CN1268720C - Aromatization catalyst and clean gasoline producing process - Google Patents
Aromatization catalyst and clean gasoline producing process Download PDFInfo
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- CN1268720C CN1268720C CN 02133129 CN02133129A CN1268720C CN 1268720 C CN1268720 C CN 1268720C CN 02133129 CN02133129 CN 02133129 CN 02133129 A CN02133129 A CN 02133129A CN 1268720 C CN1268720 C CN 1268720C
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Abstract
The present invention relates to a process for producing aromatization catalysts and clean gasoline, which is characterized in that FCC gasoline containing high sulfur and high olefin is processed into clean gasoline by using a combined process for hydrofining and aromatizing a two-section catalyst. A molecular sieve catalyst with small crystal particles is used by the aromatization catalyst of the process, and the aromatization catalyst is hydrothermally treated so that the strong acid quantity of the catalyst is reduced. The process has the advantages for improving the yield of gasoline and reducing the antiknock index loss of products when the sulfur is removed and the olefin content is reduced; meanwhile, the diene easily coked at high temperature is removed in the hydrofining process, and the stability of the aromatization catalyst is improved. The process is mainly used processing poor-quality FCC gasoline into high-quality gasoline containing low sulfur and low olefin.
Description
1, technical field
The present invention relates to a kind of fluid catalytic cracking (FCC) inferior patrol and produce the aromatized catalyst and the technology of low-sulfur, low olefin-content clean gasoline by high sulfur content, high olefin content.
2, background technology
Along with people's environmental consciousness improves rapidly, the atmospheric pollution that vehicle exhaust causes is paid close attention to by people day by day.Because the sulphur and the olefin(e) centent that reduce in the gasoline can reduce restorative organic compound (VOCs), oxynitride (NO in the vehicle exhaust
X) and emission of harmful substances such as sulfurous gas.At present, main in the world developed country is limited in the sulphur content of motor spirit below the 200 μ g/g, and olefin(e) centent is limited in 30.0 (v) below the %.Catalytic gasoline accounts for the large percentage that gasoline is in harmonious proportion usually, there is bavin refinery gasoline harmonic proportion to reach 80%～90%, the catalytic gasoline sulphur content is 500 μ g/g～2000 μ g/g, and olefin(e) centent is 40.0, and (v) (v) %, research octane number (RON) (abbreviating RON as) is 90～94 in %～55.0.Therefore the sulphur content and the olefin(e) centent that reduce catalytic gasoline are to produce the key that satisfies new demand quality gasoline.
Though adopt traditional hydrofining technology can remove sulfide and olefin(e) compound in the catalytic 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, during catalytic gasoline desulfurization degree 90%, 5.0～8.0 units of anti-knock index ((R+M)/2) loss consume a large amount of hydrogen simultaneously.The loss that how to reduce the saturated octane value that causes of alkene is the difficult point of catalytic gasoline in hydrogenating desulfurization and reduction olefin(e) centent problem.
U.S.Pat.No.5,362,376 technologies of having introduced a kind of catalyzed gasoline hydrogenation desulfurization and having selected shape hydrocracking two-stage catalytic agent combination.The catalytically cracked gasoline last running that is characterized in prefractionation is at first carried out hydrogenating desulfurization by a kind of hydrogenating desulfurization Mo-Co or Mo-Ni catalyzer, desulfurization product passes through mesopore, tart NiO/HZSM-5 molecular sieve catalyst shape slective cracking more then, with the macromolecular alkane shape slective cracking of low-octane straight chain is high-octane small molecules hydro carbons, 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 together with the light fractions of FCC naphtha of prefractionation.This patent points out that the too weak meeting of the acidity of acid molecular sieve catalyst reduces catalytic activity, influences the effect of octane value recovering; Acidity of catalyst can cause the generation of excessive fragmentation reaction too by force, influences the liquid gasoline product yield of desulfurization catalytic gasoline.
Chinese patent application numbers 93102129 discloses a kind of catalytic modification of poor quality gasoline-aromatization method.Thick pressure gasoline is catalytic reforming under conditions of non-hydrogen at first, and then carries out aromizing on Zn-Al or Zn-Al-rare earth HZSM-5, and the temperature of aromizing is 480 ℃～650 ℃, and pressure is 0.05MPa～1.5MPa.Final yield of gasoline is 55m%～75m%.Because the aromatized catalyst coking deactivation is very fast, general aromatized catalyst will be regenerated once in 15 days, therefore, need two aromatization reactor blocked operations.
