CN1331991C - Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline - Google Patents
Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline Download PDFInfo
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- CN1331991C CN1331991C CNB2004100827044A CN200410082704A CN1331991C CN 1331991 C CN1331991 C CN 1331991C CN B2004100827044 A CNB2004100827044 A CN B2004100827044A CN 200410082704 A CN200410082704 A CN 200410082704A CN 1331991 C CN1331991 C CN 1331991C
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Abstract
The present invention relates to a hydrogenation and modification method for reducing sulfur and olefin contents of inferior-quality gasoline. The present invention comprises the following steps: inferior-quality whole-fraction gasoline is selectively hydrogenated to remove diene and then is pre-fractionated, the light fraction is carried out modification reaction which comprises aromatization, isomerization and benzene alkylation, the heavy fraction is carried out selective hydrodesulfurization reaction, and the reaction products of the light fraction and the heavy fraction are mixed to obtain the final clean gasoline. The method of the present invention has the advantages that the raw material of the inferior-quality gasoline is processed into clean fuel, and minimum octane value loss, high yield of gasoline and stable operation are kept when sulfur is removed and olefin is reduced, all the prior arts can not simultaneously meet the requirements. The method of the present invention can be used for processing inferior-quality catalytically cracked gasoline, coking gasoline, catalytic cracking gasoline, pressure gasoline, etc. into high-quality clean gasoline products.
Description
Technical field
The present invention relates to a kind of hydrogenation modification method of inferior patrol, more particularly, is a kind of hydrotreatment combination process that reduces sulphur and olefin(e) centent in the catalytically cracked gasoline.
Background technology
Along with the increasingly stringent of environmental regulation, the atmospheric pollution that vehicle exhaust causes is paid close attention to by people day by day.The sulphur and the olefin(e) centent that reduce in the gasoline can reduce emission of harmful substances amounts such as volatile organic compounds in the vehicle exhaust (VOCs), oxynitride (NOX), sulfurous gas significantly.What therefore, oneself had all been formulated in countries in the world turns to the clean gasoline new standard of sign with low-sulfur and low alkene.
Catalytic cracking (FCC) sulfur in gasoline content is generally 200～2000 μ g/g, and olefin(e) centent is generally 40.0v%～50.0v%, and research octane number (RON) (abbreviating RON as) is generally 90～94.Catalytically cracked gasoline is the main gasoline component of some refinerys, and harmonic proportion can reach 80%～90% sometimes.Therefore, the sulphur content and the olefin(e) centent of reduction catalytically cracked gasoline are the keys that satisfies the clean gasoline new spec.
Though adopt traditional hydrofining technology can remove sulfide and olefin(e) compound in the catalytically cracked gasoline effectively, but because the higher low-octane alkane of the saturated generation of hydrogenation of olefins of octane value, so, adopt traditional Hydrobon catalyst and technology when desulfurization and reducing olefin(e) centent, must follow the rapid decline of gasoline octane rating.Generally, the desulfurization degree of catalytic gasoline is 90% o'clock, and 5.0～8.0 units of anti-knock index ((R+M)/2) loss consume a large amount of hydrogen simultaneously.How reducing the saturated loss of octane number that causes of alkene is the difficult point of catalytic gasoline in hydrogenating desulfurization and reduction olefin(e) centent technology.
Propose many methods in the prior art and removed sulfide and alkene in the catalytic gasoline, simultaneously, reduced the loss of product octane value as far as possible.CN1488721A has introduced a kind of gasoline selective hydrodesulfurizationmodification (HDS) catalyzer and technology, the FCC gasoline last running that is characterized in the process prefractionation is after combination catalyst (low metal/high metal content) is gone up HDS, intermediate product mixes with lighting end again, thereby avoided in the lighting end hydrogenation of alkene saturated, reduced the saturated loss that causes octane value of hydrogenation because of alkene.It is limited that its weak point is that olefin(e) centent reduces amplitude, and when requiring high desulfurization rate, octane value has certain loss.US5,362,376 have introduced the technology of a kind of catalyzed gasoline hydrogenation desulfurization and shape slective cracking combination.The catalytically cracked gasoline last running that is characterized in prefractionation is after hydrogenating desulfurization, pass through mesopore, tart NiO/HZSM-5 molecular sieve catalyst shape slective cracking again, thereby recover because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization process, and then be in harmonious proportion with lighting end, its weak point mainly is that the yield of gasoline reduces, when requiring high desulfurization rate, yield of gasoline and loss of octane number are bigger especially.CN1350051A discloses a kind of catalyzer that is used for modifying inferior gasoline to prepare clean gasoline, can reduce its alkene, benzene and sulphur content, and keeps not reducing octane value.But its desulfurization performance is limited, and gasoline products does rising, and promptly the yield of gasoline will reduce.
