CN104560186A - Catalytic conversion method capable of realizing maximum gasoline production - Google Patents
Catalytic conversion method capable of realizing maximum gasoline production Download PDFInfo
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- CN104560186A CN104560186A CN201310517650.9A CN201310517650A CN104560186A CN 104560186 A CN104560186 A CN 104560186A CN 201310517650 A CN201310517650 A CN 201310517650A CN 104560186 A CN104560186 A CN 104560186A
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- catalytic cracking
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a catalytic conversion method capable of realizing maximum gasoline production. Catalytic cracking light cycle oil is cut to obtain a light fraction and a heavy fraction, wherein the heavy fraction is hydrotreated to obtain a hydrogenated heavy fraction; the light fraction and the hydrogenated heavy fraction are independently layered by use of different nozzles to go into a catalytic cracking device to have a cracking reaction in the presence of a catalytic cracking catalyst; and the reaction product is separated to obtain a product comprising gasoline and light cycle oil. According to the catalytic conversion method, the independent catalytic cracking device is adopted to process the light fraction and the hydrogenated heavy fraction of the light cycle oil and feed the fractions layer by layer; as a result, the harsh conditions needed by the catalytic cracking reactions of different fractions of the light cycle oil can be optimized and satisfied to the utmost extent, and the catalytic gasoline can be produced to the utmost extent.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon in the absence of hydrogen, more particularly, is a kind of catalysis conversion method being maximized the gasoline produced by catalytic cracking light cycle oil.
Background technology
Along with the development of crude oil heaviness and market are to the quick growth of light-end products demand, in China, the catalytic cracking technology as heavy oil lighting is rapidly developed.But, must faced by a fact be that the quality of catalytic cracking diesel oil (or claim " light cycle oil ") is but always relatively poor, density is large, and aromaticity content is high, cetane value is low, even if be also difficult to by diesel oil hydrogenation modification technology the diesel oil regulation reaching increasingly stringent.How solving catalytic cracking light cycle oil is an increasingly serious problem.Simultaneous another one problem is domestic gasoline product chronic shortage, and catalytically cracked gasoline accounts for 80% of gasoline product.Therefore, how to realize heavy feed stock maximization production stop bracket gasoline and not produce light cycle oil may being the new way solved the problem by catalytic cracking process.
US4585545 discloses one and complete for catalytic cracking light cycle oil cut is first carried out hydrotreatment, and the hydrogenated diesel oil obtained goes catalytic cracking to produce the catalysis conversion method being rich in mononuclear aromatics gasoline again.
CN1422327A discloses a kind of method of catalytic cracking light cycle oil upgrading, is the light cycle oil that the first catalytic cracking unit taking mink cell focus as raw material is produced is carried out deep hydrogenation, and the hydrogenation turning oil obtained enters the second catalytic cracking unit again.On the basis of the method, CN1423689A emphasizes that catalyst requirement in the second catalytic cracking unit is more than or equal to the large pore zeolite of about 0.7nm, optionally to improve light olefins yields containing the aperture of selecting shape zeolite and about 5-50% of 50-95%.
CN1466619A discloses a kind of method for transformation of catalytic cracking light cycle oil, that catalytic cracking riser reactor is divided into upstream and downstream two reaction zones, wherein mink cell focus injects catchment, and the hydrogenation turning oil that its catalytic cracking production light cycle oil obtains after hydrotreatment injects upstream.On the basis of the method, the charging in CN1425054A method middle and lower reaches district, except hydrogenation turning oil, also add petroleum naphtha.In the method, not only hydrogen consumption is high, and hydrogenation turning oil can have a strong impact on the conversion of the mink cell focus in downstream in upstream reaction.
Can find from disclosed document above, catalytic cracking light cycle oil being carried out to one of important channel processed is that it is first carried out hydrotreatment, and then catalytic cracking.It must be noted that, light cycle oil no matter whether hydrogenation, compare, its molecule is little with mink cell focus macromole, bond energy is large, the operating parameters therefore how controlling catalytic cracking is one of key of light cycle oil processing.In addition, if light cycle oil carries out hydrogenation, the operation control of hydrogenation process is also one of key of light cycle oil processing.
