CN1313576C - Process for hydrogenating treatment of foulty gasoline - Google Patents
Process for hydrogenating treatment of foulty gasoline Download PDFInfo
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- CN1313576C CN1313576C CNB031340105A CN03134010A CN1313576C CN 1313576 C CN1313576 C CN 1313576C CN B031340105 A CNB031340105 A CN B031340105A CN 03134010 A CN03134010 A CN 03134010A CN 1313576 C CN1313576 C CN 1313576C
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Abstract
The present invention discloses a hydroprocessing method for poor-quality gasoline, wherein hydroprocessing comprises two catalyst beds, wherein the raw material of the poor-quality gasoline and hydrogen are in contact with hydrogenation modification catalysts in the first catalyst bed, and the effluent of the first catalyst bed is divided into a light component and a heavy component. The heavy component enters the second catalyst bed to be in contact with hydrogen and hydrofining catalysts to carry out catalytic hydrodesulfurization reaction, and the effluent of the second bed is mixed with the light component separated from the first catalyst bed to form the full cut fraction of gasoline products after the effluent is cooled. Compared with the existing hydrogenation technology. The present invention has the advantages that the olefin is really reduced without reducing octane values, and the harsh requirement of the sulfur content of gasoline in the future is met. The present invention is suitable for processing poor-quality gasoline with high sulfur and high olefin.
Description
Technical field
The present invention relates to a kind of hydrotreating process for light hydrocarbons, relate to the hydroprocessing process of high-sulfur inferior patrol specifically.
Background technology
Because sulphur in the gasoline and olefin(e) centent can increase CO, NO in the vehicle exhaust
XWith emission of harmful substances such as particulate matter, cause serious environmental to pollute.Therefore, the gasoline needs that meet new environmental regulation are controlled the concentration that olefin(e) centent also reduces aromatic hydrocarbons (particularly benzene) and sulphur as far as possible.But along with the change day by day of world petroleum resource is heavy, the main source of gasoline is a pressure gasoline, this type of gasoline is the olefin(e) centent height not only, and the sulphur of gasoline products almost 90% also derives from this, so each oil refinery company of the world all falls alkene in research and development, falls the Technology of sulphur, successful is hydrogenation technique at present.But when using this technology, also produced new problem, though that is exactly the sulfide in the hydrodesulfurization energy effective elimination gasoline, alkene that simultaneously also can octane value in the gasoline is higher exceedingly hydrogenation is saturated to low-octane alkane, cause the gasoline octane rating loss to become substandard product too much, as generally speaking, the gasoline desulfur rate reaches at 90% o'clock, and RON can lose 7～10 units, has also increased the hydrogen consumption simultaneously.Therefore, in order to overcome the shortcoming of above-mentioned technology, each company of great oil refining of the world all is fit to fall alkene, desulfurization and gasoline processing technology that octane value does not reduce in exploitation competitively.
Experimental study shows that alkene mainly concentrates in the lighter fraction in pressure gasoline, and sulfide mainly concentrates in the last running.In order to reduce the loss of octane number that causes because of hydrogenation of olefins is saturated, both economical, rational way is earlier the catalytic gasoline fractionation to be light, last running, and then carries out post-treatment respectively.At above-mentioned conclusion, patent US4397739 has proposed at first gasoline rectifying to be become light constituent and heavy constituent before hydrotreatment, heavy constituent is carried out the method for specific hydrogenating desulfurization again.The give chapter and verse difference of gasoline boiling point of patent US4131537 becomes several fractions with gasoline rectifying, three kinds of cuts preferably, and then under different condition, carry out desulfurization respectively.Above-mentioned technology can be by lighter fraction caustic wash desulfuration and heavy fractioning hydrogenation desulfurization, the purpose of reach and fall alkene, falling sulphur can avoid again that the light olefin hydrogenation is saturated to cause too much loss of octane number.Also there is deficiency in above-mentioned technology, and that is exactly to reduce more for a long time at product requirement alkene, still can not avoid the too much loss of octane value, generates substandard product, and the hydrogenation saturation of olefins also can increase the hydrogen consumption greatly.
CN 1316485A has proposed a kind of technology of gasoline being carried out modification by isomerizing hydrogenation, and this technology comprises two sections cascade reactions, and first section is carried out olefin isomerization, carries out hydrogenation reaction at second section then.First section dress be olefin isomerization catalyst, second section dress be olefin hydrogenation catalyst, this two-stage catalytic agent can be respectively charged into two reactors, or in the same reactor of packing into.The present invention can guarantee under the constant situation of gasoline octane rating, the content of alkene is reduced.But also there is the bigger shortcoming of hydrogen consumption in it.