Catalytically cracked gasoline contains a certain amount of diolefine usually except the alkene that contains a large amount of (about 45.0v%), maleic value is 1.5～3.0 gram iodine/100 gram oil generally speaking.Under the high temperature, diolefine is easy to polymerization, causes the catalyzer coking, slackens the catalytic activity of catalyzer, reduces the stability of catalyzer.Can make when serious between reactor inlet and the outlet and produce bigger pressure difference (abbreviation pressure drop), shorten the on-stream time of device.Therefore, prior art activity of such catalysts less stable.
Summary of the invention
At the deficiencies in the prior art, the invention provides the method that rare hydrocarbon production premium product falls in a kind of bad gasoline desulfurization, and the loss of octane number of gasoline is little, the yield of gasoline height, running is stable.
The hydrogenation modification method that the present invention reduces inferior patrol sulphur and olefin(e) centent comprises following process:
(1), the stock oil selective hydrogenation: distillation gasoline raw material inferior complete enters the selective hydrogenation device, hydrogen exist and suitable condition under remove diolefine in the gasoline;
(2), prefractionation: the fractionation of removing alkadiene by selective hydrogenation gasoline product is lighting end and last running;
(3), lighting end upgrading: lighting end comprises one or more upgrading reactions such as aromizing, isomerization and benzene alkylation, reduces olefin(e) centent, improves the octane value of gasoline;
(4), heavy fractioning hydrogenation desulfurization: hydrogenation and removing organic sulfide;
(5), light, heavy naphtha mixing after handle step (3), (4) are obtained low alkene, low sulfur content and the higher clean gasoline product of octane value.
Method provided by the invention can be processed as inferior patrols such as catalytic cracking sulphur, clean gasoline that olefin(e) centent is low; Conversion of olefines in the lighting end is aromatic hydrocarbons (OTA, i.e. Olefins To Aromatics), has reached and has reduced content of olefin in gasoline significantly, reduces the product loss of octane number and reduces the effect that liquid yield loses; The heavy fractioning hydrogenation desulfurization, avoided because of hydrogenation of olefins saturated cause loss of octane number, reduced the hydrogen consumption of gasoline hydrogenation treating processes.While the inventive method gasoline products yield height, stable operation.
Description of drawings
Fig. 1 is a method flow synoptic diagram provided by the invention.
Reactor A filling stock oil removing alkadiene by selective hydrogenation catalyzer; Reactor B filling lighting end modifying catalyst; Reactor C filling heavy fractioning hydrogenation desulfurization catalyst;
Embodiment
Bad gasoline of the present invention is catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline etc. or its mixture.The preferred raw material of the present invention is a catalytically cracked gasoline.The maleic value of catalytically cracked gasoline is generally 1.5～5.0 gram iodine/100 gram oil; Lighting end internal olefin content is higher, is high-octane number component, and sulphur content is lower, mainly exists with the mercaptan form, is easy to remove; In the last running enrichment most of sulfide, and mainly be based on thiophene-type sulfide, need be than hydrogenation and removing under the exacting terms.
Selective hydrogenation catalyst provided by the invention can be any Hydrobon catalyst, as Pd/ aluminum oxide, Mo-Co/ aluminum oxide or W-Ni/ aluminium oxide catalyst etc.The metal oxide content sum is 0.1wt%～20.0wt%, and surplus is carrier and auxiliary agents such as aluminum oxide.Above-mentioned selective hydrogenation catalyst can adopt conventional immersion process for preparing.Metal oxide can be a step impregnation, preferably floods altogether; Steeping fluid can wait the adsorptive capacity dipping, also can be the excessive dipping of steeping fluid.
Selective hydrogenation catalyst provided by the invention uses in the low-temp reaction device.Reaction pressure is generally 1.0MPa～4.5MPa, and temperature of reaction is generally 90 ℃～260 ℃, and volume space velocity is generally 1.0h
-1～15.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; Reaction pressure is preferably 2.0MPa～3.5MPa, and temperature of reaction is preferably 120 ℃～250 ℃, and volume space velocity is preferably 4.0h
-1～10.0h
-1, hydrogen to oil volume ratio is preferably 500: 1～and 700: 1.