Summary of the invention
The object of the invention is to provide a kind of catalysis conversion method maximizing gasoline production on the basis of existing technology.
Catalysis conversion method provided by the invention comprises:
(1) catalytic cracking light cycle oil obtains lighting end and last running through cutting;
(2) step (1) described last running carries out hydrotreatment reaction under hydrogen and hydrotreating catalyst exist, and reaction product isolated obtains hydrogenation last running;
(3) step (1) described lighting end, step (2) enter riser reactor separately through different spray nozzles layering, catalytic cracking reaction is carried out under catalytic cracking catalyst exists, be separated catalytic cracking catalyst to be generated and reaction oil gas, wherein reaction oil gas is isolated to the product comprising gasoline, light cycle oil.
Preferred the method also comprises: the described catalytic cracking catalyst to be generated of step (3) gained regeneration catalyzing cracking catalyst after stripping, regeneration returns riser reactor and recycles.
The described catalytic cracking light cycle oil of step (1) be selected from allocatalysis cracking unit produce light cycle oil or/and present method catalytic cracking unit step (3) produce light cycle oil, preferred allocatalysis light cycle oil that cracking unit produces and present method catalytic cracking unit step (3) produce light cycle oil.
Method provided by the invention is specific as follows:
Catalytic cracking light cycle oil enters independent separation column and cuts, cutting temperature controls at 250 ~ 260 DEG C, preferred cutting temperature is 260 DEG C, obtains respectively not higher than the lighting end of this cutting temperature and the last running higher than this cutting temperature from the top of separation column and bottom.
Hydrotreater is removed in described last running, and under hydrogen and hydrogenation catalyst exist, carry out hydrotreatment reaction, hydroprocessing condition is: hydrogen dividing potential drop 10.0 ~ 25.0MPa, preferably 10.0 ~ 22.0MPa; Temperature of reaction 330 ~ 450 DEG C, preferably 340 ~ 380 DEG C; Volume space velocity 0.1 ~ 2.0 hour
-1, hydrogen to oil volume ratio 1000 ~ 2000Nm
3/ m
3.Reaction product isolated obtains the cut of the preferred > of initial boiling point > 250 DEG C 260 DEG C, or claims hydrogenated diesel oil, hydrogenation last running.In described hydrogenation last running, two ring aromatic content wants≤10 heavy %, the heavy % in preferably≤8.
Described activity of hydrocatalyst metal component is selected from group vib metal and/or group VIII base metal, in support selected from alumina, silicon-dioxide, amorphous aluminum silicide any one or several.Described group vib metal be molybdenum or/and tungsten, group VIII base metal is that nickel is or/and cobalt.The combination of the preferred nickel-tungsten of active metal component, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
The lighting end of light cycle oil and the hydrogenation last running obtained enter independent catalytic cracking unit, and under catalytic cracking catalyst exists, carry out cracking reaction, reaction product isolated obtains dry gas, liquefied gas, gasoline, light cycle oil, slurry oil, coke.The concrete operations condition of catalytic cracking unit is as follows:
Catalytic cracking unit can be isometrical riser reactor or reducing riser reactor.Enter riser reactor together with after the lighting end of≤260 DEG C can mix with the hydrogenation last running obtained, but preferably separately enter riser reactor separately through different spray nozzles.Wherein lighting end enters from the underlying nozzle (upstream) of riser tube, and hydrogenation last running enters from the upper strata nozzle (downstream) of riser tube.The distance of upper and lower layer nozzle is be advisable for 0.01 ~ 3 second to control the residence time of reaction oil gas in two-layer nozzle distance, preferably 0.05 ~ 1 second.The advantage that lighting end and hydrogenation last running layering enter to optimize the reaction conditions meeting different fractions catalytic cracking, thus realize farthest transforming.