Catalytically cracked gasoline contains the diolefin of 2.0v%～5.0v% usually except containing the alkene about 45.0v%.At high temperature, diolefin is easy to polymerization on the strongly-acid position on acid molecular sieve catalyst surface, causes the catalyzer coking, slackens the catalytic activity of catalyzer, reduces the effect and the stability of catalytic performance of octane value recovering.
3, summary of the invention
The object of the present invention is to provide a kind of high stability the FCC gasoline desulfur, alkene falls, reduce the catalyzer and the technology of the production clean gasoline of institute's production gasoline product anti-knock index ((R+M)/2) loss simultaneously.
The catalyzer of production clean gasoline provided by the invention comprises Hydrobon catalyst and FCC aromatization of gas catalyzer, wherein the aromatization of gas catalyzer is a benchmark with the weight percent of catalyzer, and it consists of: metal oxide content is 1.0m%～10.0m%; Molecular sieve content is 50.0m%～90.0m%; Surplus is a binding agent.
The specific surface area of above-mentioned aromatized catalyst is 300m
2/ g～600m
2/ g, pore volume are 0.15ml/g～0.55ml/g, average pore diameter 1.3nm～3.3nm.
The NH3-TPD strength of acid is distributed as under the above-mentioned aromatized catalyst differing temps: 160 ℃ are 0.800mmol/g～1.00mmol/g; 250 ℃ is 0.600mmol/g～0.800mmol/g; 350 ℃ is 0.400mmol/g～0.600mmol/g; 450 ℃ is 0.080mmol/g～0.200mmol/g.
Metal is selected from transiting group metal elements and/or alkali earth metal in the above-mentioned aromatized catalyst, as in zinc, iron, manganese, nickel, cobalt, molybdenum, tungsten, magnesium, calcium, the barium etc. one or more.In preferred magnesium oxide, zinc oxide and the nickel oxide one or more.
Molecular sieve is the hydrogen type molecular sieve of the little grain fineness number of grain fineness number in 20nm～800nm scope, as HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 or HSAPO-41 etc., particularly HZSM-5, HBeta or HL.
The hydrogen type molecular sieve of above-mentioned little grain fineness number can use separately, also can two or more mix use.
Described binding agent can be aluminum oxide, silicon oxide or aluminium oxide-silicon oxide.
The preparation method of the little grain fineness number molecular sieve catalyst of metal provided by the present invention is:
1, the preparation of little grain fineness number molecular sieve Aromatizatian catalytic agent carrier
Little grain fineness number hydrogen type molecular sieve and binding agent is even according to mixed of the present invention, grinding, adding concentration is the aqueous nitric acid of 3.0～8.0g/100ml, is rolled into extruded moulding after the wet cake of micelle shape, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～600 ℃ following roastings 3～10 hours.Take out after reducing to room temperature, prepare the little grain fineness number molecular sieve of Hydrogen Aromatizatian catalytic agent carrier.
2, the preparation of little grain fineness number molecular sieve aromatized catalyst intermediate
Nickelous nitrate, magnesium nitrate and zinc nitrate are dissolved in the deionized water, are made into the nitrate solution that oxide concentration is 2.0～6.0g/100ml.(0.50ml/g～0.70ml/g), incipient impregnation is 5～10 hours under the room temperature by the water-intake rate of above-mentioned carrier.Then, 110 ℃～140 ℃ dry down 8～15 hours, 400 ℃～500 ℃ following roastings 3～10 hours.Take out after reducing to room temperature, prepare oxidiferous little grain fineness number molecular sieve aromatized catalyst intermediate.
3, the preparation of little grain fineness number molecular sieve aromatized catalyst
A certain amount of above-mentioned little grain fineness number molecular sieve aromatized catalyst intermediate is packed in the vertical high temperature activation furnace, under the atmosphere of water flowing steam, be warming up to 450 ℃～500 ℃, and under this temperature hydrothermal treatment consists 3～20 hours, then, stop water flowing steam, with the nitrogen oxygen atmosphere of nitrogen content 95m% that the wet steam displacement of adsorbing on the catalyzer is clean, draw off after being cooled to room temperature, prepare the little grain fineness number molecular sieve aromatized catalyst that is rich in intermediate acid intensity.
