high operating cost.
Description
Technical field
The invention belongs to the method that reduces sulfur content in the diesel oil distillate.
Background technology
Along with global crude oil becomes heavy, the sulfur content in the diesel oil is more and more, causes in the toxic emission increase of pernicious gas NO, SO and particle.In order to make people can live in the clean environment clean fuel of the environmental requirement production " environmental friendliness " of increasingly stringent.Because environment control requires increasingly stringent to motor vehicle emission, diesel car also proposes higher, stricter requirement to the quality of diesel oil.
Conventional hydrofining technology technology has had desulfurization and denitrification, can solve the stability of diesel oil distillate and improve the colourity problem.In industrial production, produce desulfurized diesel oil, catalytic diesel oil and coker gas oil with sour crude oil and all utilize hydrofining technology at present, so that product reaches the requirement of the diesel oil sulfur content of corresponding codes and standards.But, then must adopt further hydrogenation technique if will reach the diesel oil of ultralow or low sulfur-bearing clean diesel standard.So, will bring problems such as investment is big, complicated operation, cost height, and need huge hydrogen producer and corresponding auxiliary equipment.
Summary of the invention
The technical problem to be solved in the present invention provides the method for sulfur content in a kind of reduction diesel oil distillate that need not high temperature, high pressure, hydrofinishing desulfurization, to reach the purpose that small investment, running cost are low, be convenient to promote.
The present invention solves the problems of the technologies described above with following technical scheme:
Processing step of the present invention is:
1. containing sodium anthraquinone sulfonate and anthraquinone sulfonic acid potassium, anthraquinone, molybdenum, nickel, the metal oxide of palladium and the catalyst of X type molecular sieve carrier, be arranged on the reaction bed in the catalytic oxidation still; Divide 3～5 beds to lay catalyst on reaction bed, gross thickness is at 500～800mm; The composition of catalyst is that the gross mass of 1.4-dihydroxy anthraquinone sodium disulfonate, 1.4-dihydroxy anthraquinone disulfonic acid potassium is 70%～80% of a catalyst gross mass, and the mass ratio of the two is 3～4: 5～4; 1.4-dihydroxy anthraquinone is 10～20% of a catalyst gross mass; The total amount of molybdenum, nickel, palladium oxide is that the mass ratio of 4%～10%, three kinds of metal oxides of catalyst gross mass is 5: 3.5: 1.5;
2. the diesel oil distillate that is rich in sulphur is sent in the catalytic oxidation still, reactor inner catalyst and diesel oil distillate volume ratio are 0.03～0.4: 1; Volume is controlled at 70%～75% of reactor dischargeable capacity;
3. be heated to 80～90 ℃, in reactor, feed compressed air, by volume air speed 50～120h
-1Flow feeds, and diesel oil distillate is 0.08～2.0: 1 with the volume of air ratio, and reactor internal reaction pressure is 0.5～1.5MPa, keeps temperature 30～65 minutes; Then stop to heat, keep oxygen supply, wait oily temperature drop to 40～50 ℃ after, emit; Enter miscella tank, adding and material in reactor total mass ratio are 0.2～1%: 1 the powdery carclazyte through oven dry, utilize dried compressed air to stir after 5～10 minutes, leave standstill 30 minutes;
4. employing plate-frame filtering, pump pressure is controlled at 0.3～0.6MPa, can obtain the diesel oil distillate of low sulfur content.
Catalyst is made into graininess, and diameter is 1～3.5mm, average length 3～6mm, crushing strength＞170N.cm-1, clover strip.
Adopt method of the present invention to reduce sulfur content in the diesel oil distillate, exempted now the generally technology of the high temperature of employing, high pressure, hydrodesulfurization, solved problem with high investment, high running cost.
The specific embodiment
Because the technology that reduces sulfur content in the diesel oil distillate at present generally adopts the method for high temperature, high pressure, hydrodesulfurization, causing must be with high investment, expensive; Principle of the present invention is to avoid adopting extreme physics and chemical technology method, use relatively mild technical measures, employing air oxidation catalyst method removes the sulphur in the diesel oil distillate, the catalyst that uses is the molecular sieve formula catalyst of superfines that contains the metal oxide of sodium anthraquinone sulfonate (potassium), 1.4-dihydroxy anthraquinone and molybdenum, nickel, palladium, and using in pilot scale has tangible desulfurized effect.