The reaction conditions of catalytic cracking unit is: temperature of reaction is 520 ~ 650 DEG C, preferably 550 ~ 590 DEG C; Agent oil quality than 5 ~ 100, preferably 8 ~ 50; Oil gas residence time 1-10 second, preferably 2 ~ 8 seconds; Pressure (absolute pressure) 0.15 ~ 0.4MPa; The weight ratio of water vapor and raw material is 0.01 ~ 0.5 preferably 0.02 ~ 0.2; Catalyst Balance Activity (MAT) >=65, preferably >=68.
Catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay.The content of each component is respectively: the heavy % of the heavy % of zeolite 10 ~ 50, the heavy % of inorganic oxide 5 ~ 90, clay 0 ~ 70.Wherein active ingredient be selected from containing or not containing rare earth Y, HY, USY or Beta zeolite in one, two or more.
The invention has the advantages that:
1, catalytic cracking unit light cycle oil is first cut, and wherein last running will remove hydrogenation, hydrogen consumption can be reduced to greatest extent;
2, the last running after the lighting end of independent catalytic cracking unit processing light cycle oil and hydrogenation is adopted and layering enters, the severe condition met needed for light cycle oil different fractions catalytic cracking reaction can be optimized to greatest extent, thus farthest produce catalytic gasoline.
Accompanying drawing explanation
Fig. 1 is the catalysis conversion method schematic flow sheet of maximization gasoline production provided by the invention.
Embodiment
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Accompanying drawing is catalysis conversion method schematic flow sheet provided by the invention.
Fig. 1 is the schematic flow sheet of preferred forms of the present invention, but does not limit the present invention.Shape, the size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.In accompanying drawing, each numbering is described as follows:
1,3-5,7,11-14 all represents pipeline; 2 is fractionation plant; 6 is diesel hydrotreating unit; 8,9 is catalytic cracking feeding nozzle; 10 is catalytic cracking reaction device.
Below in conjunction with accompanying drawing, preferred forms provided by the present invention is further described.
Catalytic cracking light cycle oil enters fractionation plant 2 through pipeline 1 and cuts, and obtains≤lighting end of 260 DEG C and the last running of > 260 DEG C.The lighting end of wherein≤260 DEG C enters catalytic cracking reaction device 10 through pipeline 3, catalytic cracking lower floor feed nozzle 8.And the last running of > 260 DEG C enters diesel hydrotreating unit 6 through pipeline 4, hydrogen introduces diesel hydrotreating unit 6 through pipeline 5 simultaneously.Product hydrogenated diesel oil after hydrogenation enters catalytic cracking reaction device 10 through pipeline 7, catalytic cracking upper strata nozzle 9.The lighting end of≤260 DEG C and hydrogenated diesel oil are in catalytic cracking unit 10, catalytic cracking reaction is carried out under catalytic cracking catalyst exists, the stop bracket gasoline that reaction product isolated obtains is drawn through pipeline 11, and another catalytic cracking reaction product light cycle oil is drawn through pipeline 12, enter fractionation plant 2 through pipeline 13,14,1 circulates.For simplicity, other products such as dry gas, liquefied gas, slurry oil etc. do not draw in the drawings.
The following examples will be further described the present invention, but not thereby limiting the invention.In embodiment, in hydrotreatment fixed-bed reactor, the hydrotreating catalyst commercial grades of filling is RN-32V; protective material commercial grades is RG-1; hydrotreating catalyst and protectant admission space ratio are 95:5, produce by Sinopec catalyzer branch office.
In embodiment, comparative example, the physico-chemical property of the catalyzer that catalytic cracking unit uses is in table 1, and its commercial grades is HAC, is produced by Sinopec catalyzer branch office.
Raw material (catalytic cracking light cycle oil) character used in embodiment, comparative example lists in table 2.
Embodiment
The present embodiment illustrates and adopts method provided by the invention, and raw material first obtains light cycle oil lighting end and light cycle oil last running through boiling range cutting, and cut point is 250 DEG C.
Light cycle oil last running enters medium-sized hydrogenation unit, and the test conditions of hydrogenation is: hydrogen dividing potential drop 12.0MPa; Average bed temperature of reaction 360 DEG C, volume space velocity 0.5 hour
-1, hydrogen to oil volume ratio 1400Nm
3/ m
3.In hydrogenation last running, two ring aromatic content is 4.9 heavy %.