The present invention is produced with hydrofining and two sections processes of aromizing by FCC gasoline production low-sulfur, low alkene clean gasoline technology, and concrete grammar is as follows:
The first stage catalytic cracking gasoline hydrofinishing: catalytically cracked gasoline is contacted with Hydrobon catalyst under hydrorefined condition, to remove the diolefin of easy polymerization coking under sulfide and the olefin(e) compound, particularly high temperature in the gasoline.
Second section light-hydrocarbon aromatized octane value recovering that carries out: with first section hydrotreated product process aromizing molecular sieve catalyst of the present invention, at reaction pressure 1.5MPa～4.5MPa, 350 ℃～450 ℃ of temperature of reaction, volume space velocity 0.5h
-1～3.0h
-1With hydrogen to oil volume ratio 200～800: under 1 the condition, with light-hydrocarbon aromatized be aromatic hydrocarbons, with the anti-knock index loss that recovers to cause because of hydrogenation of olefins in the unifining process is saturated, isomerization of carrying out and cracking reaction simultaneously also played certain booster action to octane value recovering.
Said Hydrobon catalyst can be the Hydrobon catalyst of any routine in first section, preferably Mo-Co or Mo-Ni/ aluminium oxide catalyst.Said hydrofining condition is: reaction pressure 1.5MPa～4.5MPa, 220 ℃～300 ℃ of temperature of reaction, volume space velocity 2.0h
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.
In addition, because the boiling range of catalytic gasoline is 34 ℃～190 ℃.Alkene concentrates in the lighting end (boiling range be alkene accounts for total olefin in 34 ℃～70 ℃ about 50%); Sulfide concentrates in the last running (boiling range be sulphur accounts for total sulfur in 70 ℃～190 ℃ about 95%).Therefore, if indivedual refineries do not need the alkene of FCC gasoline is reduced to lower degree, in order to reduce because of the saturated loss of octane number that causes of light olefin hydrogenation and to reduce the hydrogen consumption, both economical, rational way be earlier with the fractionation of full cut catalytic gasoline for＜70 ℃ and＞70 ℃ light, weigh two kinds of cuts.Wherein, last running enters in the above-mentioned reaction process and handles, and then mixes with lighting end.
Because first section unifining process is thermopositive reaction, generally can produce 30 ℃～100 ℃ temperature rises along reactor bed, and second section octane value recovering aromatization process is thermo-negative reaction, and need high slightly temperature, therefore, Hydrobon catalyst and the octane value recovering aromatized catalyst filling of preferably connecting.Both can connect and be contained in the same reactor.For the ease of control, preferably be contained in respectively in two reactors.
Aromatization of gas catalyzer of the present invention is selected the molecular sieve of little crystal grain for use, has short duct, helps molecular diffusion, has reduced unnecessary secondary side reaction.Steam-treated after the aromatized catalyst employing moulding of the present invention reduces the strong acid amount, in aromatization process, can reduce scission reaction, has improved the yield of gasoline, has reduced the carbon deposit of catalyzer simultaneously.Process using hydrofining of the present invention/aromizing is handled FCC gasoline, is reaching when desulfurization and reducing olefin(e) centent, and the anti-knock index loss of product is less; Simultaneously, unifining process has removed the diolefine of easy coking under the high temperature, improves the stability of the aromatization catalyzer with octane value recovering function.
4, embodiment
Example 1
This examples preparation 1.5m%NiO-0.25m%MgO/ grain fineness number is 70nm～150nm HBeta aromatized catalyst.
Take by weighing 229.6g HBeta (SiO
2/ Al
2O
3Mol ratio 33), 140.0g Al
2O
3, and their ground and mixed is even, adding 150ml concentration is the dilute nitric acid solution of 3.6g/100ml, grinds to form the suitable muffin body of humidity.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 520 ℃ of following roastings 8 hours, makes the Aromatizatian catalytic agent carrier, is numbered SA.
Take by weighing said catalyst carrier SA 100g and put into and spray jar, start rotor pump.The nickelous nitrate, the magnesium nitrate solution that 52ml are contained 1.5g NiO and 0.25g MgO in 30 minutes spray among the support of the catalyst SA.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 8 hours, makes the aromatized catalyst intermediate, is numbered IA.
Take by weighing above-mentioned aromatization catalyst intermediate IA 100ml and put into vertical catalyst activation stove, handled 8 hours, stop into water at aqua volume ratio 3: 1,460 ℃ of following steam of temperature.Use N then
2The nitrogen oxygen atmosphere replacing water steam of content 95% was controlled 30 ℃/hour and is cooled to room temperature after 4 hour, drew off, and made aromatized catalyst, was numbered CA.
