CN115873632A - Method for increasing yield of low-benzene-content gasoline - Google Patents
Method for increasing yield of low-benzene-content gasoline Download PDFInfo
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- CN115873632A CN115873632A CN202111143353.3A CN202111143353A CN115873632A CN 115873632 A CN115873632 A CN 115873632A CN 202111143353 A CN202111143353 A CN 202111143353A CN 115873632 A CN115873632 A CN 115873632A
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 154
- 239000002283 diesel fuel Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000005520 cutting process Methods 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical group [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 230000002152 alkylating effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 52
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for increasing the yield of gasoline with low benzene content includes such steps as catalytic cracking reaction of heavy raw oil in the presence of catalytic cracking catalyst to obtain the first reaction product, separating to obtain catalytically cracked gasoline and diesel oil, cutting gasoline to obtain light gasoline, medium gasoline and heavy gasoline, cutting diesel oil to obtain light diesel oil and heavy diesel oil, returning light diesel oil back to catalytic cracking reactor, hydrogenating heavy diesel oil to obtain hydrogenated heavy diesel oil, mixing hydrogenated heavy diesel oil with light gasoline, catalytic cracking reaction in catalytic cracking reactor, and alkylating reaction of medium gasoline in secondary reactor. The method of the invention can reduce the benzene content and the olefin content in the gasoline and increase the yield of the gasoline.
Description
Technical Field
The invention belongs to a catalytic conversion method of hydrocarbon oil, and particularly relates to a method for increasing the yield of catalytic cracking gasoline with low benzene and olefin content.
Background
With the development of crude oil heaviness and the rapid increase of light oil demand in the market, catalytic cracking technology for heavy oil heaviness is rapidly developed in china. However, one must face the fact that catalytically cracked diesel (or light cycle oil) has been relatively poor in quality, high in density, high in aromatics content, low in cetane number, and even by diesel hydro-upgrading technology, it has been difficult to meet increasingly stringent diesel specifications. How to solve the problem of catalytic cracking of light cycle oil is a serious problem. Meanwhile, another problem exists in that domestic finished gasoline is in short supply for a long time, and catalytic cracking gasoline accounts for 80 percent of the finished gasoline. Therefore, how to maximize the production of high octane gasoline from heavy feed oil without producing light cycle oil by the catalytic cracking process may be a new approach to solve the above problems.
The united states patent US4585545 discloses a catalytic conversion method for producing gasoline rich in monocyclic aromatic hydrocarbons by carrying out hydrotreating on a catalytic cracking light cycle oil whole fraction to obtain hydrogenated diesel oil and then carrying out catalytic cracking on the hydrogenated diesel oil.
Chinese patent application publication No. CN1422327a discloses a catalytic cracking cycle oil upgrading method, which is to deeply hydrogenate light cycle oil produced by a first catalytic cracking unit using heavy oil as a raw material, and then to perform a second catalytic cracking unit on the obtained hydrogenated cycle oil. On the basis of this method, chinese patent application publication CN1423689a emphasizes that the catalyst in the second catalytic cracking unit requires 50-95% shape selective zeolite and about 5-50% large pore zeolite with a pore size greater than or equal to about 0.7nm to selectively increase the light olefin yield.
Chinese patent application publication No. CN1466619a discloses a conversion method of catalytic cracking light cycle oil, which divides a catalytic cracking riser reactor into an upstream reaction zone and a downstream reaction zone, wherein heavy oil is injected into the downstream reaction zone, and hydrogenated cycle oil obtained by hydrotreating catalytic cracking product light cycle oil is injected into the upstream reaction zone. On the basis of the method, the feeding material of the upstream zone in the method disclosed in the Chinese patent application publication CN1425054A is added with naphtha besides the hydrogenated cycle oil. However, in the method, not only is the hydrogen consumption high, but also the hydrogenation cycle oil reacts in an upstream area to seriously affect the conversion of heavy oil in the downstream area.
There remains a need in the art for a process that reduces the benzene content of gasoline while reducing the yield of light cycle oil and increasing the yield of catalytically cracked gasoline.