Summary of the invention
In order more effectively to handle the gasoline fraction that contains alkene, sulfur-bearing with hydrogen addition technology, remedy above-mentioned the deficiencies in the prior art, the present invention proposes a kind of novel inferior patrol hydroprocessing process, this method can make inferior patrol desulfurization, to fall the alkene degree higher, and do not reduce the gasoline fraction octane value.
The hydroprocessing process of inferior patrol of the present invention, wherein hydrotreatment comprises two beds, its step is as follows:
A, bad gasoline contact with catalyst for hydro-upgrading in first beds with hydrogen, and reaction conditions is: hydrogen dividing potential drop 0.5～5.0MPa, best 1.0～4.0MPa; 320 ℃～450 ℃ of temperature, best 350 ℃～435 ℃; Liquid hourly space velocity 1.0h
-1～15.0h
-1, best 1.0h
-1～10.0h
-1Hydrogen-oil ratio 100～800, best 300～800;
B, the effluent of first beds is isolated light constituent and heavy constituent;
The heavy constituent of telling among C, the step B (being the higher part of sulphur content) enter second beds, contact with Hydrobon catalyst with hydrogen and carry out the catalytic desulfurhydrogenation reaction;
The effluent of D, second beds mixes with the isolated light constituent of first beds after cooling off and constitutes the full cut of gasoline products.
The catalyzer of first beds filling described in the above-mentioned steps A is a catalyst for hydro-upgrading, and carrier is Al
2O
3, halogen-containing Al
2O
3, one or more in SAPO-11, ZSM-12, ZSM-35, MCM-22, MCM-41, conventional ZSM-5 molecular sieve, ZSM-5 molecular sieve with small crystal grains, HBeta zeolite and the y-type zeolite etc.; So-called ZSM-5 molecular sieve with small crystal grains is meant that its size is less than 1 μ m.Auxiliary agent is TiO
2, SiO
2, ZrO
2, Al
2O
3, rare-earth oxide is (as La
2O
3) in waiting one or more.Loaded metal is a kind of or its various combination in the transition state base metals such as Co, Mo, Ni and W, also can be in the precious metals such as Pt, Re, Ir one or more, or while load base metal and precious metal.Loading for transiting state metals such as Co, Mo, Ni and W by the metal oxide compound, is generally 0.5wt%～20.0wt%, preferred 1.0wt%～15.0wt%.This kind catalyzer should have stronger hydrocracking, isomery, cyclisation functions such as (comprising aromizing).
Among the above-mentioned steps B, the product index that the effluent of first beds will satisfy according to its sulphur content carries out the separation of weight component.The isolating cut point of weight component is decided by sulphur, alkene equal size (just gasoline products sulphur, alkene equal size index) in the isolated light constituent, and the temperature that 95% of general isolated light constituent boiling range distillates a little is 95 ℃～135 ℃.
The second beds hydrodesulfurization process among the step C can adopt conventional Hydrobon catalyst, preferably adopts Mo-Co/ aluminum oxide, Mo-Ni/ aluminum oxide or W-Mo-Ni/ aluminum oxide; Adopt conventional hydrofining technology condition, reaction conditions is preferably: reaction pressure 1.0MPa～4.0MPa, 240 ℃～360 ℃ of temperature of reaction, volume space velocity 1.0h
-1～10.0h
-1With hydrogen to oil volume ratio 100～500.
First beds and second beds can be in same fixed-bed reactor, also can be in two different fixed-bed reactor.The reaction conditions of first beds shows as temperature height, operational condition harshness.In this bed, realize that mainly gasoline stocks falls alkene and do not fall octane value, and will easily remove the sulphur hydrogenation and take off; And the reaction conditions of second bed shows as that temperature is low, air speed is little, and operational condition relaxes.Mainly be that the difficulty in the gasoline stocks is removed sulphur (i.e. first beds fail to remove sulphur) hydrogenation and removing in this bed.
Reduction or rising situation according to the full cut octane value of gasoline products, determine whether the effluent of the second catalysts bed is necessary that part loops back first beds and processes, promptly when the reduction amplitude of the full cut octane value of gasoline products is big, then the effluent of the second catalysts bed is necessary that part loops back first beds and processes, otherwise then needn't.
The present invention is applicable to the various types of gasoline of processing, as straight-run spirit, catalytically cracked gasoline, coker gasoline etc., is particularly useful for processing the inferior patrol of high-sulfur, high olefin.
Compare with existing hydrogen addition technology, the present invention more helps processing the inferior patrol of high-sulfur, high olefin, and it not only can really be realized falling alkene and not fall octane value, but also can realize following harsher to content of sulfur in gasoline requirement.
Embodiment
Following embodiment further specifies of the present invention, and it does not limit use range of the present invention.