The rerum natura of aromatized catalyst carrier S A, intermediate compound I A, catalyzer CA is listed in the table 1.
Example 2
This examples preparation 3.0m%NiO-0.50m%MgO/ grain fineness number is 100nm～500nmHZSM-5 aromatized catalyst.
Take by weighing 229.6g HZSM-5 (SiO
2/ Al
2O
3Mol ratio 27), 140.0g Al
2O
3, and their ground and mixed is even, adding 150ml concentration is the dilute nitric acid solution of 5.6g/100ml, grinds to form the suitable muffin body of humidity.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 520 ℃ of following roastings 8 hours, makes the Aromatizatian catalytic agent carrier, is numbered SB.
Take by weighing said catalyst carrier SB 100g and put into and spray jar, start rotor pump.In 30 minutes, 65ml is contained 3.0g NiO and 0.50g MgO nickelous nitrate, magnesium nitrate solution spray among the support of the catalyst SB.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 8 hours, makes the aromatized catalyst intermediate, is numbered IB.
Take by weighing above-mentioned aromatization catalyst intermediate IB 100ml and put into vertical catalyst activation stove, handled 10 hours, stop into water at aqua volume ratio 5: 1,480 ℃ of following steam of temperature.Use N then
2The nitrogen oxygen atmosphere replacing water steam of content 95% was controlled 30 ℃/hour and is cooled to room temperature after 4 hour, drew off, and made aromatized catalyst, was numbered CB.
The rerum natura of aromatized catalyst carrier S B, intermediate compound I B, catalyzer CB is listed in the table 2.
Example 3
(the HBeta/HZSM-5 mass percent is this examples preparation 6.0m%NiO-1.0m%MgO-0.50m%ZnO/HBeta+HZSM-5: aromatized catalyst 50%/50%).Wherein the HBeta grain fineness number is 70nm～150nm; The HZSM-5 grain fineness number is 100nm～500nm.
Take by weighing 118.8g HBeta (SiO
2/ Al
2O
3Mol ratio 33), 106.0g HZSM-5 (SiO
2/ Al
2O
3Mol ratio 27), 140.0g Al
2O
3, and their ground and mixed is even, adding 170ml concentration is the dilute nitric acid solution of 7.6g/100ml, grinds to form the suitable muffin body of humidity.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 520 ℃ of following roastings 8 hours, makes the Aromatizatian catalytic agent carrier, is numbered SC.
Take by weighing said catalyst carrier SC 100g and put into and spray jar, start rotor pump.The nickelous nitrate, magnesium nitrate and the zinc nitrate solution that 57ml are contained 6.0g NiO, 1.0g MgO and 0.50g ZnO in 30 minutes spray support of the catalyst SC.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 8 hours, makes catalyst intermediate, is numbered IC.
Take by weighing above-mentioned catalyst intermediate IC100ml and put into perpendicular examination catalyst activation stove, handled catalyst I C intermediate 12 hours, stop into water at aqua volume ratio 3: 1,500 ℃ of following steam of temperature.Use N then
2The N of content 95%
2/ O
2Gas mixture replacing water steam was controlled 30 ℃/hour and is cooled to room temperature after 4 hour, drew off, and made aromatized catalyst, was numbered CC.
The rerum natura of aromatized catalyst carrier S C, intermediate compound I C, catalyzer CC is listed in the table 3.
Example 4
This example is the reference agent of example 3.
(the HBeta/HZSM-5 mass percent is this examples preparation 6.0m%NiO-1.0m%MgO-0.50m%ZnO/HBeta+HZSM-5: aromatized catalyst 50%/50%).Wherein HBeta and HZSM-5 are conventional molecular sieve.
(grain size is 1500nm～2000nm, SiO to take by weighing 118.8g HBeta
2/ Al
2O
3Mol ratio 35), (grain size is 1200nm～2000nm to 106.0g HZSM-5, SiO
2/ Al
2O
3Mol ratio 42), 140.0gAl
2O
3, and their ground and mixed is even, adding 170ml concentration is the dilute nitric acid solution of 7.6g/100ml, grinds to form the suitable muffin body of humidity.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 520 ℃ of following roastings 8 hours, makes the Aromatizatian catalytic agent carrier, is numbered SD.
Take by weighing said catalyst carrier SD 100g and put into and spray jar, start rotor pump.In 30 minutes, 57ml contained 6.0gNiO,, the solution spraying of nickelous nitrate, magnesium nitrate and the zinc nitrate of 1.0g MgO and 0.50g ZnO is to support of the catalyst SC.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 8 hours, makes catalyst intermediate, is numbered ID.