Disclosure of Invention
The invention aims to provide a method for increasing the yield of gasoline with low benzene content, effectively reducing the diesel-gasoline ratio and the olefin content in the gasoline.
The invention provides a method for increasing the yield of low-benzene-content gasoline, which comprises the following steps:
(1) Sending heavy raw oil into a catalytic cracking main reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and separating to obtain a catalytic cracking product and a spent catalyst;
(2) Separating the products to obtain catalytic cracking gasoline and catalytic cracking diesel oil; feeding the spent catalyst into a regenerator for regeneration, and returning the obtained regenerated catalyst to the catalytic cracking reactor;
(3) Cutting the catalytic cracking gasoline to obtain catalytic cracking light gasoline, medium gasoline and heavy gasoline;
(4) Cutting the catalytic cracking diesel to obtain a catalytic cracking diesel light fraction and a catalytic cracking diesel heavy fraction;
(5) Feeding the catalytic cracking diesel oil heavy fraction into a hydrogenation reactor, and hydrogenating under the action of hydrogen-containing gas to obtain a hydrogenation catalytic cracking heavy fraction;
(6) And (3) sending the hydrogenated heavy diesel oil, the catalytic cracking light gasoline and the catalytic cracking diesel oil light fraction into a catalytic cracking main reactor for catalytic cracking reaction.
(7) And (3) conveying gasoline in the catalytic cracking process into a catalytic cracking secondary reactor for alkylation reaction.
The hydrogenated heavy diesel oil, the catalytic cracking light gasoline and the catalytic cracking diesel oil light fraction in the step (6) can enter a catalytic cracking main reactor together with the heavy raw oil, and can also enter the catalytic cracking main reactor respectively. Preferably, the light fraction of the catalytic cracking diesel oil enters the bottom of a catalytic cracking main reactor, the hydrogenated heavy diesel oil and the catalytic cracking light gasoline enter the midstream of the catalytic cracking main reactor, and the heavy raw oil enters the downstream of the catalytic cracking main reactor.
The cutting point between the catalytic cracking light gasoline and the medium gasoline is 45-70 ℃, preferably 50-60 ℃; the cutting point between gasoline and heavy gasoline in catalytic cracking is 70-100 deg.C, preferably 80-90 deg.C.
The cutting point of the catalytic cracking diesel oil is 200-270 ℃.
The hydrogen-containing gas comprises hydrogen and catalytic cracking dry gas.
The reaction conditions in the catalytic cracking reactor were as follows: the reaction temperature is 450-650 deg.C, preferably 480-590 deg.C, and the weight hourly space velocity is 1-25 hr -1 Preferably 3 to 10 hours -1 The weight ratio of the catalytic cracking catalyst to the heavy raw oil (abbreviated as catalyst-oil ratio) is 3-30, preferably 4-15. The catalytic cracking reactor is an equal-diameter riser reactor with or without a bed reactor, or a reducing riser reactor with or without a bed reactor.
The alkylation reaction conditions in step (7) are as follows: the reaction temperature is 300-500 deg.C, preferably 350-430 deg.C, and the weight hourly space velocity is 0.2-15 hr -1 Preferably 0.5 to 10 hours -1 The weight ratio of the catalytic cracking catalyst to gasoline in catalytic cracking is 3-20, preferably 4-15.
The heavy raw oil is selected from straight-run wax oil, coker wax oil, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residue, atmospheric residue, and any combination thereof.
The catalytic cracking catalyst comprises 10-50 wt% zeolite selected from the group consisting of rare earth-containing or non-rare earth-containing Y-type zeolite, HY-type zeolite, USY-type zeolite, beta zeolite, and any combination thereof, 5-90 wt% inorganic oxide selected from the group consisting of silica, aluminum trioxide, or any combination thereof, and 0-70 wt% clay; the clay is selected from kaolin and/or halloysite.