After described bad gasoline was handled through selective hydrogenation catalyst, maleic value was generally 0.01～1.0 gram iodine/100 gram oil, preferably less than 0.5 gram iodine/100 gram oil.
Raw material prefractionation of the present invention will cut into gently through the full cut inferior patrol of removing alkadiene by selective hydrogenation, last running, and cut point is 70 ℃～120 ℃, best 85 ℃～100 ℃; Lighting end contains 70%～90% alkene of full cut inferior patrol and 10%～20% sulfide; Last running contains 10%～30% alkene of full cut inferior patrol and 80%～90% sulfide.
Lighting end modifying catalyst provided by the invention is a kind ofly to have based on the aromizing function, have the catalyzer of isomerization and alkylation function concurrently, and in addition, this catalyzer also has certain desulfurization, particularly the function of mercaptan removal sulphur.Catalyzer is active ingredient with the transition metal oxide, is carrier with little grain fineness number hydrogen type molecular sieve, and surplus is a binding agent.Metal oxide content is 1.0wt%～10.0wt%.Transition metal oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999, and can also contain the lanthanide rare metal oxide is lanthanum trioxide and/or cerium oxide.Particularly nickel oxide, molybdenum oxide, zinc oxide, lanthanum trioxide etc.; Molecular sieve content is 50.0wt%～90.0wt%.Molecular sieve is that grain fineness number is at 20nm～500nm, be preferably the hydrogen type molecular sieve of the little grain fineness number in 40nm～200nm scope, as among HZSM-5, HZSM-22, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and the HSAPO-41 etc. one or more, particularly HZSM-5 and/or HZSM-22.Described binding agent is titanium oxide, aluminum oxide, silicon oxide or aluminium oxide-silicon oxide.Above-mentioned ultrafine particle zeolite aromatized catalyst is to adopt immersion process for preparing.Oxide compound can be a step impregnation, preferably floods altogether; Steeping fluid can wait the adsorptive capacity dipping, also can be the excessive dipping of steeping fluid.The composition of modifying catalyst and preparation etc. can be undertaken by CN1488723A.
Lighting end upgrading reaction pressure provided by the invention is generally 1.0MPa～4.5MPa, and temperature of reaction is generally 360 ℃～460 ℃, and volume space velocity is generally 1.0h
-1～5.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; Reaction pressure is preferably 2.0MPa～3.5MPa, and temperature of reaction is preferably 380 ℃～440 ℃, and volume space velocity is preferably 2.0h
-1～4.0h
-1, hydrogen to oil volume ratio is preferably 500～700: 1.
Heavy fractioning hydrogenation desulfurization catalyst system provided by the invention is to be made up of at least a low-metal content and at least a high metals content catalysts along the reagent flow direction.Catalyzer comprises VIB and/or one or more base metals of VIII family, auxiliary agent and unformed aluminum oxide or silica-alumina supports.Top low-metal content catalyst metal oxide content is 1.0wt%～10.0wt%, particularly 3.0wt%～6.0wt%, and auxiliary agent content is 1.0wt%～5.0wt%, particularly 1.5wt%～3.0wt%; The high metals content catalysts metal oxide content in bottom is 8.0wt%～18.0wt%, particularly 10.0wt%～15.0wt%; Auxiliary agent content is 1.0wt%～5.0wt%, particularly 1.5wt%～3.0wt%.VIB, VIII family metal be generally W, Mo, Ni, Co etc. one or more, auxiliary agent is K and/or P.Above-mentioned catalyzer is to adopt immersion process for preparing.Oxide compound can be a step impregnation, preferably floods altogether; Steeping fluid can wait the adsorptive capacity dipping, also can be the excessive dipping of steeping fluid.Specifically can select described catalyzer of CN1488721A and technological process.
Heavy fractioning hydrogenation desulphurization reaction pressure provided by the invention is generally 1.0MPa～4.5MPa, and temperature of reaction is generally 230 ℃～330 ℃, and volume space velocity is generally 1.0h
-1～10.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; Reaction pressure is preferably 2.0MPa～3.5MPa, and temperature of reaction is preferably 240 ℃～280 ℃, and volume space velocity is preferably 3.0h
-1～6.0h
-1, hydrogen to oil volume ratio is preferably 500～700: 1.