Take by weighing above-mentioned catalyst intermediate ID100ml and put into perpendicular examination catalyst activation stove, handled catalyst intermediate ID 12 hours, stop into water at aqua volume ratio 3: 1,500 ℃ of following steam of temperature.Use N then
2The N of content 95%
2/ O
2Gas mixture replacing water steam was controlled 30 ℃/hour and is cooled to room temperature after 4 hour, drew off, and made aromatized catalyst, was numbered CD.
The rerum natura of aromatized catalyst carrier S D, intermediate compound I D, catalyzer CD is listed in the table 4.
Example 5
This examples preparation 6.0m%MoO
3-1.0m%MnO-0.50m%ZnO/HSAPO-41.
(grain size is 300nm～700nm), 140.0g Al to take by weighing 229.6g HSAPO-41
2O
3, and their ground and mixed is even, adding 170ml concentration is the dilute nitric acid solution of 7.6g/100ml, grinds to form the suitable muffin body of humidity.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 520 ℃ of following roastings 8 hours, makes the Aromatizatian catalytic agent carrier, is numbered SE.
Take by weighing said catalyst carrier SE 100g and put into and spray jar, start rotor pump.In 30 minutes, 57ml is contained 6.0gMoO
3,, the solution spraying of ammonium molybdate, manganous nitrate and the zinc nitrate of 1.0g MnO and 0.50g ZnO is to support of the catalyst SE.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 8 hours, makes catalyst intermediate, is numbered IE.
Take by weighing above-mentioned catalyst intermediate IE100ml and put into perpendicular examination catalyst activation stove, handled catalyst intermediate IE 12 hours, stop into water at aqua volume ratio 3: 1,500 ℃ of following steam of temperature.Use N then
2The N of content 95%
2/ O
2Gas mixture replacing water steam was controlled 30 ℃/hour and is cooled to room temperature after 4 hour, drew off, and made aromatized catalyst, was numbered CE.
The rerum natura of aromatized catalyst carrier S E, intermediate compound I E, catalyzer CE is listed in the table 5.
The rerum natura of table 1 aromatized catalyst carrier S A, intermediate compound I A, catalyzer CA
| Project | Carrier S A | Intermediate compound I A | Catalyzer CA | |
| Specific surface area, m 2/ g pore volume, ml/g average pore diameter, nm | 540 0.45 2.80 | 500 0.40 2.50 | 505 0.40 2.51 | |
| Acid distributes | 160℃ 250℃ 350℃ 450℃ | 0.940 0.730 0.610 0.458 | 0.990 0.770 0.620 0.460 | 0.920 0.720 0.570 0.123 |
The rerum natura of table 2 aromatized catalyst carrier S B, intermediate compound I B, catalyzer CB
| Project | Carrier S B | Intermediate compound I B | Catalyzer CB | |
| Specific surface area, m 2/ g pore volume, ml/g average pore diameter, nm | 350 0.25 1.95 | 330 0.22 1.85 | 335 0.23 1.87 | |
| Acid distributes | 160℃ 250℃ 350℃ 450℃ | 0.820 0.640 0.530 0.400 | 0.830 0.680 0.550 0.410 | 0.810 0.640 0.430 0.107 |
The rerum natura of table 3 aromatized catalyst carrier S C, intermediate compound I C, catalyzer CC
| Project | Carrier S C | Intermediate compound I C | Catalyzer CC | |
| Specific surface area, m 2/ g pore volume, ml/g average pore diameter, nm | 400 0.38 2.30 | 395 0.32 2.25 | 397 0.33 2.27 | |
| Acid distributes | 160℃ 250℃ 350℃ 450℃ | 0.888 0.703 0.585 0.439 | 0.901 0.745 0.600 0.442 | 0.876 0.723 0.580 0.109 |
The rerum natura of table 4 aromatized catalyst carrier S D, intermediate compound I D, catalyzer CD
| Project | Carrier S D | Intermediate compound I D | Catalyzer CD | |
| Specific surface area, m 2/ g pore volume, ml/g average pore diameter, nm | 375 0.32 2.05 | 361 0.30 1.95 | 365 0.30 1.97 | |
| Acid distributes | 160℃ 250℃ 350℃ 450℃ | 0.820 0.680 0.550 0.410 | 0.850 0.702 0.560 0.415 | 0.810 0.687 0.530 0.100 |
The rerum natura of table 5 aromatized catalyst carrier S E, intermediate compound I E, catalyzer CE
| Project | Carrier S E | Intermediate compound I E | Catalyzer CE | |
| Specific surface area, m 2/ g pore volume, ml/g average pore diameter, nm | 275 0.22 3.88 | 261 0.21 3.80 | 265 0.30 3.82 | |
| Acid distributes | 160℃ 250℃ 350℃ 450℃ | 0.760 0.600 0.450 0.200 | 0.840 0.632 0.458 0.205 | 0.830 0.620 0.410 0.008 |
Example 6
The octane value recovering performance of the more above-mentioned aromatized catalyst of this example and carbon deposit performance.