Embodiment 1～6
The main hydrogenation effect of investigating hydrogenation technique of the present invention of this test.With gasoline desulfur, alkene falls, octane value recovering is an example.Raw materials used oil properties sees Table 1 in this test.Hydrogenation reaction is all carried out in this test on the long run test device.Required catalyzer sees Table 2.The stock oil feeding temperature is 160 ℃, and operational condition and the test-results thereof of each embodiment see Table 3.
Table 1 stock oil main character
| Density, g/cm 3 | 0.732 |
| S，μg/g | 1635 |
| Alkene, v% | 52.9 |
| RON | 93.8 |
| Boiling range, ℃ 5%～95% | 52～185 |
Table 2 catalyzer physico-chemical property
| Heterogeneous catalyst | Hydrobon catalyst | |
| Catalytic active component | Ni | Mo、Co |
| Shape | Bar shaped | Bar shaped |
| Diameter, mm | 2.15 | 1.9 |
| Specific surface area, m 2/g | 454.4 | 198 |
| Pore volume, ml/g | 0.383 | 0.380 |
| Metal component (oxide compound meter), wt% NiO MoO 3 CoO | 3.5 - - | - 18.6 5.3 |
| Carrier | HBeta | Aluminum oxide |
The operational condition of each embodiment of table 3 and experimental result thereof
| Embodiment | 1 | 2 | 3 |
| Operational condition reaction pressure/MPa temperature of reaction/℃ first beds, second beds liquid hourly space velocity/h -1First beds, the second beds hydrogen to oil volume ratio, first beds, second beds | 1.0 370 320 4.0 4.0 300 200 | 2.0 390 320 4.0 5.0 300 200 | 3.0 420 320 6.0 6.0 300 300 |
| The light constituent cut point, T95/ ℃ | 120 | 120 | 120 |
| Full distillate oil character S, μ g/g alkene, v% RON loss | 90 28.1 -0.7 | 58 23.0 -1.3 | 32 19.0 -1.9 |
Operational condition and the experimental result thereof of continuous each embodiment of table 3
| Embodiment | 4 | 5 | 6 |
| Operational condition reaction pressure/MPa temperature of reaction/℃ first beds, second beds liquid hourly space velocity/h -1First beds, the second beds hydrogen to oil volume ratio, first beds, second beds | 2.5 390 340 6.0 4.0 300 200 | 2.5 390 340 6.0 4.0 300 200 | 2.5 390 340 6.0 4.0 300 200 |
| Light constituent cut point/T95/ ℃ | 95 | 110 | 135 |
| Full distillate oil character S, μ g/g alkene, v% RON loss | 5.6 14.1 0.7 | 45 21.0 -1.5 | 26 28.3 -1.8 |
Claims (9)
1, a kind of hydroprocessing process of inferior patrol, wherein hydrotreatment comprises two beds, step is as follows:
A, bad gasoline contact with catalyst for hydro-upgrading in first beds with hydrogen, and reaction conditions is: hydrogen dividing potential drop 0.5～5.0MPa, 320 ℃～450 ℃ of temperature, liquid hourly space velocity 1.0h
-1～15.0h
-1, hydrogen to oil volume ratio 100～800;
The effluent of B, first beds is separated into light constituent and heavy constituent, and the temperature that 95% of described light constituent boiling range distillates a little is 95 ℃～135 ℃;
The heavy constituent of telling among C, the step B enter second beds, contact with Hydrobon catalyst with hydrogen and carry out the catalytic desulfurhydrogenation reaction;
The effluent of D, second beds mixes with the isolated light constituent of first beds after cooling off and constitutes the full cut of gasoline products.
2, in accordance with the method for claim 1, it is characterized in that the catalyst for hydro-upgrading of first beds filling, its carrier is Al
2O
3, halogen-containing Al
2O
3, in SAPO-11, ZSM-12, ZSM-35, MCM-22, MCM-41, conventional ZSM-5 molecular sieve, ZSM-5 molecular sieve with small crystal grains, HBeta zeolite and the y-type zeolite one or more; The metal of load is one or more among Co, Mo, Ni, W, Pt, Re and the Ir.
3, in accordance with the method for claim 1, it is characterized in that the catalyst for hydro-upgrading of first beds filling, the metal of load is one or more among Co, Mo, Ni and the W, and by the metal oxide compound, its total content is 0.5wt%～20.0wt%.
4,, it is characterized in that the catalyst for hydro-upgrading of first beds filling adds TiO according to the arbitrary described method of claim 1～3
2, SiO
2, ZrO
2With in the rare-earth oxide one or more as auxiliary agent.