Step (5) is carried out in the presence of a hydrotreating catalyst, the hydrotreating catalyst comprising an active metal component and a carrier, the active metal component being a group VIB metal and/or a group VIII non-noble metal, the carrier being selected from the group consisting of alumina, silica, amorphous silica-alumina, and any combination thereof; preferably, the hydrotreating catalyst comprises 30 wt% of active metal component and 70 wt% of support. The active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
The hydrotreating conditions in step (5) were as follows: hydrogen partial pressure of 1.0-10.0MPa, preferably 1.5-5.5MPa, reaction temperature of 330-450 deg.C, preferably 340-380 deg.C, weight hourly space velocity of 0.1-10.0 hr -1 Preferably 0.1 to 3.0h -1 The hydrogen-oil volume ratio is 100-2000Nm3/m3, preferably 350-2000Nm3/m3.
Compared with the prior art, the invention has the following technical effects:
the method can reduce the benzene and olefin contents of the gasoline under the condition of low hydrogen consumption, greatly reduce the diesel-gasoline ratio and improve the gasoline yield.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic flow chart of one embodiment of the present invention.
FIG. 2 is a schematic flow chart of another embodiment of the present invention.
In the drawings:
1 heavy raw oil pipeline, 2 catalytic cracking gasoline pipeline, 3 catalytic cracking diesel oil pipeline,
4 light gasoline pipeline, 5 heavy gasoline pipeline, 6 catalytic cracking diesel oil light fraction pipeline, 7 catalytic cracking diesel oil heavy fraction pipeline,
8 hydrogen-containing gas pipeline, 9 hydrogenation heavy diesel oil pipeline, 10 catalytic cracking main reactor,
11 gasoline cutting tower, 12 diesel oil cutting tower, 13 diesel oil hydrogenation device,
14 catalytic cracking secondary reactor, 15 middle gasoline pipeline, 16 low benzene gasoline pipeline and 17 pipeline.
Detailed Description
The following embodiments are two specific embodiments of the present invention, but the present invention is not limited thereto.
Two specific embodiments provided by the invention are described below with reference to the accompanying drawings.
The flow of FIG. 1 is illustrated as follows: heavy raw oil enters a catalytic cracking main reactor 10 from a heavy raw oil pipeline 1, catalytic cracking gasoline enters a gasoline cutting tower 11 from a catalytic cracking gasoline pipeline 2 and is separated into light gasoline, medium gasoline and heavy gasoline, the heavy gasoline is led out of the device through a heavy gasoline pipeline 5, the light gasoline returns to the catalytic cracking main reactor 10 through a light gasoline pipeline 4, a pipeline 17 and the heavy raw oil pipeline 1 in sequence for reaction, the medium gasoline is sent to a catalytic cracking secondary reactor 14 through a medium gasoline pipeline 15 for strengthening alkylation reaction of olefin and benzene to obtain low benzene gasoline, the device is led out through a pipeline 16, the catalytic cracking diesel enters a diesel cutting tower 12 through a catalytic cracking diesel pipeline 3 and is separated into catalytic cracking diesel light fraction and catalytic cracking diesel heavy fraction, the catalytic cracking diesel light fraction passes through a catalytic cracking diesel light fraction pipeline 6 and a heavy raw oil pipeline 1 in sequence and returns to the catalytic cracking main reactor 10 for catalytic cracking reaction, the catalytic cracking diesel heavy fraction enters a diesel hydrogenation device 13 through a catalytic cracking diesel heavy fraction pipeline 7, the raw oil is hydrogenated under the action of hydrogen-containing gas from a hydrogen-containing gas pipeline 8, and the heavy raw oil pipeline 9 and the catalytic cracking reactor 1 in sequence for catalytic cracking reaction. For simplicity, the outlet lines for other catalytic cracking reaction products, such as dry gas, liquefied gas, oil slurry, etc., are not shown in the figure.
The flow of fig. 2 is similar to the flow of fig. 1, and the difference is that the positions of the catalytically cracked diesel light fraction, the light gasoline and the hydrogenated heavy diesel oil entering the catalytic cracking main reactor 10 are different, the catalytically cracked diesel light fraction enters the upstream of the catalytic cracking main reactor 10 through the catalytically cracked diesel light fraction pipeline 6, and the light gasoline and the hydrogenated heavy diesel oil are respectively led out through the light gasoline pipeline 4 and the hydrogenated heavy diesel oil pipeline 9 and enter the midstream of the catalytic cracking main reactor 10 through the pipeline 17.