Test is to carry out on the device of two reactors in series, and each reactor can be adorned the 100ml catalyzer.Pack in first reactor～kind of traditional hydrogenating desulfurization MoO
3(12m%)-CoO (4m%)/Al
2O
3Catalyzer 20ml dilutes with porcelain is husky with 2: 1 ratios; The above-mentioned aromatized catalyst 40ml that packs in second reactor, with 2: 1 ratios with the husky dilution of porcelain.Airtight qualified after, at first carry out presulfiding of catalyst.Vulcanized oil is a straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0v%; Sulfide stress is 1.6MPa, temperature be 230 ℃ following 8 hours, 280 ℃ are following 8 hours; The vulcanized oil volume space velocity is 2.0h
-1Sulfuration is brought up to 3.2MPa with reaction pressure after finishing.Continue into vulcanized oil, in 3 hours, one instead is cooled to 260 ℃, and two instead are warming up to 385 ℃.Then the full cut catalytic gasoline of swap-in or＞70 ℃ of last running raw materials, an anti-volume space velocity is 4.0h
-1, two anti-volume space velocities are 2.0h
-1After stablizing 8 hours, sampling analysis.Each test period is controlled at into and turned round 500 hours behind the catalytic gasoline raw material, stops test then, draws off the coke content on the catalyst analysis catalyzer.
Table 6 has been listed the used catalytic gasoline raw material of evaluation test oil properties; Table 7 has been listed the result of the test of full cut FCC gasoline feeding; It is＞70 ℃ of last running chargings that table 8 has been listed the prefractionation of FCC gasoline, is the result of the test that is in harmonious proportion with＜70 ℃ of lighting ends then.
Table 6 catalytic gasoline raw material oil properties
| Project | Full cut catalytic gasoline | ＜70 ℃ of cuts | ＞70 ℃ of cuts |
| Yield, m% density, the g/ml sulphur content, μ g/g olefin(e) centent, the v% aromaticity content, the v% research octane number (RON), the RON motor-method octane number, the MON anti-knock index, (R+M)/2 | 100 0.7170 400 43.0 15.0 92.0 78.0 85.0 | 33.0 0.6610 50 63.5 4.0 94.2 85.0 89.6 | 67.0 0.7536 550 30.5 20.3 89.0 79.0 84.0 |
The full cut catalytic gasoline desulfurization of table 7/the fall character of olefin product and the coke content of catalyzer
| Catalyzer | Sulphur content | Olefin(e) centent | Aromaticity content | (R+M)/2 loss | Liquid yield | Carbon deposit m% |
| μg/g | v％ | v％ | m％ | |||
| Catalyst intermediate IA | 45 | 20.5 | 24.1 | 1.6 | 83 | 12.2 |
| Catalyzer CA | 49 | 19.2 | 24.5 | 1.9 | 88 | 7.0 |
| Catalyst intermediate IB | 40 | 23.7 | 25.0 | 1.4 | 86 | 14.1 |
| Catalyzer CB | 46 | 21.3 | 25.6 | 1.6 | 93 | 8.6 |
| Catalyst intermediate IC | 34 | 22.6 | 24.6 | 1.2 | 85 | 10.5 |
| Catalyzer CC | 40 | 20.0 | 25.0 | 1.5 | 90 | 6.0 |
| Catalyst intermediate ID | 50 | 26.1 | 23.2 | 1.7 | 86 | 13.2 |
| Catalyzer CD | 54 | 24.0 | 23.7 | 2.0 | 92 | 8.0 |
| Catalyst intermediate IE | 51 | 28.9 | 21.5 | 1.5 | 90 | 9.6 |
| Catalyzer CE | 57 | 26.1 | 23.3 | 1.7 | 95 | 4.8 |
From table 7 more as can be seen, little crystal grain NiO-MgO/HZSM-5 catalyzer CB compares with little crystal grain NiO-MgO/HBeta catalyzer CA, under the desulfurization degree situation close with the alkene saturation exponent, the former aromizing selectivity is higher, loss of octane number is lower, yield of gasoline is high slightly, but catalyzer coke content is obviously higher.As can be seen, little crystal grain HZSM-5 molecular sieve catalyst strength of acid is lower, thereby has reduced the cracking activity that carries out on the strong acid center, has improved yield of gasoline from table 1 and table 2; Little crystal grain HZSM-5 molecular sieve catalyst average pore diameter is less, thereby has increased the residence time of reactant molecule in catalyst pores, has deepened the degree of secondary side reactions such as hydrogen transference, polymerization coking, causes the coke content on the catalyzer to increase.Compound little crystal grain NiO-MgO-ZnO/HZSM-5+HBeta catalyzer CC shows both synergistic effects.The sulphur content and the olefin(e) centent of FCC gasoline can be reduced to less than 50 μ g/g with less than 20v% by 400 μ g/g and 43.0v% respectively, and anti-knock index ((R+M)/2) loses less than 1.5 units, the quality of gasoline yield reaches 90m%.