5, in accordance with the method for claim 1, the reaction conditions that it is characterized in that first beds described in the steps A is: hydrogen dividing potential drop 1.0～4.0MPa, 350 ℃～435 ℃ of temperature, liquid hourly space velocity 1.0h
-1～10.0h
-1, hydrogen-oil ratio 300～800.
6, in accordance with the method for claim 1, it is characterized in that the used Hydrobon catalyst of second beds described in the step C is Mo-Co/ aluminum oxide, Mo-Ni/ aluminum oxide or W-Mo-Ni/ aluminum oxide.
7, in accordance with the method for claim 1, it is characterized in that the hydrofining technology condition described in the step C is: reaction pressure 1.0MPa～4.0MPa, 240 ℃～360 ℃ of temperature of reaction, volume space velocity 1.0h
-1～10.0h
-1With hydrogen to oil volume ratio 100～500.
8, in accordance with the method for claim 1, the effluent that it is characterized in that the second catalysts bed partly loops back first beds and processes.
9, in accordance with the method for claim 1, it is characterized in that bad gasoline is straight-run spirit, catalytically cracked gasoline, coker gasoline or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031340105A CN1313576C (en) | 2003-09-15 | 2003-09-15 | Process for hydrogenating treatment of foulty gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031340105A CN1313576C (en) | 2003-09-15 | 2003-09-15 | Process for hydrogenating treatment of foulty gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597864A CN1597864A (en) | 2005-03-23 |
| CN1313576C true CN1313576C (en) | 2007-05-02 |
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|---|---|---|---|
| CNB031340105A Expired - Lifetime CN1313576C (en) | 2003-09-15 | 2003-09-15 | Process for hydrogenating treatment of foulty gasoline |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376827B (en) * | 2007-08-27 | 2012-04-04 | 中国石油化工股份有限公司 | Mixed hydrogenation technological process for coker gasoline and once run kerosene |
| CN101434851B (en) * | 2007-11-15 | 2012-02-29 | 中国石油化工股份有限公司 | Mixed hydrogenation process for coker gasoline and coking kerosene |
| US9017545B2 (en) * | 2011-11-10 | 2015-04-28 | China Petroleum & Chemical Corporation | Process for hydrotreating inferior naphtha fraction |
| CN106929098B (en) * | 2015-12-30 | 2018-10-16 | 中国石油天然气股份有限公司 | A kind of method of poor quality gasoline hydrogenation modification |
| CN106929099B (en) * | 2015-12-30 | 2018-10-16 | 中国石油天然气股份有限公司 | A kind of method of inferior patrol hydro-upgrading |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397739A (en) * | 1980-02-19 | 1983-08-09 | Institut Francais Du Petrole | Process for desulfurizing a catalytic cracking or steam cracking effluent |
| CN1253993A (en) * | 1998-11-18 | 2000-05-24 | 法国石油公司 | Production method of low-sulfur gasoline |
| EP1031622A1 (en) * | 1999-02-24 | 2000-08-30 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
| JP2001009856A (en) * | 1999-06-22 | 2001-01-16 | Premark Rwp Holdings Inc | Coated press surface for wear-resistant laminated body and manufacture of laminated body using same |
| CN1316914A (en) * | 1998-09-10 | 2001-10-10 | 催化蒸馏技术公司 | Process for simultaneous treatment and fractionation of light naphtha hydrocarbon streams |
| US6495029B1 (en) * | 1997-08-22 | 2002-12-17 | Exxon Research And Engineering Company | Countercurrent desulfurization process for refractory organosulfur heterocycles |
-
2003
- 2003-09-15 CN CNB031340105A patent/CN1313576C/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397739A (en) * | 1980-02-19 | 1983-08-09 | Institut Francais Du Petrole | Process for desulfurizing a catalytic cracking or steam cracking effluent |
| US6495029B1 (en) * | 1997-08-22 | 2002-12-17 | Exxon Research And Engineering Company | Countercurrent desulfurization process for refractory organosulfur heterocycles |
| CN1316914A (en) * | 1998-09-10 | 2001-10-10 | 催化蒸馏技术公司 | Process for simultaneous treatment and fractionation of light naphtha hydrocarbon streams |
| CN1253993A (en) * | 1998-11-18 | 2000-05-24 | 法国石油公司 | Production method of low-sulfur gasoline |
| US6334948B1 (en) * | 1998-11-18 | 2002-01-01 | Institut Francais Du Petrole | Process for producing gasoline with a low sulphur content |
| EP1031622A1 (en) * | 1999-02-24 | 2000-08-30 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
| JP2001009856A (en) * | 1999-06-22 | 2001-01-16 | Premark Rwp Holdings Inc | Coated press surface for wear-resistant laminated body and manufacture of laminated body using same |
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|---|---|
| CN1597864A (en) | 2005-03-23 |
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