Because the product temperature of lighting end reforming reactor outlet is higher, therefore, can satisfy the requirement of heavy fractioning hydrogenation desulphurization reaction to temperature by the method for itself and the heat exchange of last running raw material, the requirement of selective hydrogenation is satisfied in heavy fractioning hydrogenation desulfurization product and full distillation gasoline raw material heat exchange.Process furnace is heated to lighting end the requirement of upgrading reaction pair temperature.Therefore, the present invention has effectively utilized heat, has reduced energy consumption.
Material choice hydrogenation, lighting end upgrading and heavy fractioning hydrogenation desulfurization are operated under close pressure, can satisfy the needs of reactive system hydrogen recycle with same recycle compressor, help save energy, and save facility investment.
Further specify the solution of the present invention and effect below by embodiment, but therefore do not limit the present invention.Above-mentioned processing condition and catalyzer are conventional, and concrete selection can be determined by this area general knowledge according to the requirement of raw material properties, product etc.
Embodiment 1
Present embodiment has provided a kind of high-sulfur, high olefin content FCC gasoline desulfur inferior, has fallen the effect of alkene.
(1), stock oil selective hydrogenation
Adorn MoO in the reactor A
3(9.0wt%)-NiO (4.5wt%)-WO
3(19.0wt%)/Al
2O
3Selective hydrogenation catalyst;
Reaction pressure is 2.8MPa, and temperature of reaction is 180 ℃, and volume space velocity is 6.0h
-1, hydrogen to oil volume ratio is 600: 1.
Table 1 has been listed the character of full cut FCC gasoline stocks and selective hydrogenation product
Character before and after the full cut FCC gasoline selective hydrogenation of table 1
| Project | Full cut FCC gasoline | The selective hydrogenation product |
| Maleic value, gI/100g | 2.54 | 0.05 |
| Density, g/ml | 0.7290 | 0.7291 |
| Sulphur content, μ g/g | 1600 | 1520 |
| Mercaptans content, μ g/g | 34.5 | 16.9 |
| Olefin(e) centent, v% | 52.9 | 51.2 |
| Aromaticity content, v% | 18.4 | 18.3 |
| Research octane number (RON), RON | 91.7 | 91.5 |
(2), stock oil prefractionation
Table 2 listed with 90 ℃ be cut point, FCC gasoline is the character of lighting end and last running after the fractionation selective hydrogenation.
Catalytic gasoline and character light, last running after table 2 selective hydrogenation
| Project | The selective hydrogenation product | ＜90 ℃ of lighting ends | ＞90 ℃ of last running |
| Yield, wt% | 100 | 45.0 | 55.0 |
| Maleic value, gI/100g | 0.05 | 0.04 | 0.06 |
| Density, g/ml | 0.7291 | 0.6632 | 0.7848 |
| Sulphur content, μ g/g | 1520 | 260 | 2400 |
| Mercaptans content, μ g/g | 16.9 | 22.0 | 12.0 |
| Olefin(e) centent, v% | 51.2 | 62.9 | 36.9 |
| Aromaticity content, v% | 18.3 | 3.6 | 32.8 |
| Research octane number (RON), RON | 91.5 | 94.3 | 87.0 |
| Boiling range/℃ (initial boiling point～final boiling point) | 35～185 | 35～95 | 87～185 |
(3), lighting end upgrading
A kind of La packs in the reactor B
2O
3-ZnO/HZSM-5 aromatized catalyst, this catalyzer La
2O
3For 2.0wt%, ZnO are 1.5wt%, the HZSM-5 grain fineness number is 20nm～80nm, SiO
2/ Al
2O
3Mol ratio 28.
Reaction pressure is 2.8MPa, and temperature of reaction is 400 ℃, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is preferably 600: 1.Table 3 has been listed the character of lighting end upgrading raw material and product
The character of table 3 lighting end upgrading raw material and product
| Project | The lighting end raw material | The lighting end upgraded product |
| Yield, wt% | - | 95.3 |
| Density, g/ml | 0.6632 | 0.7025 |
| Sulphur content, μ g/g | 260 | 42 |
| Mercaptans content, μ g/g | 23.0 | 2.0 |
| Olefin(e) centent, v% | 62.9 | 23.8 |
| Aromaticity content, v% | 3.6 | 14.8 |
| Research octane number (RON), RON | 94.3 | 93.7 |
| Boiling range/℃ (initial boiling point～final boiling point) | 35～95 | 36～110 |
(4), heavy fractioning hydrogenation desulfurization
A kind of low-metal content MoO packs among the reactor C
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3With a kind of high metal content WO
3(12.0wt%)-NiO (4.5wt%)-P
2O
5(1.5wt%)/Al
2O
3Combination catalyst.