From table 7, relatively it can also be seen that, compound little crystal grain NiO-MgO-ZnO/HZSM-5+HBeta catalyzer CC compares with the compound NiO-MgO-ZnO/HZSM-5+HBeta catalyzer CD of conventional micron order crystal grain, and the former has shown higher aromizing selectivity, lower carbon deposition activity.From table 3 and table 4 as can be seen, this be because, little crystal grain NiO-MgO-ZnO/HZSM-5+HBeta catalyzer has bigger specific surface area, short and bigger duct, helps the diffusion of molecule, has suppressed secondary side reactions such as polymerization, coking to a certain extent.
From table 7, relatively it can also be seen that, the hydrothermal treatment consists rear catalyst is compared with the catalyst intermediate of hydrothermal treatment consists not, under the situation that reaches close desulfurization degree and alkene saturation exponent, loss of octane number is the same substantially, but the former improves 5 percentage points, coke content reduction by 40% than latter's quality of gasoline yield.From table 1～table 4 as can be seen, this is because hydrothermal treatment consists has reduced the concentration of strong acid center on the catalyst surface, has suppressed the scission reaction leading than strong acid center, has improved the liquid yield of gasoline; Also suppressed the degree of depth polymerization that the hydrogen transfer reactions of hydro carbons causes, thereby reduced the carbon deposit of hydro carbons at acid molecular sieve catalyst.
Table 8 catalytic gasoline prefractionation scheme desulfurization/the fall character of olefin product
| Project | Sulphur content | Olefin(e) centent | Aromaticity content | (R+M)/2 loss | Liquid yield |
| μg/g | v％ | v％ | m％ | ||
| After＞70 ℃ of hydrotreatments | 55 | 10.5 | 28.1 | 2.4 | 94 |
| After gently, reblending | 50 | 24.9 | 22.5 | 1.4 | 93 |
Catalyzer: CE
As can be seen from Table 8, adopt catalytic gasoline prefractionation scheme the sulphur content and the olefin(e) centent of FCC gasoline can be reduced to 50 μ g/g and 25v% by 400 μ g/g and 43.0v% respectively, and 1.4 units of anti-knock index ((R+M)/2) loss, the quality of gasoline yield reaches 93m%.
Claims (11)
1, a kind of aromatized catalyst is characterized in that the weight percent with catalyzer is a benchmark, and it consists of: metal oxide content is 1.0m%～10.0m%, and molecular sieve content is 50.0m%～90.0m%, and surplus is a binding agent; Wherein molecular sieve is the hydrogen type molecular sieve of grain fineness number in 20nm～800nm scope.
2, according to the described aromatized catalyst of claim 1, it is characterized in that the NH3-TPD strength of acid of described aromatized catalyst is distributed as: 160 ℃ are 0.800mmol/g～1.00mmol/g; 250 ℃ is 0.600mmol/g～0.800mmol/g; 350 ℃ is 0.400mmol/g～0.600mmol/g; 450 ℃ is 0.080mmol/g～0.200mmol/g.
3, according to claim 1 or 2 described aromatized catalysts, the specific surface area that it is characterized in that described catalyzer is 300m2/g～600m2/g, and pore volume is 0.15ml/g～0.55ml/g, average pore diameter 1.3nm～3.3nm.