The following examples further illustrate the invention but are not intended to limit the invention thereto. In the examples and the comparative examples, the hydrotreating reactor was a medium-sized fixed bed reactor, in which a hydrotreating catalyst having a commercial designation of RN-32V and a protectant having a commercial designation of RG-1 were loaded, and the loading volume ratios of the hydrotreating catalyst and the protectant were 95, which were all produced by china petrochemical catalyst companies.
The physicochemical properties of the catalysts used in the catalytic cracking units of the examples and comparative examples are shown in Table 1, which is commercially available under the designation MLC-500, manufactured by China petrochemical catalyst division.
Properties of the stock oils used in examples and comparative examples are shown in tables 2 to 4, and product distribution is shown in Table 5.
Example 1
This example illustrates the use of the method of the present invention as provided in FIG. 1.
This example illustrates the use of the method of the present invention as provided in FIG. 1.
The atmospheric residuum contacts with a catalytic cracking catalyst MLC-500 to carry out catalytic cracking reaction, the reaction temperature is 500 ℃, and the weight hourly space velocity is 10h -1 Separating to obtain catalytic cracking gasoline and catalytic cracking diesel oil, wherein the catalyst-to-oil ratio is 6; cutting the catalytic cracking gasoline, wherein the cutting point between the catalytic cracking light gasoline and the middle gasoline is 60 ℃, and the cutting point between the catalytic cracking middle gasoline and the heavy gasoline is 90 ℃, so as to obtain the catalytic cracking light gasoline, the middle gasoline and the heavy gasoline; cutting the catalytic cracking diesel oil at a cutting point of 250 ℃ to obtain a catalytic cracking diesel oil light fraction and a catalytic cracking diesel oil heavy fraction; feeding the heavy fraction of the catalytic cracking diesel oil into a hydrogenation reactor for hydrogenation under the action of hydrogen-containing gas, a hydrogenation protective agent RG-1 and a hydrotreating catalyst RN-32V, wherein the hydrogen partial pressure is 10MPa, the reaction temperature is 350 ℃, the volume space velocity is 2 h-1, and the hydrogen-oil volume ratio is 600Nm3/m3, so as to obtain the hydrogenated heavy diesel oil; carrying out catalytic cracking reaction on the heavy fraction of the hydrocatalytic cracked diesel oil, the catalytic cracked light gasoline and the light fraction of the catalytic cracked diesel oil; the alkylation reaction is promoted by optimizing the reaction conditions of medium gasoline, the reaction temperature is 400 ℃, and the weight hourly space velocity is 10h -1 The catalyst-oil ratio is 6, the benzene content in the gasoline is reduced to 1.5% from the original 3.42% after alkylation reaction, and the olefin content of the gasoline is only 17.47%. The catalytic cracking reaction conditions of the hydrogenated heavy diesel oil are that the reaction temperature is 490 ℃, and the weight hourly space velocity is 10 hours -1 The agent-oil ratio is 6; the catalytic cracking reaction conditions of the light gasoline are that the reaction temperature is 500 ℃, and the weight hourly space velocity is 10 hours -1 The agent-oil ratio is 6; the catalytic cracking reaction conditions of the light fraction of the catalytic cracking diesel oil are 490 ℃, and the weight hourly space velocity is 10 hours -1 Ratio of solvent to oil 6(ii) a The reaction results are shown in Table 5.
Example 2
This example illustrates the use of the method of the present invention as provided in figure 2.