Reaction pressure is 2.8MPa, and temperature of reaction is 270 ℃, and volume space velocity is 4.0h
-1, hydrogen to oil volume ratio is preferably 600: 1.Table 4 has been listed the character of heavy fractioning hydrogenation desulfurization material and product
The character of table 4 heavy fractioning hydrogenation desulfurization material and product
| Project | The last running raw material | The heavy fractioning hydrogenation desulfurization product |
| Yield, wt% | - | 99.8 |
| Density, g/ml | 0.7848 | 0.7920 |
| Sulphur content, μ g/g | 2400 | 150 |
| Mercaptans content, μ g/g | 12.0 | 14.0 |
| Olefin(e) centent, v% | 36.9 | 16.0 |
| Aromaticity content, v% | 32.8 | 32.6 |
| Research octane number (RON), RON | 87.0 | 83.2 |
| Boiling range/℃ (initial boiling point～final boiling point) | 87～185 | 88～187 |
(5), light, the heavy naphtha after the processing is in harmonious proportion
Light, heavy naphtha after handle step (3), (4) are mixed, obtain low alkene, low sulfur content and the higher clean gasoline product of octane value.Light, character that heavy naphtha is in harmonious proportion after table 5 has been listed raw material FCC gasoline and handled
Table 5 raw material FCC gasoline with handle after light, character that heavy naphtha is in harmonious proportion
| Project | Full cut FCC gasoline | The present invention handles product |
| Density, g/ml | 0.7290 | 0.7291 |
| Sulphur content, μ g/g | 1600 | 120 |
| Mercaptans content, μ g/g | 34.5 | 7.0 |
| Olefin(e) centent, v% | 52.9 | 16.2 |
| Aromaticity content, v% | 18.4 | 27.3 |
| Research octane number (RON) (RON) | 91.7 | 90.0 |
| Anti-knock index ((R+M)/2) | 86.0 | 85.5 |
| Yield, wt% | 98.1 |
As can be seen from Table 5: method of the present invention can be reduced to the sulphur content of FCC gasoline ≯ 150% μ g/g by 1600 μ g/g, olefin(e) centent is reduced to ≯ 18v% by 52.9v%, research octane number (RON) RON loses ≯ 1.7 units, anti-knock index (R+M)/2) loss is not more than 0.5 unit, C
5 +Yield of gasoline ≮ 98.0wt% can be processed as the high-quality cleaning product with the full distillation gasoline of FCC inferior.
Embodiment 2
Present embodiment has provided a kind of moderate sulfur, olefin(e) centent FCC gasoline desulfur inferior, has fallen the effect of alkene.
(1), stock oil selective hydrogenation
Adorn 0.25wt%Pd/Al in the reactor A
2O
3Selective hydrogenation catalyst;
Reaction pressure is 3.2MPa, and temperature of reaction is 130 ℃, and volume space velocity is 8.0h
-1, hydrogen to oil volume ratio is 600: 1.
Table 6 has been listed the character of full cut FCC gasoline stocks and selective hydrogenation product
Character before and after the full cut FCC gasoline selective hydrogenation of table 6
| Project | Full cut FCC gasoline | The selective hydrogenation product |
| Maleic value, gI/100g | 1.45 | 0.03 |
| Density, g/ml | 0.7210 | 0.7211 |
| Sulphur content, μ g/g | 662 | 608 |
| Mercaptans content, μ g/g | 30.5 | 12.9 |
| Olefin(e) centent, v% | 40.5 | 39.2 |
| Aromaticity content, v% | 19.5 | 19.4 |
| Research octane number (RON), RON | 93.2 | 93.0 |
(2), stock oil prefractionation
Table 7 listed with 100 ℃ be cut point, FCC gasoline is the character of lighting end and last running after the fractionation selective hydrogenation.