Processing step of the present invention is:
1. containing sodium anthraquinone sulfonate and anthraquinone sulfonic acid potassium, anthraquinone, molybdenum, nickel, the metal oxide of palladium and the catalyst of X type molecular sieve carrier, be arranged on the reaction bed in the catalytic oxidation still; Divide 3～5 beds to lay catalyst on reaction bed, gross thickness is at 500～800mm.The composition of catalyst and preparation method are open in the Chinese patent application of applying on the same day with the present invention " reduces oxidation-desulfurizing catalyst of sulphur content of diesel fraction and preparation method thereof ".
2. the diesel oil distillate that is rich in sulphur is sent in the catalytic oxidation still, reactor inner catalyst and diesel oil distillate volume ratio are 0.03～0.4: 1; Volume is controlled at 70%～75% of reactor dischargeable capacity.
3. be heated to 80～90 ℃, in reactor, feed compressed air, by 50～120h
-1(volume space velocity/h
-1) the flow feeding, diesel oil distillate is 0.08～2.0: 1 with the volume of air ratio, pressure remains on 0.5～1.5Mpa in reactor, keeps temperature 30～65 minutes; Then stop to heat, keep oxygen supply, wait oily temperature drop to 40～50 ℃ after, emit; Enter miscella tank, adding and material in reactor total mass ratio are 0.2～1%: 1 the powdery carclazyte through oven dry, utilize dried compressed air to stir after 5～10 minutes, leave standstill 30 minutes.
4. employing plate-frame filtering, pump pressure is controlled at 0.3～0.6MPa, can obtain the diesel oil distillate of low sulfur content.
Catalyst can be made into graininess, and diameter is 1～3.5mm, average length 3～6mm, crushing strength＞170N.cm-1, clover strip.
The applicant bores in Zhong Haimao south that to reach the effect that fuel oil company produces as a trial in carrying out be gratifying.
Below be to reduce several embodiment of sulfur content in the diesel oil distillate and the index behind the oxidation sweetening with said method:
Embodiment 1:
Divide 4 beds to lay catalyst, gross thickness 500mm on the reaction bed in reactor; Reactor inner catalyst and diesel oil distillate volume ratio are 0.3: 1, and cumulative volume is 70% of a reactor dischargeable capacity; Diesel oil distillate and volume of air were heated to 80 ℃ than 0.08: 1 in the reactor, and compressed air is air speed 50h by volume
-1Flow feeds, and reaction pressure is 0.5MPa, keeps temperature 32 minutes;
The index that obtains behind the oxidation sweetening:
| Project | Raw material | Behind the oxidation sweetening | Project | Raw material | Behind the oxidation sweetening |
| Sulphur ug/g | 1768 | 171 | Water-soluble soda acid | Do not have | Do not have |
| Acidity mgKOH/100ml | 118.2 | 11.1 | Mechanical admixture | Do not have | Do not have |
| Density (20 ℃) g/cm-3 | 0.865 | 0.855 | Copper corrosion (50 ℃ of 3h) | 2 | 1 |
Embodiment 2
Divide 3 beds to lay catalyst, gross thickness 600mm on the reaction bed in reactor; Reactor inner catalyst and diesel oil distillate volume ratio are 0.032: 1, and cumulative volume is 75% of a reactor dischargeable capacity; Be heated to 90 ℃, compressed air is air speed 100h by volume
-1Flow feeds, and diesel oil distillate and volume of air are than 0.1: 1, and reaction pressure is 1MPa, maintenance temperature 58 minutes;
The index that obtains behind the oxidation sweetening:
| Project | Raw material | Behind the oxidation sweetening | Project | Raw material | Behind the oxidation sweetening |
| Sulphur ug/g | 9900 | 241 | Water-soluble soda acid | Do not have | Do not have |
| Acidity mgKOH/ (100ml) | 4.44 | 1.6 | Mechanical admixture | Do not have | Do not have |
| Density (20 ℃) g/cm-3 | 0.882 | 0.879 | Copper corrosion | 2 | 1 |
Embodiment 3
Divide 5 beds to lay catalyst, gross thickness 800mm on the reaction bed in reactor; Reactor inner catalyst and diesel oil distillate volume ratio are 0.04: 1, and cumulative volume is 72% of a reactor dischargeable capacity; Be heated to 85 ℃, compressed air is air speed 120h by volume
-1Flow feeds, and diesel oil distillate and volume of air be than 1.5: 1, pressure 1.2Mpa, maintenance temperature, time of repose 62 minutes.