The atmospheric residue is contacted with a catalytic cracking catalyst MLC-500 to carry out catalytic cracking reaction, the reaction temperature is 480 ℃, and the weight hourly space velocity is 10h -1 Separating to obtain catalytic cracking gasoline and catalytic cracking diesel oil, wherein the catalyst-to-oil ratio is 6 and the reaction pressure is normal pressure; cutting the catalytic cracking gasoline, wherein the cutting point between the catalytic cracking light gasoline and the medium gasoline is 60 ℃, and the cutting point between the catalytic cracking medium gasoline and the heavy gasoline is 90 ℃, so as to obtain the catalytic cracking light gasoline, the medium gasoline and the heavy gasoline; cutting the catalytic cracking diesel at a cutting point of 250 ℃ to obtain a catalytic cracking diesel light fraction and a catalytic cracking diesel heavy fraction; the heavy fraction of the catalytic cracking diesel oil is sent into a hydrogenation reactor to be hydrogenated under the action of hydrogen-containing gas, hydrogenation protective agent RG-1 and hydrogenation treatment catalyst RN-32V, the hydrogen partial pressure is 10MPa, the reaction temperature is 350 ℃, and the volume space velocity is 2 hours -1 Hydrogen to oil volume ratio of 600Nm 3 /m 3 Obtaining hydrogenated heavy diesel oil; carrying out catalytic cracking reaction on the heavy fraction of the hydrocatalytic cracked diesel oil, the catalytic cracked light gasoline and the light fraction of the catalytic cracked diesel oil; in the catalytic cracking, gasoline is subjected to hydroisomerization reaction. The catalytic cracking reaction conditions of the hydrogenated heavy diesel oil are that the reaction temperature is 500 ℃, and the weight hourly space velocity is 10 hours -1 The agent-oil ratio is 6; the catalytic cracking reaction conditions of the light gasoline are that the reaction temperature is 500 ℃, and the weight hourly space velocity is 10 hours -1 The agent-oil ratio is 6; the catalytic cracking reaction conditions of the light fraction of the catalytic cracking diesel oil are 510 ℃, and the weight hourly space velocity is 10 hours -1 The agent-oil ratio is 6; the alkylation reaction is promoted by optimizing the reaction conditions of medium gasoline, the reaction temperature is 400 ℃, and the weight hourly space velocity is 10h -1 The catalyst-oil ratio is 6, the benzene content in the gasoline is reduced to 1.5% from the original 3.42% after alkylation reaction, and the olefin content of the gasoline is only 17.47%. The reaction results are shown in Table 5.
Comparative example
The atmospheric residuum is used as raw material, the reaction temperature is 500 ℃, the catalyst-oil ratio is 6, and the weight hourly space velocity is 10 hours -1 Under the conditions of catalytic crackingThe reaction was carried out, and the reaction product was analyzed, the results of which are shown in Table 5.
It can be seen from the data in table 5 that gasoline and diesel oil are cut by the method of the present invention, the heavy fraction of the catalytically cracked diesel oil is hydrogenated and then returns to the catalytic cracking device for feeding with light gasoline and the light fraction of the catalytically cracked diesel oil, and the medium gasoline is optimized and strengthened in alkylation reaction through reaction conditions to promote the alkylation reaction of olefin and benzene, so that the benzene content and the olefin content in the gasoline can be significantly reduced, and the conversion of the catalytically cracked diesel oil into the catalytically cracked gasoline can be promoted to increase the gasoline yield.
TABLE 1 catalytic cracking catalyst Properties
| Name (R) | MLC-500 |
| Mass composition/%) | |
| Al 2 O 3 | 55.9 |
| SiO 2 | 37.0 |
| RE 2 O 3 | 3.3 |
| P 2 O 5 | 0.45 |
| Physical Properties | |
| Specific surface area/(m) 2 /g) | 116 |
| Area of matrix/(m) 2 /g) | 68 |
| Area of micropores/(m) 2 /g) | 48 |
| Pore volume/(mL/g) | 0.195 |
| Micropore volume/(mL/g) | 0.023 |
| Micro-inverse activity/%) | 54 |