Catalytic gasoline and character light, last running after table 7 selective hydrogenation
| Project | The selective hydrogenation product | ＜100 ℃ of lighting ends | ＞100 ℃ of last running |
| Yield, wt% | 100 | 39.1 | 60.9 |
| Maleic value, gI/100g | 0.03 | 0.02 | 0.03 |
| Density, g/ml | 0.7211 | 0.6831 | 0.7888 |
| Sulphur content, μ g/g | 608 | 160 | 880 |
| Mercaptans content, μ g/g | 12.9 | 17.0 | 11.0 |
| Olefin(e) centent, v% | 39.2 | 49.9 | 30.9 |
| Aromaticity content, v% | 19.4 | 5.6 | 33.8 |
| Research octane number (RON), RON | 93.0 | 94.5 | 91.2 |
| Boiling range/℃ (initial boiling point～final boiling point) | 33～181 | 33～102 | 95～181 |
(3), lighting end upgrading
A kind of La packs in the reactor B
2O
3-NiO-MoO
3/ HZSM-22 aromatized catalyst, this catalyzer La
2O
3Be 3.0wt%, NiO is 2.0wt%, MoO
3Be 3.0wt%.The HZSM-22 grain fineness number is 50nm～100nm, SiO
2/ Al
2O
3Mol ratio 36.
Reaction pressure is 3.2MPa, and temperature of reaction is 420 ℃, and volume space velocity is 3.0h
-1, hydrogen to oil volume ratio is preferably 700: 1.Table 8 has been listed the character of lighting end upgrading raw material and product
The character of table 8 lighting end upgrading raw material and product
| Project | The lighting end raw material | The lighting end upgraded product |
| Yield, wt% | - | 96.3 |
| Density, g/ml | 0.6831 | 0.7058 |
| Sulphur content, μ g/g | 160 | 20 |
| Mercaptans content, μ g/g | 17.0 | 2.0 |
| Olefin(e) centent, v% | 49.9 | 18.2 |
| Aromaticity content, v% | 5.6 | 16.8 |
| Research octane number (RON), RON | 94.5 | 94.0 |
| Boiling range/℃ (initial boiling point～final boiling point) | 33～102 | 35～120 |
(4), heavy fractioning hydrogenation desulfurization
A kind of low-metal content MoO packs among the reactor C
3(3.0wt%)-NiO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3With a kind of high metal content MoO
3(12.0wt%)-CoO (4.0wt%)-P
2O
5(1.5wt%)/Al
2O
3Combination catalyst.
Reaction pressure is 3.2MPa, and temperature of reaction is 250 ℃, and volume space velocity is 5.0h
-1, hydrogen to oil volume ratio is preferably 600: 1.Table 9 has been listed the character of heavy fractioning hydrogenation desulfurization material and product
The character of table 9 heavy fractioning hydrogenation desulfurization material and product
| Project | The last running raw material | The heavy fractioning hydrogenation desulfurization product |
| Yield, wt% | - | 99.9 |
| Density, g/ml | 0.7888 | 0.7890 |
| Sulphur content, μ g/g | 880 | 60 |
| Mercaptans content, μ g/g | 11.0 | 9.0 |
| Olefin(e) centent, v% | 30.9 | 14.2 |
| Aromaticity content, v% | 33.8 | 33.6 |
| Research octane number (RON), RON | 91.2 | 88.0 |
| Boiling range/℃ (initial boiling point～final boiling point) | 95～181 | 96～182 |
(5), light, the heavy naphtha after the processing is in harmonious proportion
Light, heavy naphtha after handle step (3), (4) are mixed, obtain low alkene, low sulfur content and the higher clean gasoline product of octane value.Light, character that heavy naphtha is in harmonious proportion after table 10 has been listed raw material FCC gasoline and handled
Table 10 raw material FCC gasoline with handle after light, character that heavy naphtha is in harmonious proportion
| Project | Full cut FCC gasoline | The present invention handles product |
| Density, g/ml | 0.7210 | 0.7291 |
| Sulphur content, μ g/g | 662 | 45 |
| Mercaptans content, μ g/g | 30.5 | 5.0 |
| Olefin(e) centent, v% | 40.5 | 15.0 |
| Aromaticity content, v% | 19.5 | 28.8 |
| Research octane number (RON) (RON) | 93.2 | 91.8 |
| Motor-method octane number (MON) | 80.4 | 80.0 |
| Anti-knock index ((R+M)/2) | 86.8 | 85.9 |
| Yield, wt% | - | 98.5 |
As can be seen from Table 10: method of the present invention can be reduced to the sulphur content of FCC gasoline ≯ 50% μ g/g by 662 μ g/g, olefin(e) centent is reduced to ≯ 15v% by 40.5v%, research octane number (RON) RON loses ≯ 1.4 units, anti-knock index (R+M)/2) loss is not more than 1.0 units, C
5 +Yield of gasoline ≮ 98.0wt% can be processed as the high-quality cleaning product with the full distillation gasoline of FCC inferior.