4,, it is characterized in that described metal oxide is selected from one or more in zinc, magnesium, iron, manganese, nickel, cobalt, molybdenum and the tungsten according to claim 1 or 2 described aromatized catalysts.
5,, it is characterized in that described molecular sieve is one or more among HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and the HSAPO-41 according to claim 1 or 2 described aromatized catalysts.
6, according to claim 1 or 2 described aromatized catalysts, it is characterized in that the aromatized catalyst preparation process is: molecular sieve and binding agent are made carrier, impregnating metal component, drying, roasting, handle 3～10 hours under 450 ℃～500 ℃ water vapour atmospheres then.
7, the application of the described catalyzer of claim 1 in FCC gasoline production low-sulfur, low alkene clean gasoline technology, detailed process is as follows:
The first stage catalytic cracking gasoline hydrofinishing: catalytically cracked gasoline is contacted with Hydrobon catalyst under hydrorefined condition, to remove the diolefin of easy polymerization coking under sulfide and the olefin(e) compound, particularly high temperature in the gasoline;
Second section light-hydrocarbon aromatized octane value recovering that carries out: with first section hydrotreated product through the described aromizing molecular sieve catalyst of claim 1, will be light-hydrocarbon aromatized be aromatic hydrocarbons, with the recovery octane value.
8, according to the described technology of claim 7, it is characterized in that described hydrofining employing Mo-Co or Mo-Ni/ aluminium oxide catalyst, the hydrofining condition is: reaction pressure 1.5MPa～4.5MPa, 220 ℃～300 ℃ of temperature of reaction, volume space velocity 2.0h
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.
9, according to the described technology of claim 7, it is characterized in that described aromatization condition is: reaction pressure 1.5MPa～4.5MPa, 350 ℃～450 ℃ of temperature of reaction, volume space velocity 0.5h
-1～3.0h
-1With hydrogen to oil volume ratio 200～800: 1.
10, according to the described technology of claim 7, it is characterized in that full cut catalytic gasoline branch is entered hydrofining and aromatized catalyst system, carry out hydrotreatment, obtain the clean gasoline product of low-sulfur, low olefin-content.
11, according to the described technology of claim 7, it is characterized in that with the fractionation of full cut catalytic gasoline for＜70 ℃ and＞70 ℃ light, weigh two kinds of cuts, wherein last running enters hydrofining and aromatized catalyst system, carry out hydrotreatment, reaction product is mixed the clean gasoline product that obtains low-sulfur, low olefin-content with lighting end.
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| CN1294240C (en) * | 2004-07-06 | 2007-01-10 | 中国石油化工股份有限公司 | Depth hydrogenation treatment method of faulty gasoline |
| US7431827B2 (en) * | 2004-10-27 | 2008-10-07 | Catalytic Distillation Technologies | Process for the production of low sulfur, low olefin gasoline |
| CN100345943C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Process for hydrodesulphurization and olefin reduction of gasoline |
| CN101081997B (en) * | 2006-05-31 | 2012-05-16 | 中国石油大学(北京) | Catalytically cracked gasoline non-hydrogen aromatization modified catalyst and preparation method thereof |
| CN101161791B (en) * | 2006-10-12 | 2012-01-25 | 中国石油化工股份有限公司 | Method for producing clean gasoline |
| CN101492610B (en) * | 2008-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Method for deep desulfurization olefin hydrocarbon reduction of gasoline |
| US9523701B2 (en) | 2009-07-29 | 2016-12-20 | Dynex Technologies, Inc. | Sample plate systems and methods |
| CN102451747B (en) * | 2010-10-21 | 2013-08-21 | 中国石油化工股份有限公司 | C8 alkylaromatic side chain isomerization catalyst and preparation method thereof |
| CN105772070B (en) * | 2016-02-23 | 2019-07-16 | 新疆恒晟能源科技股份有限公司 | A kind of catalyst and preparation method thereof for the modification of gasoline non-hydrogen |
| CN110088247B (en) | 2016-10-21 | 2021-10-08 | 中国石油化工股份有限公司 | Gasoline treatment method |
| RU2742646C2 (en) | 2016-10-21 | 2021-02-09 | Чайна Петролеум Энд Кемикал Корпорейшн | Method of gasoline treatment |
| CN110624600B (en) * | 2019-10-12 | 2021-01-12 | 厦门大学 | Catalyst for preparing ethylbenzene and xylene by alkylating toluene and methanol, preparation and application thereof |
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