Light cycle oil last running after light cycle oil lighting end and hydrogenation enters the upper and lower layer nozzle of medium-sized catalytic cracking riser reaction unit respectively, and wherein underlying nozzle is entered in lighting end, and hydrogenation double distilled is divided into upper strata nozzle.The distance of upper and lower two-layer nozzle is the residence time of reaction oil gas in two-layer nozzle distance is 0.5 second.The main operating parameters of kitty cracker is: temperature of reaction 570 DEG C; Agent oil quality is than 20; 7 seconds oil gas residence time; Pressure (absolute pressure) 0.25MPa; The weight ratio of water vapor and raw material is 0.06.The micro-activity (MAT) of poiser is 68.
Comparative example 1
Medium-sized tester is identical with embodiment with catalyzer.The same embodiment of boiling range cut point of light cycle oil, enters from the underlying nozzle of kitty cracker after the last running mixing just after light cycle oil lighting end and hydrogenation.The wherein same embodiment of the hydroconversion condition of the last running of light cycle oil.The same embodiment of operational condition of kitty cracker.
Comparative example 2
Medium-sized tester is identical with embodiment with catalyzer.Light cycle oil cuts without boiling range, and full cut directly removes hydrogenation unit hydrogenation, and the full cut of the light cycle oil after hydrogenation directly enters the underlying nozzle of kitty cracker.The wherein same embodiment of hydroconversion condition of the full cut of light cycle oil.The same embodiment of operational condition of kitty cracker.
Catalytic cracking product distribution and hydrogen consumption are in table 3.
Contrast comparative example 1 and comparative example 2 can find, adopt the method for boiling range cutting, obviously can reduce hydrogen consumption in hydrogenation process, and hydrogen consumption is reduced to 2.6% from 4.3%.Can find, although products distribution makes moderate progress, be not clearly simultaneously.And comparative example and comparative example 2, then can find, not only hydrogen consumption is reduced to 2.6% from 4.3%, and products distribution is obviously improved, and when showing single-pass conversion, gasoline yield is increased to 64.5% from 58.9%; In addition gasoline octane rating RON is increased to 96.1 from 94.0.In addition, no matter be embodiment or comparative example, even single-pass conversion, be also not difficult to find that the inventive method has very high gasoline yield.
Table 1HAC catalyst property
Table 2 stock oil character
| Stock oil title | Catalytic cracking light cycle oil |
| Density (20 DEG C), kg/m 3 | 948.8 |
| Zero pour, DEG C | -24 |
| Aniline point, DEG C | <30 |
| 10% carbon residue, heavy % | 0.37 |
| Molecular-weight average | 187 |
| Boiling range, DEG C | |
| Initial boiling point | 190 |
| 5% | 213 |
| 10% | 222 |
| 30% | 247 |
| 50% | 272 |
| 70% | 303 |
| 90% | 348 |
| 95% | 363 |
| Final boiling point | 369 |
| Mass spectroscopy quality forms, % | |
| Paraffinic hydrocarbons | 10.7 |
| Total naphthenic hydrocarbon | 4.6 |
| Total aromatic hydrocarbons | 84.7 |
| Mononuclear aromatics | 31.7 |
| Double ring arene | 45.0 |
| Total mass | 100.0 |
Table 3
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Hydrogen consumes, % | 2.6 | 2.6 | 4.3 |
| Product slates, heavy % | |||
| Dry gas | 1.8 | 2.1 | 2.2 |
| Liquefied gas | 23.4 | 24.8 | 25.4 |
| Gasoline | 64.5 | 59.5 | 58.9 |
| Solar oil | 8.4 | 10.8 | 10.9 |
| Heavy oil | 0.2 | 0.7 | 0.6 |
| Coke | 1.7 | 2.1 | 2.0 |
| Add up to | 100.0 | 100.0 | 100.0 |
| Gasoline octane rating | |||
| RON | 96.1 | 94.8 | 94.0 |
| MON | 84.2 | 82.8 | 82.1 |
Claims (17)
1. maximize a catalysis conversion method for gasoline production, it is characterized in that the method comprises:
(1) catalytic cracking light cycle oil obtains lighting end and last running through cutting;
(2) step (1) described last running carries out hydrotreatment reaction under hydrogen and hydrotreating catalyst exist, and reaction product isolated obtains hydrogenation last running;
(3) step (1) described lighting end, the described hydrogenation last running of step (2) enter riser reactor separately through different spray nozzles layering, catalytic cracking reaction is carried out under catalytic cracking catalyst exists, be separated catalytic cracking catalyst to be generated and reaction oil gas, wherein reaction oil gas is isolated to the product comprising gasoline, light cycle oil.