In addition, method hydrogen consumption of the present invention is low, but the long period steady running.
Claims (12)
1, a kind of hydrogenation modification method that reduces inferior patrol sulphur and olefin(e) centent comprises following process:
(1), the stock oil selective hydrogenation: distillation gasoline raw material inferior complete enters the selective hydrogenation device, hydrogen exist and suitable condition under remove diolefine in the gasoline;
(2), prefractionation: the fractionation of removing alkadiene by selective hydrogenation gasoline product is lighting end and last running;
(3), lighting end upgrading: lighting end comprises one or more upgrading reactions of aromizing, isomerization and benzene alkylation, reduces olefin(e) centent, improves the octane value of gasoline;
(4), heavy fractioning hydrogenation desulfurization: hydrogenation and removing organic sulfide;
(5), light, heavy naphtha mixing after handle step (3), (4) are obtained low alkene, low sulfur content and the higher clean gasoline product of octane value;
Wherein the described selective hydrogenation condition of step (1) is: reaction pressure 1.0MPa～4.5MPa, 90 ℃～260 ℃ of temperature of reaction, volume space velocity 1.0h
-1～15.0h
-1, hydrogen to oil volume ratio 200: 1～1000: 1; The described lighting end upgrading of step (3) reaction conditions is: reaction pressure 1.0MPa～4.5MPa, 360 ℃～460 ℃ of temperature of reaction, volume space velocity 1.0h
-1～5.0h
-1, hydrogen to oil volume ratio 200: 1～1000: 1; The described heavy fractioning hydrogenation desulphurization reaction of step (4) condition is: reaction pressure 1.0MPa～4.5MPa, 230 ℃～330 ℃ of temperature of reaction, volume space velocity 1.0h
-1～10.0h
-1, hydrogen to oil volume ratio 200: 1～1000: 1.
2, in accordance with the method for claim 1, it is characterized in that the full distillation gasoline of described poor quality is catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline etc. or its mixture.
3, in accordance with the method for claim 1, it is characterized in that the described selective hydrogenation condition of step (1) is: reaction pressure 2.0MPa～3.5MPa, 120 ℃～250 ℃ of temperature of reaction, volume space velocity 4.0h
-1～10.0h
-1, hydrogen to oil volume ratio 500: 1～700: 1; The described lighting end upgrading of step (3) reaction conditions is: reaction pressure 2.0MPa～3.5MPa, 380 ℃～440 ℃ of temperature of reaction, volume space velocity 2.0h
-1～4.0h
-1, hydrogen to oil volume ratio 500～700: 1; The described heavy fractioning hydrogenation desulfurization condition of step (4) is: reaction pressure 2.0MPa～3.5MPa, 240 ℃～280 ℃ of temperature of reaction, volume space velocity 3.0h
-1～6.0h
-1, hydrogen to oil volume ratio 500～700: 1.
4, in accordance with the method for claim 1, the cut point that it is characterized in that described lighting end of step (2) and last running is 70 ℃～120 ℃.
5, in accordance with the method for claim 1, the cut point that it is characterized in that described lighting end of step (2) and last running is 85 ℃～100 ℃.
6, in accordance with the method for claim 1, it is characterized in that the described modifying catalyst containing metal of step (3) oxide compound is 1.0wt%～10.0wt%, contain molecular sieve 50.0wt%～90.0wt%, and tackiness agent.
7, in accordance with the method for claim 6, it is characterized in that described metal oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999; Molecular sieve is the hydrogen type molecular sieve of the little grain fineness number of grain fineness number in 20nm～500nm scope, molecular screening one or more in HZSM-5, HZSM-22, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and HSAPO-41.
8, in accordance with the method for claim 7, it is characterized in that described metal oxide also contains lanthanum trioxide and/or cerium oxide, the zeolite crystal degree is 40nm～200nm.