The index that obtains behind the oxidation sweetening:
| Project | Raw material | Behind the oxidation sweetening | Project | Raw material | Behind the oxidation sweetening |
| Sulphur/ug/g | 11200 | 302 | Water-soluble soda acid | Do not have | |
| Acidity mgKOH. (100ml) | 8.66 | 0.89 | Mechanical admixture | Do not have | Do not have |
| Density (20 ℃) g/cm-3 | 0.849 | 0.827 | Copper corrosion | 2 | 1 |
Claims (2)
1. method that reduces sulfur content in the diesel oil distillate is characterized in that processing step is:
1. the catalyst of metal oxide that contains sodium anthraquinone sulfonate and anthraquinone sulfonic acid potassium, anthraquinone, molybdenum, nickel, palladium and X type molecular sieve carrier, be arranged on the reaction bed in the catalytic oxidation still; Divide 3～5 beds to lay catalyst on reaction bed, gross thickness is at 500～800mm; The composition of catalyst is that the gross mass of 1.4-dihydroxy anthraquinone sodium disulfonate, 1.4-dihydroxy anthraquinone disulfonic acid potassium accounts for 70%～80% of catalyst gross mass, and the mass ratio of the two is 3～4: 5～4; 1.4-dihydroxy anthraquinone accounts for 10%～20% of catalyst gross mass; The mass ratio that the total amount of molybdenum, nickel, palladium oxide accounts for 4%～10%, three kinds of metal oxides of catalyst gross mass is 5: 3.5: 1.5;
2.. the diesel oil distillate that is rich in sulphur is sent in the catalytic oxidation still, and reactor inner catalyst and diesel oil distillate volume ratio are 0.03～0.4: 1; Volume is controlled at 70%～75% of reactor dischargeable capacity;
3.. be heated to 80～90 ℃, in reactor, feed compressed air, by volume air speed 50～120h
-1Flow feeds, and diesel oil distillate is 0.08～2.0: 1 with the volume of air ratio, and reactor internal reaction pressure is 0.5～1.5MPa, keeps temperature 30～65 minutes; Then stop to heat, keep oxygen supply, wait oily temperature drop to 40～50 ℃ after, emit; Enter miscella tank, adding and material in reactor total mass ratio are 0.2%～1%: 1 the powdery carclazyte through oven dry, utilize dried compressed air to stir after 5～10 minutes, leave standstill 30 minutes;
4.. adopt plate-frame filtering, pump pressure is controlled at 0.3～0.6MPa, can obtain the diesel oil distillate of low sulfur content.
2. the method for sulfur content in the reduction diesel oil distillate as claimed in claim 1 is characterized in that catalyst is made into the particle that the cross section is the clover strip, and diameter is 1～3.5mm, average length 3～6mm, crushing strength＞170N.cm
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010101322396A CN101798519B (en) | 2010-03-25 | 2010-03-25 | Method for reducing content of sulphur in diesel distillate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101322396A CN101798519B (en) | 2010-03-25 | 2010-03-25 | Method for reducing content of sulphur in diesel distillate |
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| CN101798519A CN101798519A (en) | 2010-08-11 |
| CN101798519B true CN101798519B (en) | 2011-09-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6544409B2 (en) * | 2001-05-16 | 2003-04-08 | Petroleo Brasileiro S.A. - Petrobras | Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams |
| US8663459B2 (en) * | 2006-03-03 | 2014-03-04 | Saudi Arabian Oil Company | Catalytic process for deep oxidative desulfurization of liquid transportation fuels |
| CN101099919A (en) * | 2007-07-26 | 2008-01-09 | 山东大学 | Normal temperature high efficient remover for hydrogen sulfide and its preparation method and application |
| US20090242459A1 (en) * | 2008-03-26 | 2009-10-01 | General Electric Company | Oxidative desulfurization of fuel oil |
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