| Sieving volume composition/% | |
| 0 to 40 microns | 20.0 |
| 0 to 80 microns | 63.7 |
| 0 to 149 micrometers | 96.2 |
| Average particle size/micron | 67.6 |
TABLE 2 atmospheric residuum Properties
| Analysis item | Atmospheric residuum |
| Sulfur content,% (w) | 0.726 |
| Nitrogen content% | 0.16 |
| Metal content | |
| Fe，mg/kg | 6.2 |
| Ni，mg/kg | 6.1 |
| V，mg/kg | 3.1 |
| Na，mg/kg | 0.5 |
| Ca，mg/kg | 0.4 |
| Carbon content,% (w) | 87.02 |
| Hydrogen content,% (w) | 12.09 |
| Density (20 ℃), kg/m 3 | 934.3 |
| Refractive index (70 ℃ C.) | 1.5057 |
| Viscosity (80 ℃ C.), mm 2 /s | 29.34 |
| Viscosity (100 ℃ C.), mm 2 /s | 15.61 |
| Carbon residue,% (w) | 4.29 |
| Total acid value of mgKOH/g | 0.81 |
| Freezing point, DEG C | 32 |
| Basic nitrogen, mg/kg | 457 |
TABLE 3 light and Medium gasoline fraction Properties
| Item | Light gasoline fraction | Middle gasoline fraction |
| Boiling point Range/. Degree.C | <60 | 60-90 |
| Hydrocarbon group mass composition% | ||
| N-alkanes | 8.03 | 5.23 |
| Isoalkanes | 45.77 | 36.72 |
| Olefins | 39.04 | 39.07 |
| Cycloalkanes | 0.71 | 14.56 |
| Aromatic hydrocarbons | 0.18 | 4.34 |
| Benzene/wt% | 0.18 | 3.42 |
TABLE 4 heavy fraction of catalytically cracked diesel, light fraction of catalytically cracked diesel and hydrogenated heavy diesel
TABLE 5 product distribution
| Product distribution | Comparative example | Example 1 | Example 2 |
| Dry gas | 1.67 | 2.99 | 2.34 |
| Liquefied gas | 15.22 | 21.46 | 19.78 |
| Gasoline (gasoline) | 36.57 | 47.71 | 52.07 |
| Light cycle oil | 27.19 | 7.54 | 8.15 |
| Oil slurry | 8.51 | 5.78 | 6.44 |
| Coke | 10.84 | 14.51 | 11.22 |
| Total up to | 100 | 100 | 100 |
| Composition of gasoline% | |||
| N-alkanes | 3.46 | 4.44 | 4.55 |
| Isoalkanes | 29.96 | 35.13 | 36.96 |
| Olefins | 16.35 | 10.37 | 10.38 |
| Cycloalkanes | 8.59 | 10.46 | 10.31 |
| Aromatic hydrocarbons | 40.58 | 38.89 | 37.02 |
| Benzene content in gasoline/wt% | 1.2 | 0.82 | 0.79 |
Claims (14)
1. A method for increasing the yield of low benzene content gasoline comprises the following steps:
(1) Sending heavy raw oil into a catalytic cracking main reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and separating to obtain a catalytic cracking product and a spent catalyst;
(2) Separating the products to obtain catalytic cracking gasoline and catalytic cracking diesel oil; feeding the spent catalyst into a regenerator for regeneration, and returning the obtained regenerated catalyst to the catalytic cracking reactor;
(3) Cutting the catalytic cracking gasoline to obtain catalytic cracking light gasoline, medium gasoline and heavy gasoline;
(4) Cutting the catalytic cracking diesel to obtain a catalytic cracking diesel light fraction and a catalytic cracking diesel heavy fraction;
(5) The catalytic cracking diesel oil heavy fraction is sent into a hydrogenation reactor to be hydrogenated under the action of hydrogen-containing gas to obtain hydrogenated heavy diesel oil;
(6) Sending hydrogenated heavy diesel oil, catalytic cracking light gasoline and catalytic cracking diesel oil light fractions into a catalytic cracking main reactor for catalytic cracking reaction;
(7) And (3) conveying gasoline in the catalytic cracking process into a catalytic cracking secondary reactor for alkylation reaction.
2. The method according to claim 1, characterized in that the hydrogenated heavy diesel oil, the catalytically cracked light gasoline and the catalytically cracked diesel oil light fraction of step (6) can be fed into the catalytic cracking main reactor together with the heavy raw oil, or can be fed into different positions of the catalytic cracking main reactor respectively.
3. The process of claim 2, wherein the light fraction of catalytically cracked diesel oil is fed into the upstream of the catalytic cracking main reactor, the hydrogenated heavy diesel oil and catalytically cracked light gasoline are fed into the midstream of the catalytic cracking main reactor, and the heavy raw oil is fed into the downstream of the catalytic cracking main reactor.