9, in accordance with the method for claim 1, it is characterized in that the described heavy fractioning hydrogenation desulfurization catalyst of step (4) system is to form along at least a low-metal content of reagent flow direction and at least a high metals content catalysts, catalyzer by VIB and or one or more base metals of VIII family, auxiliary agent and unformed aluminum oxide or silica-alumina supports form.
10, in accordance with the method for claim 9, it is characterized in that described low-metal content catalyst metal oxide content is 1.0wt%～10.0wt%, auxiliary agent content is 1.0wt%～5.0wt%, the high metals content catalysts metal oxide content in bottom is 8.0wt%～18.0wt%, auxiliary agent content is 1.0wt%～5.0wt%, and auxiliary agent is K and/or P.
11, in accordance with the method for claim 9, it is characterized in that described low-metal content catalyst metal oxide content is 3.0wt%～6.0wt%, auxiliary agent content is 1.5wt%～3.0wt%; The high metals content catalysts metal oxide content in bottom is 10.0wt%～15.0wt%, and auxiliary agent content is 1.5wt%～3.0wt%.
12, in accordance with the method for claim 1, it is characterized in that the product and the heat exchange of last running raw material of the outlet of lighting end reforming reactor, heavy fractioning hydrogenation desulfurization product and full distillation gasoline raw material heat exchange.
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| CNB2004100827044A CN1331991C (en) | 2004-10-29 | 2004-10-29 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
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| CNB2004100827044A CN1331991C (en) | 2004-10-29 | 2004-10-29 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
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| CN1331991C true CN1331991C (en) | 2007-08-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101368111B (en) * | 2007-08-16 | 2013-04-24 | 中国石油天然气集团公司 | Hydrogenation modification method for catalytically cracked gasoline |
| CA2705592A1 (en) * | 2007-11-19 | 2009-05-29 | Shell Internationale Research Maatschappij B.V. | Catalyst particles, process for the preparation of an olefinic product, and process for the preparation of an oxygenate conversion catalyst |
| CN101845322B (en) * | 2010-05-12 | 2012-10-17 | 中国石油天然气股份有限公司 | Production method for reducing sulfur and olefin content in gasoline |
| CN102041086A (en) * | 2011-01-17 | 2011-05-04 | 江苏佳誉信实业有限公司 | Selective hydrodesulfurization method for high-sulfur high-olefin catalytic gasoline |
| CN102618328B (en) * | 2011-01-31 | 2015-02-11 | 北京安耐吉能源工程技术有限公司 | Gasoline processing method |
| CN102618329B (en) * | 2011-01-31 | 2014-06-04 | 北京安耐吉能源工程技术有限公司 | Gasoline processing method |
| CN102618325B (en) * | 2011-01-31 | 2014-06-04 | 北京安耐吉能源工程技术有限公司 | Gasoline processing method |
| RU2451058C1 (en) * | 2011-03-30 | 2012-05-20 | Общество с ограниченной ответственностью "Научно-производственная фирма "ОЛКАТ" | Method to produce high-octane component of engine fuel |
| CN102994148B (en) * | 2011-09-15 | 2014-12-24 | 中国石油天然气股份有限公司 | Deep desulfurization method for gasoline |
| CN103102965B (en) * | 2011-11-10 | 2014-12-31 | 中国石油化工股份有限公司 | Diene-containing gasoline distillate series connection hydrotreating method |
| CN103131465A (en) * | 2011-11-28 | 2013-06-05 | 上海河图工程股份有限公司 | Method for reducing benzene content in gasoline |
| RU2487161C1 (en) * | 2012-05-05 | 2013-07-10 | Общество с ограниченной ответственностью "Научно-производственная фирма "ОЛКАТ" | Method for production of high-octane petrol |
| CN109097104B (en) * | 2018-09-11 | 2019-11-08 | 福州大学 | A kind of FCC gasoline method for modifying |
| CN115368936B (en) * | 2021-05-17 | 2024-03-26 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline modification method and product |
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|---|---|---|---|---|
| US5362376A (en) * | 1991-08-15 | 1994-11-08 | Mobil Oil Corporation | Gasoline upgrading process using large crystal intermediate pore size zeolites |
| CN1488721A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
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| US5362376A (en) * | 1991-08-15 | 1994-11-08 | Mobil Oil Corporation | Gasoline upgrading process using large crystal intermediate pore size zeolites |
| CN1488721A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
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