2., according to the method for claim 1, it is characterized in that step (3) described light cycle oil returns step (1).
3. according to the method for claim 1, it is characterized in that the method also comprises: the described catalytic cracking catalyst to be generated of step (3) gained regeneration catalyzing cracking catalyst after stripping, regeneration returns riser reactor and recycles.
4., according to the method for claim 1, it is characterized in that the cutting temperature of described light cycle oil is 250 ~ 260 DEG C.
5., according to the method for claim 1, it is characterized in that the condition of described step (2) described hydrotreatment is hydrogen dividing potential drop 10.0 ~ 25.0MPa, temperature of reaction 330 ~ 450 DEG C, volume space velocity 0.1 ~ 2.0 hour
-1, hydrogen to oil volume ratio 1000 ~ 2000Nm
3/ m
3.
6. according to the method for claim 1, it is characterized in that the active metal component of described step (2) described hydrotreating catalyst is selected from group vib metal and/or group VIII base metal, in support selected from alumina, silicon-dioxide, amorphous aluminum silicide any one or several.
7. according to the method for claim 6, it is characterized in that described group vib metal be molybdenum or/and tungsten, group VIII base metal is that nickel is or/and cobalt.
8., according to the method for claim 6, it is characterized in that described active metal component is selected from the combination of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
9., according to the method for claim 1, it is characterized in that in hydrogenation last running, two ring aromatic content is not more than 10 heavy %.
10., according to the method for claim 9, it is characterized in that in hydrogenation last running, two ring aromatic content is not more than 8 heavy %.
11., according to the method for claim 1, is characterized in that described riser reactor is isometrical riser reactor or reducing riser reactor.
12., according to the method for claim 1, it is characterized in that lighting end enters from the underlying nozzle of riser tube, and hydrogenation last running enter from the upper strata nozzle of riser tube.
13., according to the method for claim 12, is characterized in that the distance of upper and lower layer nozzle is 0.01 ~ 3 second to control the residence time of reaction oil gas in two-layer nozzle distance.
14., according to the method for claim 13, is characterized in that the distance of upper and lower layer nozzle is 0.05 ~ 1 second to control the residence time of reaction oil gas in two-layer nozzle distance.
15. according to the method for claim 1, it is characterized in that the reaction conditions of catalytic cracking unit is: temperature of reaction is 520 ~ 650 DEG C, agent oil quality is than 5 ~ 100, oil gas residence time 1-10 second, pressure 0.15 ~ 0.4MPa, the weight ratio of water vapor and raw material is 0.01 ~ 0.5, and Catalyst Balance Activity is not less than 65.
16. according to the method for claim 15, it is characterized in that the reaction conditions of catalytic cracking unit is: temperature of reaction is 550 ~ 590 DEG C, agent oil quality than 8 ~ 50,2 ~ 8 seconds oil gas residence time, the weight ratio of water vapor and raw material is 0.02 ~ 0.2, and Catalyst Balance Activity is not less than 68.
17. according to the method for claim 1, it is characterized in that step (3) described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, the content of each component is respectively: the heavy % of the heavy % of zeolite 10 ~ 50, the heavy % of inorganic oxide 5 ~ 90, clay 0 ~ 70, wherein active ingredient be selected from containing or not containing Y, HY, USY or Beta zeolite of rare earth one, two or more.
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| CN110551527A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Method for producing gasoline rich in aromatic hydrocarbon |
| CN110551526A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Processing method of catalytic cracking light cycle oil |
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