4. Process according to claim 1, characterized in that the cut point between the catalytically cracked light gasoline and medium gasoline is 45-70 ℃, preferably 50-60 ℃; the cutting point between gasoline and heavy gasoline in catalytic cracking is 70-100 ℃, preferably not more than 80-90 ℃.
5. The process according to claim 1, characterized in that the catalytically cracked diesel cut point is from 200 to 270 ℃.
6. The method of claim 1, wherein the hydrogen-containing gas comprises hydrogen gas, catalytic cracking dry gas.
7. The process according to claim 1, characterized in that the catalytic cracking reaction conditions are as follows: the reaction temperature is 450-650 deg.C, preferably 480-590 deg.C, and the weight hourly space velocity is 1-25 hr -1 Preferably 3 to 10 hours -1 Catalytic cracking catalyst and heavy feedstockThe oil weight ratio is 3-30, preferably 4-15.
8. The process according to claim 1, characterized in that the alkylation reaction conditions in step (7) are as follows: the reaction temperature is 300-500 ℃, preferably 350-430 ℃, and the weight hourly space velocity is 0.2-15 hours -1 Preferably 0.5 to 10 hours -1 The weight ratio of the catalytic cracking catalyst to gasoline in catalytic cracking is 3-20, preferably 4-15.
9. The process according to claim 1, characterized in that the main reactor is a constant diameter riser reactor with or without a bed reactor or a variable diameter riser reactor with or without a bed reactor.
10. The process according to any of claims 1-3, characterized in that the heavy feedstock oil is selected from the group consisting of virgin wax oil, coker wax oil, deasphalted oil, hydrofinished oil, hydrocracked tail oil, vacuum residuum, atmospheric residuum, and any combination thereof.
11. The process according to claim 1, characterized in that the catalytic cracking catalyst comprises 10-50 wt% of a zeolite selected from the group consisting of rare earth-containing or non-containing Y-type zeolite, HY-type zeolite, USY-type zeolite, beta zeolite and any combination thereof, 5-90 wt% of an inorganic oxide selected from the group consisting of silica, aluminum trioxide or any combination thereof, and 0-70 wt% of a clay; the clay is selected from kaolin and/or halloysite.
12. The process of claim 1, wherein step (5) is carried out in the presence of a hydrotreating catalyst comprising an active metal component which is a group VIB metal and/or a non-noble group VIII metal and a support selected from the group consisting of alumina, silica, amorphous silica-alumina, and any combination thereof; preferably, the hydrotreating catalyst comprises 30 wt% of active metal component and 70 wt% of support.
13. The method of claim 12, wherein the active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, or cobalt-molybdenum.
14. The process according to claim 1, characterized in that the hydrotreating conditions of step (5) are as follows: hydrogen partial pressure of 1.0-10.0MPa, preferably 1.5-5.5MPa, reaction temperature of 330-450 deg.C, preferably 340-380 deg.C, weight hourly space velocity of 0.1-10.0 hr -1 Preferably 0.1 to 3.0h -1 Hydrogen to oil volume ratio of 100-2000Nm 3 /m 3 Preferably 350-2000Nm 3 /m 3 。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
| US20190093028A1 (en) * | 2017-09-26 | 2019-03-28 | China Petroleum & Chemical Corporation | Catalytic Cracking Process with Increased Production of a Gasoline Having a Low Olefin Content and a High Octane number |
| CN109554195A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of catalyst cracking method reducing diesel and gasoline ratio |
| CN109554193A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of catalyst cracking method increasing production low alkene and high-knock rating gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
| US20190093028A1 (en) * | 2017-09-26 | 2019-03-28 | China Petroleum & Chemical Corporation | Catalytic Cracking Process with Increased Production of a Gasoline Having a Low Olefin Content and a High Octane number |
| CN109554195A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of catalyst cracking method reducing diesel and gasoline ratio |
| CN109554193A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of catalyst cracking method increasing production low alkene and high-knock rating gasoline |
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